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  • 1
    ISSN: 1572-8862
    Keywords: Vanadium ; phenylhydrazine ; nitrogenase ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Addition of phenylhydrazine to a mixture of VCl3 · THF/N,N-propyl-bis (salicyladimine) and sodium hydride yielded a trinuclear vanadium complex, V3(μ3-O)(μ-Cl)Cl6(μ-η1-η1PhNHNH2)2(PhNHN H2)2(THF), containing two bridging and two terminal phenylhydrazine ligands. The product has been crystallographically characterized (P21/n, a=12.949(2) Å,b=24.061(4) Å,c=22.504(4) Å, β=107.22(1) deg.,V=6697(2) Å3 withZ=4) and was found to contain the first example of bridging monosubstituted hydrazine (phenylhydrazine) ligands.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Molecular engineering 3 (1993), S. 43-59 
    ISSN: 1572-8951
    Keywords: Heteropolymolybdates ; heteropolytungstates ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The chemistry of polynuclear oxometalate anions is dominated by molybdenum and tungsten in their highest oxidation state. During the past twenty years this class of compounds has attracted much attention because of their variable applications, e.g. as reagents in analytical procedures, as industrial catalysts and as potential anticancer drugs. In order to obtain model systems for the investigation of the catalytic activity of heteropolyanions we have synthesized and structurally characterized some organo derivatives of polyoxoanions. We secondly focus on Sb(III) and Bi(III) heteropolytungstates to examine the important influence of the unshared electron pair on the resulting structures and properties. Some of these compounds may be regarded as supramolecular aggregates showing inclusion phenomena. In 9 two [SbW9O33]9− anions are linked by a set of six sodium ions forming a nearly planar hexagon. The sodium ions are enveloped by an oxygen cage formed by terminal oxygen atoms of the polyanions and by water molecules. Furthermore, the four anions [Sb2W22O74(OH)2]12−, [Sb2W20Fe2O70(H2O)6]8−, [Sb2W20Co2O70(H2O)6]10− and [Bi2W20Fe2O68(OH)2(H2O)6]6− (in10, 11, 12, 13) may be regarded as transition metal complexes of novel [Sb2W20O70]14− or [Bi2W20O70]14− anions which are serving as ligands. The octahedral coordination sphere of each transition metal is formed by three oxygen atoms of the anion and completed by three water molecules. The Sb(III) heteropolyanion, [Na2Sb8W36O132(H2O)4]22− in (14) includes two sodium and four antimony ions besides four water molecules. Each anion consists of four β-B-SbW9-Keggin fragments linked together by four SbO4-groups, incorporating two sodium and four water molecules effecting an additional connection of the subunits.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 271 (1993), S. 50-55 
    ISSN: 1435-1536
    Keywords: Polytetrafluoroethylene ; copolymer ; crystal structure ; chain folding
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Molecular-mechanics calculations are performed on model folds proposed in the literature for single crystals of polytetrafluoroethylene crystallized in the phase stable below 19°C, in order to evaluate how they are modified when a fluorine atom is substituted by a bulky group, as occurs in fluorinated copolymers of tetrafluoroethylene. Only intramolecular effects are taken into account (isolated-chain model). An exhaustive analysis has been carried out of tetrafluoroethylene-hexafluoropropylene copolymer. Moreover, the lower energy folds found for such a copolymer have been examined for copolymers with chlorotrifluoroethylene and perfluoroalkylvinylethers, as comonomers. Our calculations show that all the considered comonomers can be arranged in the model folds proposed for the homopolymer, according to the imposed geometric constraints.
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  • 4
    ISSN: 1572-9001
    Keywords: Atomic displacement ; molecular motion ; vibrational analysis ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Atomic displacement parameters determined from a single-crystal X-ray-diffraction study on K2Ru(SO4)2 * 6H2O are analyzed in the molecular mean field approximation. The motion of SO2 2− can be described with a rigid-body model, whereas for [Ru(H2O)6]2+ internal stretching motion and coupling between stretching motion and overall translation are found to be necessary for explaining the observed atomic displacement parameters. Frequencies and force constants of internal motion are not significantly affected by such couplings. K2Ru(SO4)2 * 6H2O crystallizes in the monoclinic space groupP21/c (No. 14), witha = 6.1211(7)Å,b = 12.226(2) Å,c = 8.916(2)Å,β = 105.11(1)°,Z = 2 at 160 K anda = 6.1402(7)Å,b = 12.274(2)Å,c = 8.957(1)Å,β = 105.25(1)°,Z = 2 at 295 K. The structure was refined to a finalR(F) of 0.017 at 160 K and of 0.019 at 295 K for 1438 and 1299 observed reflections withF 0 〉 6σ(F0) and sin θ/λ 〉 0.617 Å1−.
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  • 5
    ISSN: 1572-8862
    Keywords: Platinum ; ruthenium ; crystal structure ; heteronuclear cluster
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract From the reaction of Ru(CO)5 and Pt(COD)2, COD = 1, 5-cyclooctadiene, the new platinum-ruthenium heteronuclear cluster complex Pt2Ru4(CO)18,1, was obtained in 60% yield.1 has a folded ladder-like structure with alternating pairs of ruthenium atoms and platinum atoms. The cluster of1 can be split to yield the known compound PtRu2(CO)8(η2-dppe),2, (54% yield) by reaction with 1, 2-bis(diphenylphosphino)ethane, dppe, at 25°C. When1 was treated with excess dppe at 40°C, thebis-diphos compound3, PtRu2(CO)6(μ-η2-dppe)2 was obtained (39% yield). Under the similar reaction conditions,2 was converted to3 in 44% yield. All these complexes were characterized by single crystal X-ray diffraction analyses. Compounds2 and3 both contain a triangular cluster of one platinum and two ruthenium atoms, but in2 the bidentate ligand, dppe, chelates the platinum atom and in3 the two dppe ligands bridge the two Pt-Ru metal-metal bonds. Crystal data for1: space group C2/c,a=12.542(2)Å,b=15.350(4)Å,c=15.252(3)Å, β=105.32(2)°,Z=4, 2192 reflections,R=0.025. For2: space group P21/c,a=14.351(2)Å,b=13.486(3)Å,c=19.218(3)Å, β=108.48(1)°,Z=4, 3029 reflections,R=0.027. For3: space group P21/c,a=18.836(6)Å,b=15.559(5)Å,c=23.259(7)Å, β=111.26(2)°,Z=4, 4204 reflections,R=0.038.
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  • 6
    ISSN: 1572-8862
    Keywords: Tungsten ; chloride ; hexatungsten ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The hexanuclear tungsten cluster complex [W6(μ3-Cl)8Cl6]2−,1 was isolated as a salt of the cation (MeO2CCH2)2N(H)CH2CH2N(CH2CO2Me)2+, EDTEH+, by crystallization from methanol solvent of the product obtained from the reaction of (H3O)2[W6(μ3-Cl)8Cl3] with the disodium salt of ethylenediaminetetraacetic acid. The compound was charcterized by single-crystal X-ray diffraction analysis. The cluster anion contains an octahedral arrangement of six tungsten atoms with chloride ligands bridging the eight triangular faces of the cluster and one chloride ligand terminally coordinated to each of the six tungsten atoms. The cation (EDTEH)+ achieves its positive charge by protonation of one of the nitrogen atoms. Crystal data: space group = P21/a,a=10.689(2) Å,b=22.931(6) Å,c=12.093(3) Å, β=98.41(2)°,Z=2, 2476 reflections,R=0.028.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of polymers and the environment 1 (1993), S. 65-80 
    ISSN: 1572-8900
    Keywords: Biodegradable plastic ; microbial degradation ; bacterial poly(d-(−)-3-hydroxybutyrate) ; crystal structure ; physiological behavior
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract As one of a series of studies concerning the relationship between the higher-order structure and the biodegradability of a biodegradable plastic, the effects of the crystal structure of the plastic on microbial degradation were investigated. Bacterial poly(d-(−)-3-hydroxybutyrate) (PHB) films which had a wide range of crystallinity were prepared by the melt-quenching method. Results of the microbial degradation indicated that the development of crystallinity evidently depressed the microbial degradability. From scanning electron microscopy (SEM) observations, it is suggested that the microbial degradation proceeded in at least two manners. One was preferential degradation of the amorphous region leaving the crystalline lamellae intact, which was considered to be a homogeneous enzymatic degradation over the surface. The other was nonpreferential spherical degradation on the surface. The SEMs indicate that the spherical holes were the result of colonization by degrading bacteria. The holes varied in size and number with the change of crystal structure. Therefore, it is considered that the crystal structure of PHB also influenced the physiological behavior of the degrading bacteria on the PHB surface.
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  • 8
    ISSN: 1572-9001
    Keywords: Cobaltocene ; molecular geometry ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The molecular and crystal structures of the monoclinic modification of cobaltocene Cp2Co (P21/n, Z=2) was determined at 100 K and 297 K with new sets of X-ray diffraction data (MoKα radiation, 3995 and 6534 reflections, refinement toR = 0.026 and 0.030 using 1061 and 1299 independent observable reflections, respectively). At 297 K the structure is disordered (similar to the isomorphous ferrocene and nickelocene) with two distinct orientations of the ring, differing in occupancy factors (80% and 20%) and by a rotation angle in the ring plane of approximately 34°. Just as for nickelocene but in contrast to ferrocene, no sharp phase transition was found on cooling Cp2Co to 100 K, but an essential ordering of the Cp-ring position was detected with a decrease of the contribution of the second minor orientation to nearly 10%. On the basis of a careful analysis of the molecular geometry, crystal packing, and anisotropic atomic displacement parameters, a dynamic temperature-dependent nature of the disorder in Cp2Co is assumed.
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  • 9
    ISSN: 1572-8862
    Keywords: Molybdenum ; acetate, carboxylate ; hexamolybdenum ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The hexamolybdenum cluster complex [Mo6(μ3-Cl)8(O2CMe)6]2−, 1 was isolated as the Bu4N+ salt in 71% yield from the reaction of (Bu4N)2[Mo6(μ3-Cl)8Cl6] with AgO2CMe in CH2Cl2 solvent. The compound was characterized by single crystal X-ray diffraction analysis. The cluster contains an octahedral arrangement of six molybdenum atoms with eight chloride ligands bridging the eight trianglar faces and six carboxylate ligands terminally coordinated through one oxygen atom to each of the six molybdenum atoms. Crystal data: space group =P21/n,a=10.713(3)Å,b=14.43(1)Å,c=21.919(4)Å, β=94.37(2)°,Z=2, 1965 reflections,R=0.036.
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  • 10
    ISSN: 1573-1111
    Keywords: 12-membered crown ethers ; crystal structure ; conformation peculiarities ; X-ray analysis ; CH...O contacts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal structures of two 12-membered crown ethers, benzo-12-crown-4 (1) and naphtho-12-crown-4 (2), have been determined by X-ray analysis. Both structures are molecular. Compound1 is monoclonic,P21/b,a=8.466(3),b=8.019(3),c=33.590(10) Å, γ=90.99(3)o. The unit cell contains two crystallographically independent molecules of1 with similar conformations. Compound2 is also monoclinic,P21/a,a=24.148(8),b=14.535(4),c=7.987(5) Å, γ=102.87(2)o. Two independent molecules in the unit cell have significantly different conformations.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 15 (1993), S. 159-165 
    ISSN: 1573-1111
    Keywords: Dibenzo-30-crown-10 ; crystal structure ; complexation ; dysprosium isothiocyanate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Crystalline [Dy(NCS)3(dibenzo-30-crown-10)(H2O)2]·H2O·MeCN can be obtained by slowly evaporating a reaction mixture of Dy(NCS)3·nH2O with dibenzo-30-crown-10 in a solution of acetonitrile. The material crystallizes in the monoclinic space groupP21/n, the cell parameters area=11.450(5),b=23.284(4),c=18.424(6)Å, β=106.28(4)°,V=4715Å3,M=968.47,D x=1.36 g cm−1, μ=17.80 cm−1,F(000)=1972,Z=4.2740 independently observed [I≥3σI] reflections were used in the final least-squares refinement leading to an agreement index ofR=0.085. The Dy(III) ion coordination geometry approximates a square antiprism, involving two water oxygens and three dibenzo-30-crown-10 oxygen atoms and three isthiocyanate nitrogens. Hydrogen bonds are formed between the two water molecules and four uncoordinated crown ether oxygen atoms.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 15 (1993), S. 341-349 
    ISSN: 1573-1111
    Keywords: Molecular asymmetry ; calixarene ; acetone ; clathrate ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal and molecular structure of the 1:1 clathrate of the asymmetric calix[4]arene,1, and acetone has been determined by X-ray analysis. The crystal data are: tetragonal, space groupP4/n,a=b=12.574(6),c=12.572(6) Å,V=1988(2) Å3,Z=2,D x =1.111 g cm−3,D m =1.108 g cm−3. Least-squares refinement based on 1131 observed reflections withF 0〉3σ(F 0) and anisotropic temperature factors led toR=0.096. In spite of the molecular asymmetric calixarene1 the crystal structure has high symmetry, because a part of the host and guest molecules are in disordered states.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 15 (1993), S. 385-398 
    ISSN: 1573-1111
    Keywords: Hydrogen bonding ; alicyclic diol ; helical tubulate ; crystal structure ; ferrocene ; squalene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The inclusion compounds of 2,8-dimethyltricyclo[5.3.1.13,9]dodecane-syn-2,syn-8-diol,3, with ferrocene and with squalene have been prepared. The crystal structures of these helical tubulate compounds: (3)3·(ferrocene)0.75 [P3121,a=b=13.7480(6),c=7.0312(5) Å,Z=1,R=0.038] and (3)3·(squalene)0.23 [P3121,a=b=13.677(1),c=7.0533(9) Å,Z=1,R=0.042] are described.
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  • 14
    ISSN: 1573-1111
    Keywords: Werner clathrate ; nickel octahedral complex ; tetrahydrofuran ; crystal structure ; NMR ; molecular recognition ; hydrocarbon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper addresses the general question: what are the significant guest properties selected by this host when interacting with guest molecules in the liquid phase, resulting in cocrystallization of the host and guest? In particular, to what extent do π electrons in a guest molecule effect its potential as a guest? Werner clathrates of the host [Ni(NCS)2(4-ViPy)4] with mixtures of tetrahydrofuran (THF) and cyclic hydrocarbons as guests have been synthesised and their structures elucidated. Clathrate (1): [Ni(NCS)2(4-ViPy)4](1.78 THF)(0.22 cyclohexane), crystallizes in the orthorhombic space groupP bcn a=9.976(6),b=20.630(25),c=19.861 (4) Å,V=4087Å3,Z=4,R=0.087 for 1461 reflections; (2): [Ni(NCS)2(4-ViPy)4](1.76 THF)(0.24 cyclohexene),P bcn ,a=9.987(7),b=20.614(4),c=19.898(4)Å,V=4096Å3,Z=4,R=0.084 for 1304 reflections; (3): [Ni(NCS)2(4-ViPy)4](0.48 THF)(0.52 1,3-cyclohexadiene), tetragonalI41/a,a=16.898(3),b=16.898(3),c=26.463(6)Å,V=7556Å3,Z=8,R=0.120 for 1698 reflections; (4): [Ni(NCS)2(4-ViPy)4](0.36 THF)(1.04 1,4-cyclohexadiene),I41/a,a=16.986(4),b=16.986(4),c=25.896(15)Å,V=7472Å3,Z=8,R=0.103 for 2025 reflections; (5): [Ni(NCS)2(4-ViPy)4](0.35 THF)(1.05 benzene),I41/a,a=17.102(10),b=17.102(10),c=25.498(8)Å,V=7458Å3,Z=8,R=0.118 for 2200 reflections; (6): [Ni(NCS)2(4-ViPy)4](3 benzene), triclinicP1,a=10.432(24),b=11.155(9),c=21.581(7)Å, α=78.70(5), β=82.60(7), γ=74.09(13)°,V=2361Å3,Z=2,R=0.078 for 3427 reflections. Host-guest ratios and, for mixtures of guests, guest1/guest2 ratios, were elucidated by density and NMR. We show that the conformational freedom of the substituted pyridines is not the primary reason for the clathrating ability of Werner hosts. All six structures show no host-guest interaction at the level of van der Waals interactions. As non-bonding interactions are not observed between the host and guest, this study shows that the above host's selectivity by enclathration of particular guest molecules cannot be accounted for by solid state structural analysis.
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  • 15
    ISSN: 1573-1111
    Keywords: Iminophosphoranes ; amine inclusion compounds ; 13C CPMAS NMR spectroscopy ; salt-like crystalline aggregates ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The crystal and molecular structure is reported for the inclusion compound 2-[o-(triphenylphosphoranylidenamino)benzyliden]amino-1H-2,3-dihydroindazol-3-one/isopropylamine/water3b. The crystal structure consists of discrete dimeric salt-like aggregates joined together by strong N+−H...−O−C hydrogen bonds between pairs of centrosymmetrically-related indazolonate anions and isopropylammonium cations. Six other inclusion compounds have been prepared and characterized by NMR [with propylamine (3a), withtert-butylamine (3c), withsec-butylamine (3d), withtert-pentylamine (3e), with 1-methylbutylamine (3f) and withiso-pentylamine (3g)]. Two different arrangements are found, both with the host being in the anionic form. The guests are either: (i) one protonated amine and one water molecule (3b and3f); or (ii) one protonated amine and the corresponding neutral amine (3a, 3c, 3d, 3e and3g).
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 16 (1993), S. 267-272 
    ISSN: 1573-1111
    Keywords: Crown ether ; ytterbium nitrate ; phen ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The title complex was prepared by reacting Yb(NO3)3 (12-crown-4) with 1,10-phenanthroline (hereafter phen) in acetone. It crystallized in the triclinic space group $$P\bar 1$$ witha=10.095(5),b=17.415(4),c=8.710(2) Å α=92.45(2), β=115.83(3), γ=74.08(3)0 andD c=1.85 g cm−3;Z=2. The metal ion in this complex is nine-coordinated to three bidentate nitrate ions, two nitrogen atoms of a phen and a water molecule. The crown ligand is hydrogen bonded to the coordination water molecule. The symmetry change of the crown ether is also discussed.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 16 (1993), S. 205-213 
    ISSN: 0887-3585
    Keywords: calcium binding ; crystal structure ; protein stability ; site-directed mutagenesis ; subtilisin ; X-ray crystallography ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A version of subtilisin BPN′ lacking the high affinity calcium site (site A) has been produced through genetic engineering methods, and its crystal structure refined at 1.8 Å resolution. This protein and the corresponding version containing the calcium A site are describedand compared. The deletion of residues 75-83 was made in the context of four site-specific replacements previously shown to stabilize subtilisin. The helix that in wild type is interrupted by the calcium binding loop, is continuous in the deletion mutant, with normal geometry. A few residues adjacent to the loop, principally those that were involved in calcium coordination, are repositioned and/or destabilized by the deletion. Because refolding is greatly facilitated by the absence of the Caloop, this proteinoffers a new vehicle for analysis and dissection of the folding reaction. This is among the largest internal changes to a protein to be described at atomic resolution. © Wiley-Liss, Inc.
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  • 18
    ISSN: 0887-3585
    Keywords: thrombin ; bifunctional inhibitor ; crystal structure ; hirutonis ; drugdesing ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The crystal structure of the complexes of hirutonin-2 and hirutonin-6 with human α-thrombin have been solved and refined to R-factors of 0.169 (2.0 Å resolution) and 0.162 (201Å), respectively. Hirutonins belong to a family of bifunctional inhibitors bearing a noncleavable moiety mimicking the scissile bond. Hirutonin-2 is an analog of (D)Phe-Pro-Arg-Gly-hirudin49-65; hirutonin-6 has the same N-terminal tripeptide connected to a shortened fibrinogen exosite-binding part by a short, non-peptidyl linker. The hirutonin-6 molecule is well defined in the electron density with the exception of the C-terminal Leu-h61. The linker follows near the bottom of the canyon connecting the active site with the exosite, forms a short antiparallel β-sheet-like arrangement with Leu-40-Leu41 and makes van der Waals contacts with Glu39-Leu40-Leu41 of thrombin. In the thrombin-hirutonin-2 complex, the N- and C-terminal parts of the inhibitor are well or dered (except the C-terminal Gln-h65) while the central portion of the linker is partially disordered. The glycine analog in the P1′ position of hirutonin-2 assumes a conformation similar to that of the canonical form (Bode and Huber (1992) Eur. J. Biochem. 204 : 433-451) and supports the identification of the S1′ site as restricted by His57, Trp60D, Lys60F, and the Cys42-Cys58 disulfide bridge. The carbonyl oxygen of the P1 arginine residue is located in the oxyanion hole formed by the NH groups of Gly193 and Ser195, while the carbonyl carbon is positioned within a short distance, 2.8 Å, from the Oγ of Ser195. This resembles the conformation of the substrate-like inhibitors bound to other serine proteases. The N-terminal (D)Phe-pro-Arg fragment common to both inhibitors binds to thrombin in a fashion very similar to that of other inhibitors having this motif. The binding of the C-terminus of hirutonins to the fibrinogen-binding exosite is similar to that observed in hirudin and hirulog complexes. © 1993 Wiley-Liss, Inc.
    Additional Material: 9 Ill.
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  • 19
    ISSN: 1573-9171
    Keywords: titanasilanes ; titanasilazanes ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An X-ray structural study of two titanium-containing organosilicon compounds, (Me3Si)3SiTi(NEt2)3 (1) and ClTi[N(SiMe3)2]3 (2), has been performed. The conformation of molecule1 in a crystal is staggered (approximate inherentC 3 symmetry), the Ti-Si and Ti-N bond lengths are 2.671(2) and 1.874–1.890(5) Å, respectively. A crystal of1 consists of one type of enantiomers (the space group is P41212; the absolute configuration has been determined). The structure of2 studied previously has been refined to the value of R=0.029 on the basis of 3442 reflections (the absolute structure has been determined), the Ti-Cl and Ti-N bond lengths are 2.260(1) and 1.926(1) Å, respectively. The strong distortions in the symmetry of the valence environment of the N atoms in the molecules of1, 2, and related structures are caused by electronic effects, in which the conformation of the relevant molecular fragments plays a determining role.
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  • 20
    ISSN: 1573-9171
    Keywords: synthesis ; crystal structure ; azepinethiones ; trimethylsilyl derivative
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The title compounds were prepared and X-ray analysis was performed (R = 0.064 and 0.035 for 1309 and 1637 reflections, respectively). In the former the intramolecular S→Si coordination interactions are absent and the Si atom has undistorted tetrahedral coordination with an S...Si distance of 4.034 Å. Crystals of the latter are built of centrosymmetric dimeric H-complexes (S...H(N) 2.58 Å, the S...HN angle 168°).
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  • 21
    ISSN: 1573-9171
    Keywords: peroxosolvates ; potassium fluoride ; monoperoxosolvate ; thermal stability ; crystal structure ; hydrogen bond
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Potassium fluoride peroxosolvate KF-H2O2 was obtained upon action of a 30% aqueous solution of hydrogen peroxide on solid potassium fluoride dihydrate. As compared to other peroxosolvates, KF-H2O2 is characterized by the highest thermal stability: the decomposition rate constantk 1, at 120°C is 1.4 10−3 min−1, the enthalpy of H2O2 addition to KF is 8.1 kcal/ mol. The correlation between the high stability of KF-H2O2 and the absence of catalytic properties of KF towards H2O2, and the formation of strong intermolecular O-H...F and intramolecular O-H...O hydrogen bonds in the crystal is discussed.
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  • 22
    ISSN: 1573-9171
    Keywords: synthesis ; crystal structure ; pentacoordinated silicon ; chelate cycle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The X-ray diffraction structural study of the (N-Si)-chelate of 2-(chlorodimethyl-silylmethylthio)-1-pyrroline was carried out (R = 0.033 for 1894 reflections). The Si atom has a somewhat distorted trigonal bipyramidal coordination with the Cl and N atoms in axial positions. The Si-Cl and Si-N distances (2.423(1) and 1.945(1) Å) belong, respectively, to the longest and shortest known Si-Cl and Si-N distances in pentacoordinated silicon derivatives with an axial N-Si-Cl moiety.
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  • 23
    ISSN: 1573-9171
    Keywords: iron(II) and ruthenium(II) complexes ; synthesis ; carbonyl, cyclopentadienyl, benzoate ligands ; crystal structure ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Complexes of Fe(II) and Ru(II) of the general formula Cp(OC)2MOC(O)C6H4X-p, where M=Fe, X=H, F (1, 2) or M=Ru, X=H, F (3, 4) have been prepared by reactingp-XC6H4COOAg with [CpFe(CO)2]2 or CpRu(CO)2I. The crystal structures of complexes1–3 have been determined using X-ray diffraction. Compounds1 and3 are isomorphous. The COO group in1–3 is coordinated as a monodentate ligand. As the latter and the CO ligands are electronically non-equivalent, the coordination of the Cp ligand to the metal is slightly asymmetric.
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  • 24
    Electronic Resource
    Electronic Resource
    Springer
    Russian chemical bulletin 42 (1993), S. 1149-1151 
    ISSN: 1573-9171
    Keywords: Pt(dddt)2 ; organic conductors ; 5,6-dihydro-1,4-dithiin-2,3-dithiolate((dddt)2−) ; sulfur-containing platinum complexes ; crystal structure ; synthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A neutral metal complex, [Pt(dddt)2]° (1), has been obtained by oxidation of the [Pt(dddt)2]− anion with excess (Bu4N)AuBr4 in nitrobenzene. Crystallographic data for 1∶a=17.854(9) Å,b=18.409(9) Å,c=4.717(5) Å, γ=68.83(2)°, space group P21/n,Z=4,d calc=2.55 g/cm3. In1 two independent centrosymmetric [Pt(dddt)2]° molecules are packed in stacks that form layers parallel to the (110) plane. The molecules of1 in the layers have shortened S...S contacts 3.491(9) Å, and 3.594(10) Å. The average bond lengths Pt-S 2.242(7) Å, S-C 1.71(2) Å and C=C 1.40(3) Å, together with the square-planar coordination of Pt in PtS4, suggest considerable conjugation in the metal cycles.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Russian chemical bulletin 42 (1993), S. 1415-1417 
    ISSN: 1573-9171
    Keywords: vanadatrane ; crystal structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An X-ray diffraction study of a substituted vanadatrane-1-one (space groupPna21,R= 0.019 for 1394 reflections, the absolute structure was determined) showed that the geometry of its atrane framework is similar to that of the Si- and Ge-analogs. The bond lengths are: V=O, 1.614(2) Å; V←N, 2.329(2) Å; V-O, 1.800–1.806(2) Å. The deviation of the V atom having distorted trigonal bipyramidal coordination from the equatorial plane of the O atoms is 0.35 Å, the 0=V←N bond angle is 179.4(1)°.
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  • 26
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1923-1940 
    ISSN: 0887-6266
    Keywords: poly(4,4′-oxybibenzoate) ; polymerization ; morphology ; transitions ; crystal structure ; disclination domains ; Iamellae ; single crystals ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 4-Acetoxy 4′-carboxy biphenyl has been polymerized from solution, the bulk melt, and in constrained thin films, all below the melting point of the monomer as measured by differential scanning calorimetry (DSC). An isothermal sublimation-recrystallization-melting (and chemical change)-polymerization-crystallization process is proposed. From solution and in the thin films, single crystals consisting of ca. 100 Å thick lamellae are observed, with evidence for monomer addition-reaction on the end (top and bottom) surfaces. The bulk samples are fibrous, the “fibers” consisting of whisker-like single crystals. The polymer is highly heat and radiation (electron beam) resistant, with numerous successive electron diffraction (ED) patterns from the same crystal or sheared sample permitting comparison of the changes in ED patterns with transitions seen by DSC at ca. 350, 530, and 590°C. Phase I (a = 7.8, b = 5.5, c = 10.8 Å), a possible phase II (a = 15.6, b = 3.6 Å c = unknown), and a phase III (a = 9.0, b = 5.2 = √3a, c = 10.8 Å). Phases I and II are seen in samples polymerized at temperatures at and below 310°C; phase III is observed in samples polymerized at and above 350°C and in sheared samples. © 1993 John Wiley & Sons, Inc.
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  • 27
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1713-1723 
    ISSN: 0887-6266
    Keywords: phthalocyanine siloxane ; crystal structure ; epitaxial growth ; high-resolution electron microscopy ; molecular imaging ; polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of SiPc(OH)2 (Pc = phthalocyanine) were formed epitaxially on the (001) surface of mica by vacuum deposition and were then polymerized by heat treatment. The molecular packing of the SiPc(OH)2 was determined by electron diffraction and high-resolution electron microscopy as triclinic\documentclass{article}\pagestyle{empty}\begin{document}${\rm P\bar 1} $\end{document} having dimensions a = 0.727, b = 1.307, c = 0.688 nm, α = 102.5, β = 104.2, and γ = 97.4°. This monomer crystal grows with its c-axis parallel to the a-axis of the substrate mica and its bc-plane parallel to the (001) surface of mica. By heat treatment at 320°C, the SiPc(OH)2 polymerized with the c-axis of the polymer parallel to the c-axis of the monomer. At 420°C, the c-axis of the polymer became parallel to the a*-axis of the monomer (i.e., perpendicular to the film surface). From high-resolution electron microscopy of partially polymerized specimens, the polymerization was shown to start at the edges of small monomer crystals. This may be considered to be due to the volume expansion during the polymerization. © 1993 John Wiley & Sons, Inc.
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  • 28
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1759-1767 
    ISSN: 0887-6266
    Keywords: rigid rod polymer ; thermotropic ; aromatic polyester ; fiber ; modulus ; crystal structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fiber spinning and mechanical properties of four rigid polyesters with alkoxy substituents of different length and placement were evaluated. Properties of oriented fibers from the polymer with dodecyloxy substituents on the terephthalate moiety, PTA12HQ, were significantly affected by the crystal modification. At room temperature the following properties (tensile modulus E, tensile strength σb, and strain at break εb) could be obtained: E = 9.5 GPa, σb = 85 MPa and εb = 1.1% for phase Lf (the “frozen in layered mesophase”); E = 10.4 GPa, σb = 59 MPa and εb = 0.6% for modification A; E = 17.3 GPa, σb = 158 MPa and εb = 1.2% for modification B. Because of the higher amount of main chains per cross sectional area the polymer with hexyloxy side chains, PTA6HQ, showed better properties at a comparable degree of molecular orientation: E = 24 GPa, σb = 270 MPa, εb = 1.4%. Fibers obtained from the polyester with dodecyloxy substituents on the hydroquinone moiety, PTAHQ12, were too brittle to handle. The polyester with dodecyloxy substituents on both moieties, PTA12HQ12, was spun from the isotropic melt. Because of the obtained low degree of orientation, properties (E = 1 GPa, σb = 40 MPa, and εb = 6.3%) were governed by interactions between the chains (the main chains are not load-bearing). © 1993 John Wiley & Sons, Inc.
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  • 29
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 181-188 
    ISSN: 0044-2313
    Keywords: Samarium(II) fluoroaluminate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: SmAlF5  -  a New Samarium(II) Fluoroaluminate with Al2F10 Bioctahedra and [AlF2/2F4/1] Chains.SmAlF5 has been obtained as orange-red transparent single crystals while heating mixtures of SmF3, Sm-powder and AlF3 (2:1:3) in a niobium crucible under Ar after 7-10 d at about 750°C. SmAlF5 crystallises in I 4/m (Nr. 87) with a=1 414.4(4), c=722.2(3) pm and Z=8 (CAD4, 4 340 IO, Rw=1.7%).The crystal structure of SmAlF5 is isotypic to BaTiF5. Characteristic building units are linear chains of trans-corner sharing AlF6 octahedra, which are connected via corners to two further AlF6 octahedra. Isolated Al2F10 octahedra lie disordered between such chains. The Sm atoms connect the AlF6 octahedra to a three-dimensional network. Measurements of the magnetic susceptibility show the temperature dependence typically found for Sm2+. The Madelung part of the lattice energy has been calculated and is discussed.
    Notes: SmAlF5 wurde in Form orangeroter transparenter Einkristalle beim Erhitzen von SmF3, Sm-Pulver und AlF3 (2:1:3) im Niobtiegel unter Ar nach 7-10 d bei ca. 750°C erhalten. SmAlF5 kristallisiert in I4/m (Nr. 87) mit a=1 414,4(4), c=722,2(3) pm und Z=8 (CAD4, 4 340 IO, Rw=1,7%).Die Kristallstruktur von SmAlF5 ist isotyp zu BaTiF5. Charakteristische Baugruppen sind lineare Ketten trans-Spitzen verknüpfter AlF6-Oktaeder, die über Spitzen mit zwei weiteren AlF6-Oktaedern verknüpft sind. Isolierte Al2F10-Oktaederdoppel liegen fehlgeordnet zwischen solchen Ketten. Die Sm-Atome verknüpfen die AlF6-Oktaeder zum dreidimensionalen Gerüst. Messungen der magnetischen Suszeptibität zeigen die für Sm2+ typische Temperaturabhängigkeit. Der Madelunganteil der Gitterenergie wurde berechnet und diskutiert.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 537-539 
    ISSN: 0044-2313
    Keywords: Sodium-barium-oxo/peroxo-aurate(III) ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the first Alkaline-Alkaline-Earth-Oxo/Peroxo-Aurate(III): NaBa4AuO4(O2)2The hitherto unknown compound NaBa4AuO4(O2)2 was prepared by oxidizing of barium gold alloy with Na2O2 in closed Ag-bombs. X-ray single crystal investigation led to tetragonal symmetry space group D4h17I4/mmm, a = 5.939; c = 15.393 Å, Z = 2. NaBa4AuO4(O2)2 shows a distorted square antiprismatic surrounding of Ba2+ by four peroxo groups on one side and four O2- on the opposite. Au3+ shows the usual square planar polygons of AuO4. Na+ is coordinated by four O2- ions in the base of an octahedron and two peroxo groups in the apical positions.
    Notes: Die bisher unbekannte Verbindung NaBa4AuO4(O2)2 wurde durch Reaktion einer Barium-Gold-Legierung mit Na2O2 im geschlossenen Silberbömbchen dargestellt. Die Kristallstruktur wurde röntgenographisch an Einkristallen untersucht. NaBa4AuO4(O2)2 kristallisiert tetragonal, Raumgruppe D4h17-I4/mmm, a = 5,939; c = 15,393 Å, Z = 2. Ba2+ ist verzerrt quadratisch antiprismatisch von vier Peroxogruppen auf der einen und vier O2--Ionen auf der Gegenseite koordiniert. Au3+ zeigt quadratisch planare Koordination von O2- und Na+ ist von vier O2--Ionen in der Oktaederbasisfläche und zwei Peroxogruppen in trans-Stellung dazu koordiniert.
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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 476-488 
    ISSN: 0044-2313
    Keywords: Dialkali metal dichalcogenides ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Dialkali Metal Dichalcogenides β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 and Rb2Te2The first presentation of pure samples of α- and β-Rb2S2, α- and β-K2Te2, and Rb2Te2 is described. Using single crystals of K2S2 and K2Se2, received by ammonothermal synthesis, the structure of the Na2O2 type and by using single crystals of β-Na2S2 and β-K2Te2 the Li2O2 type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na2O2 type to the Li2O2 type will be explained by means of the examples α-/β-Na2S2 and α-/β-K2Te2. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb2S2 is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.
    Notes: Die erstmalige Darstellung phasenreiner Proben von α- und β-Rb2S2, von α- und β-K2Te2 und von Rb2Te2 wird beschrieben. Mit Hilfe von ammonothermal synthetisierten Einkristallen des K2S2 und des K2Se2 wird die Struktur des Na2O2-Typs, mit Einkristallen des β-Na2S2 und des β-K2Te2 die des Li2O2-Typs verfeinert. Durch kombinierte temperaturabhängige Guinier-, Neutronenbeugungs-, thermoanalytische und Raman-spektroskopische Untersuchungen wird die Natur des monotropen Phasenübergangs vom Na2O2-Typ zum Li2O2-Typ an Hand der Beispiele α-/β-Na2S2 und α-/β-K2Te2 aufgeklärt. Ein weiterer Fall von Dimorphie, der ebenfalls monotrope Übergang von α-Rb2S2(Rb2O2-Typ) zu β-Rb2S2(Na2O2-Typ), wird vorgestellt. Die Existenzgebiete der Strukturfelder bei den Dialkalimentalldichalkogeniden werden mittels des Modells der polaren Kovalenz gegeneinander abgegrenzt.
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  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 70-72 
    ISSN: 0044-2313
    Keywords: Sodium thioargentate ; cluster ; preparation ; crystal structure ; extended Hückel calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: NaAg3S2, a Thioargentate Containing the Anionic Cluster [Ag6S4]2-.Dark-red octahedrally shaped crystals of NaAg3S2 could be obtained by the reaction of NaAg(CN)2 and NaCN in a stream of hydrogen sulfide at 630 K. NaAg3S2 crystallizes cubic, a=12.358(1) Å, space group Fd3m, Z=16. The structure was determined from four-circle diffractometer data. NaAg3S2 contains the anionic cluster [Ag6S4]2-. The structure can be traced back to the spinel structure typ. An extended Hückel calculation for the cluster anion, which is considered to be isolated, shows weak bonding silver-silver interactions. NaAg3S2 is diamagnetic at room temperature.
    Notes: Dunkelrote oktaederförmige Kristalle der Verbindung NaAg3S2 wurden bei der Umsetzung von Natriumcyanoargentat mit Natriumcyanid im Schwefelwasserstoffstrom bei 630 K erhalten. NaAg3S2 kristallisiert kubisch, a=12,358(1) Å, Raumgruppe Fd3m, Z=16. Die Struktur wurde über Einkristalle mit Vierkreisdiffraktometerdaten bestimmt. NaAg3S2 enthält als Clusteranion die Baugruppe [Ag6S4]2-. Die Struktur läßt sich auf den Spinelltyp zurückführen. Eine Extended-Hückel-Rechnung für das als isoliert angenommene Clusteranion ergibt schwache bindende Wechselwirkungen zwischen den Silberatomen. NaAg3S2 ist bei Raumtemperatur diamagnetisch.
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  • 33
    ISSN: 0044-2313
    Keywords: Aluminium chloride triammoniate ; tetraammine dichloro aluminium-diammine tetrachloro aluminate ; synthesis ; crystal structure ; IR spectrum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: AlCl3 · 3NH3  -  a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl2(NH3)4]+[AlCl4(NH3)2]-.AlCl3 · 3 NH3 ≙ [AlCl2(NH3)4]+ [AlCl4(NH3)2]- forms during the reaction of two mole NH3 with AlCl3(NH3) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH3. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm P\bar 1,}\,{\rm Z}\,{\rm = }\,{\rm 2} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}\,{\rm = }\,{\rm 5}{\rm .713(2)}\,{\rm {\AA},}} \hfill & {{\rm b}\,{\rm = }\,{\rm 6}{\rm .512}\,{\rm {\AA}},} \hfill & {{\rm c}\,{\rm = }\,{\rm 9}{\rm .499(3)}\,{\rm {\AA}}} \hfill \\ {{\rm \alpha }\,{\rm = }\,8{\rm 6}{\rm .39(3)}^ \circ,} \hfill & {{\rm \beta }\,{\rm = }\,{\rm 87}{\rm .13(3)}^ \circ } \hfill & {{\rm \gamma }\,{\rm = }\,{\rm 84}{\rm .82(3)}^ \circ } \hfill \\ \end{array} $$\end{document}The compound contains elongated [AlCl2(NH3)4]+ octahedra and compressed [AlCl4(NH3)2]- octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ≤ d(N - H … Cl) ≤ 3.589 Å stabilize the atomic arrangement.
    Notes: AlCl3 · 3NH3 ≙ [AlCl2(NH3)4]+ · [AlCl4(NH3)2]- entsteht bei der Umsetzung von AlCl3(NH3) mit zwei Mol NH3 bei T ≥ 200°C. Wiederholtes Aufheizen und Abkühlen im Temperaturbereich von 200°C bis 250°C führt innerhalb von 48 h zu homogenen Produkten unter vollständiger Aufnahme der vorgegebenen NH3-Menge. Durch langsame Sublimation im Vakuum bei 200°C lassen sich meist stark verwachsene Kristalle des Triammoniakats züchten. Röntgenographisch wurde die Struktur bestimmt: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm P\bar 1,}\,{\rm Z}\,{\rm = }\,{\rm 2} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm a}\,{\rm = }\,{\rm 5,713(2)}\,{\rm {\AA},}} \hfill & {{\rm b}\,{\rm = }\,{\rm 6,512}\,{\rm {\AA}},} \hfill & {{\rm c}\,{\rm = }\,{\rm 9,499(3)}\,{\rm {\AA}}} \hfill \\ {{\rm \alpha }\,{\rm = }\,8{\rm 6,39(3)}^ \circ,} \hfill & {{\rm \beta }\,{\rm = }\,{\rm 87,13(3)}^ \circ } \hfill & {{\rm \gamma }\,{\rm = }\,{\rm 84,82(3)}^ \circ } \hfill \\ \end{array} $$\end{document} R/Rw = 5,5/7,0 bei Z(Fo2 〉 3σ Fo2) = 1106 und Z(Var.) = 67Die Verbindung ist aus elongierten [AlCl2(NH3)4]′ -und gestauchten [AlCl4(NH3)2]--Oktaedern aufgebaut. Neben ionogenen Bindungsanteilen ist die Atomanordnung durch H-Brückenbindungen mit 3,369 Å ≤d(N—H … Cl) ≤ 3,589 Å stabilisiert.
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  • 34
    ISSN: 0044-2313
    Keywords: Silver vanadium bronze ; copper vanadium bronze ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Novel Means of Synthesis for Vanadium Bronzes. Crystal Structure of β—Ag0.33V2O5. Refinement of the Crystal Structure of ∊—Cu0.76V2O5Ag0.33V2O5 and Cu0.76V2O5 were obtained by heating equimolar mixtures of AgI + V2O5 (700°C) and CuI + V2O5 (525°C), respectively, in sealed quartz glass ampoules. In each case, one of the well-formed crystals served for an X-ray structure analysis. Ag0.33V2O5 has the structure known of the β phase of the vanadium bronzes, i. e. layers of edge-sharing, distorted VO6 octahedra are liked by certain common octahedron vertices, the Ag atoms randomly occupy two positions with occupation probabilities of 0.5. Cu0.76V2O5 has the previously determined structure of the ∊ phase, however, its space group is not Cm but C2/m.
    Notes: Ag0,33V2O2 und Cu0,76V2O5 wurden durch zweiwöchiges Erhitzen von äquimolaren Gemischen AgI + V2O5 (700°C) bzw. CuI + V2O (525°C) in einer Quarzglasampulle erhalten. Mit je einem der gut ausgebildeten Kristalle wurden eine Röntgenstrukturanalyse durchgeführt. Ag0,33V2O5 hat die für die β-Phase der Vanadiumbronzen bekannte Struktur, d. h. Schichten aus verzerrten, kantenverknüpften VO6-Oktaedern sind über bestimmte Oktaederecken verknüpft, die Ag-Atome nehmen statistisch zwei Atomlagen der Koordinationszahl 7 mit halber Besetzungswahrscheinlichkeit ein. Cu0,76V2O5 hat die früher bereits bestimmte Struktur der ∊-Phase, deren Raumgruppe jedoch nicht Cm sondern C2/m ist.
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  • 35
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 318-320 
    ISSN: 0044-2313
    Keywords: Indium ; phosphorus ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of [{(tBu2P)2InCl}2]The reaction of InCl3 with tBu2PSiMe3 leads to [{(tBu2P)2InCl}2] (1). 1 crystallizes in the space group P21/c. The lattice constants (at 216 K) are: a = 945.9(5) pm, b = 1 604.1(9) pm, c = 1 636.8(8) pm, β = 100.55(4)°. 1 contains a planar In2P2 ring. Each In atom is coordinated by two bridging tBu2P groups, a terminal tBu2P group and a terminal Cl atom. The coordination geometry of the In atoms is roughly tetrahedral.
    Notes: InCl3 reagiert mit tBu2PSiMe3 in Toluol als Lösungsmittel zu [{(tBu2P)2InCl}2] (1). 1 kristallisiert in der Raumgruppe P21/c mit den Gitterkonstanten (bei 216 K): a = 945,9(5) pm, b = 1 604,1(9) pm, c = 1 636,8(8) pm, β = 100,55(4)°. Nach der Kristallstrukturanalyse enthält 1 einen planaren In2P2-Ring. Die In-Atome sind jeweils verzerrt tetraedrisch koordiniert von zwei verbrückenden tBu2P-Gruppen, einer terminalen tBu2P-Gruppe und einem terminalen Chloratom.
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  • 36
    ISSN: 0044-2313
    Keywords: Lanthanoid nickel carbides, Ln4Ni2C5 ; crystal structure ; magnetic susceptibility ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Darstellung und Kristallstruktur der isotypen Carbide Ln4Ni2C5 (Ln = Er, Tm, Yb und Lu)Die Titelverbindungen wurden durch Reaktion der Elemente in einer Lithiumschmelze hergestellt und ihre Kristallstruktur aus Einkristalldaten der Ytterbiumverbindung bestimmt. Sie kristallisieren rhombisch, Pmm2, a = 352,88(6) pm, b = 1 143,0(3) pm, c = 366,16(6) pm, Z = 1, R = 0,020 für 1 261 Strukturfaktoren und 29 variable Parameter. Die Struktur enthält eine Abfolge von Schichten, wie sie von CeNiC2 und ScC (NaCl Typ) bekannt sind. Dementsprechend enthält sie C2-Paare mit einem C—C-Abstand von 138(1) pm und isolierte Kohlenstoffatome. Zusammen mit den Nickelatomen bilden die C2-Paare eindimensional-unendliche Verbände der Zusammensetzung [Ni2C4]n. Das fünfte Kohlenstoffatom ist oktaedrisch von Ytterbiumatomen umgeben. Daher kann die Verbindung mit (formalen) Oxidationszahlen gemäß der Formel (Yb3+)4[Ni2C48-]C4- beschrieben werden. Die magnetischen Suszeptibilitäten von Yb4Ni2C5 zeigen Curie-Weiss-Verhalten mit einem magnetischen Moment von μexp = 4,44 μB in guter Übereinstimmung mit dem für Yb3+ zu erwartenden Wert von μeff = 4,53 μB.
    Notes: The title compounds were prepared from the elemental components in a lithium flux. Their crystal structure was determined for the ytterbium compound from single-crystal X-ray data. It is orthorhombic, Pmm2, a = 352.88(6) pm, b = 1 143.0(3) pm, c = 366.16(6) pm, Z = 1, R = 0.020 for 1 261 structure factors and 29 variable parameters. The structure may be viewed as an intergrowth of slabs consisting of the CeNiC2 and the ScC (NaCl type) structures. It thus contains C2 pairs with a C—C distance of 138(1) pm and isolated carbon atoms. Together with the nickel atoms the C2 pairs form one-dimensionally infinite building elements [Ni2C4]n. The fifth carbon atom is octahedrally coordinated by ytterbium atoms. Accordingly the compound may be rationalized to a first approximation with the formula (Yb3+)4[Ni2C48-]C4-. Yb4Ni2C5 shows Curie-Weiss behaviour with a magnetic moment of μexp = 4.44 μB per ytterbium atom in good agreement with the theoretical moment of μeff = 4.53 μB for Yb3+.
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  • 37
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 343-346 
    ISSN: 0044-2313
    Keywords: Sodium ; barium ; nickel ; oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The First Alkalinc Alkaline Earth Oxoniccolate(II,III): NaBa2Ni22+Ni3+O6Single crystals of NaBa2Ni22+Ni3+O6 were prepared by solid state reaction. X-ray investigations led to orthorhombic symmetry, space group D2h23-Fmmm; a = 8.310; b = 11.220; c = 14.397 Å; Z = 8. Na+ is coordinated by six O2- in form of a trigonal prism and the two Ba2+ point positions show different coordination numbers C.N. = 6 + 4 and 8. The Ni2+ /Ni3+ ions are in square planar polygons, six of them are forming a so far unknown closed macro polyhedra.
    Notes: Einkristalle von NaBa2Ni22+Ni3+O6 wurden durch Feststoffreaktionen erhalten. Es kristallisiert orthorhombisch, Raumgruppe D2h23-Fmmm; mit a = 8,310; b = 11,220; c = 14,397 Å; Z = 8. Na+ ist von O2- in Form trigonaler Prismen sechsfach koordiniert und Ba2+ zeigt zwei Punktlagen mit Koordinationszahlen von C.N. = 6 + 4 und 8. Die Ni2+ /Ni3+-Ionen sind quadratisch planar koordiniert, sechs NiO4-Polygone verknüpfen zu einem für Nickel zum ersten Male beobachteten geschlossenen Riesenpolyeder.
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  • 38
    ISSN: 0044-2313
    Keywords: Tris(tri-tert-butylsilyl)heptaphosphonortricyclane P7(t-Bu3Si)3 ; synthesis ; 31P{1H} NMR data ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Characterization, and Structure of P7(t-Bu3Si)3 („Tris(supersilyl)heptaphosphane(3)“Tris(tri-tert-butylsilyl)heptaphosphanortricyclane P7(t-Bu3Si)3 1 is obtained from the reaction of (t-Bu)3Si—Si(t-Bu)3 with white phosphorus and forms colorless to pale yellow thermostable crystals. 1 is identified by the complete analysis of its 31P{1H} NMR spectrum (A[MX]3 spin system) as well as by a single crystal structure determination (space group Pca21, a = 170.76(2)pm, b = 131.14(3)pm, c = 426.61(5)pm, α = β = γ= 90°, Z = 8 formula units in the elementary cell). The steric demand of the (t-Bu)3Si-Groups causes an increase of the exocyclic bond angles at the equatorial phosphorus atoms Pe, while it does not particularly influence the P7-skeleton. Chlorine (r.t.) and bromine (70°C) degrade the P7-cage of 1 with formation of PX3 and (t-Bu)3SiX (X = Cl, Br).
    Notes: Tris(tri-tert-butylsilyl)-heptaphosphanortricyclan P7(t-Bu3Si)3 1 entsteht durch Umsetzung von (t-Bu)3Si—Si(t-Bu)3 mit weißem Phosphor und bildet farblose bis blaßgelbe thermostabile Kristalle. Die Identität von 1 wird durch die vollständige Analyse des 31P{1H}-NMR-Spektrums (A[MX]3-Spinsystem) sowie durch eine Kristallstrukturbestimmung belegt. 1 kristallisiert in der Raumgruppe Pca21 mit Z = 8 Formeleinheiten; a = 170,76(2)pm, b = 131,14(3)pm, c = 426,61(5)pm, α = β = γ= 90°. Der erhöhte Raumbedarf der (t-Bu)3Si-Gruppen führt zu einer Aufweitung der exocyclischen Bindungswinkel an den äquatorialen Phosphoratomen Pe ohne das P7-Gerüst besonders zu beeinflußen. Chlor (Raumtemperatur) und Brom (70°C) bauen den P7-Käfig von 1 unter Bildung von PX3 und (t-Bu)3SiX (X = Cl, Br,) ab.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 617-620 
    ISSN: 0044-2313
    Keywords: Potassium ; magnesium ; copper ; vanadium ; oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Crystal Structure of Potassium Magnesium Oxocuprate/-vanadate: KMg2Cu2V3O12.Single crystals of KMg2Cu2V3O12 were prepared by solid state reactions below the melting point of the reaction mixture (K2CO3, MgCO3, CuO, V2O5). It crystallizes with monoclinic symmetry space group C2h6—C2/c, a = 12.1592 Å, b = 12.7204 Å, c = 6.8557 Å, β = 111.73°, Z = 4. The structure type is characterized by VO4 tetrahedra, twisted CuO4 square units, MgO6 octahedra and a special 2 + 4 + 2 coordination around the potassium ion.
    Notes: Einkristalle von KMg2Cu2V3O12 wurden durch Feststoffreaktionen, dicht unterhalb des Schmelzpunktes des Reaktionsgemenges (K2CO3, MgCO3, CuO, V2O5), erhalten. Die Verbindung kristallisiert mit monokliner Symmetrie, Raumgruppe C2h6—C2/c, a = 12,1592 Å, b = 12,7204 Å, c = 6,8557 Å, β = 111,73°, Z = 4. Die Kristallstruktur ist durch VO4-Tetraeder, tordierte CuO4-Baugruppen, MgO6-Oktaeder und Kalium, in einer besonderen 2 + 4 + 2 Koordination charakterisiert.
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  • 40
    ISSN: 0044-2313
    Keywords: Niobum bromides ; (Nb6Br18) units ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kristallchemie einiger neuer Niobbromide mit (Nb6Br18)-Einheiten: Die Strukturen von CsErNb6Br18 und Cs2EuNb6Br18.Zwei neue Reihen von Nb6-Bromiden, CsSENb6Br18 (SE = alle Lanthanoide außer Eu und Yb, + Y) (Typ H) und M2SENb6Br18 (M = Cs, Rb, Tl; SE = Eu, Yb) (Typ R) sind dargestellt worden. Die Kristallstrukturen von CsErNb6Br18 und Cs2EuNb6Br18, isotyp mit den entsprechenden Chloriden, wurden durch Einkristall-Röntgendaten bestimmt. Die Stabilität der (Nb6Br18)-Einheit hängt von der Art und der Ladung des Gegenkations ab. Ein Vergleich zwischen den entsprechenden Reihen der Chloride und Bromide wird anhand der chemischen Eigenschaften und der Größe des Halogens diskutiert.
    Notes: Two new series of Nb6 bromides, CsRENb6Br18 (RE = all the lanthanides excepted Eu and Yb, + Y) (type H) and M2RENb6Br18 (M = Cs, Rb, Tl; RE = Eu, Yb) (type R) have been isolated. The crystal structures of CsErNb6Br18 and Cs2EuNb6Br18, isotypic with the corresponding chlorides, have been determined by single crystal X-ray diffraction data. The (Nb6Br18) intra-unit strength is related to the nature and the charge of the counter cation. A comparison between the corresponding chlorides and bromides series, based on the chemical properties and the size of the halogen is discussed.
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  • 41
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 695-698 
    ISSN: 0044-2313
    Keywords: Rhenium ; crystal structure ; hydrogen-bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Chloroacid of Trivalent Rhenium: Hydroxonium Decachloro Diaqua Trirhenate(III) Pentahydrate, H3O[Re3Cl10(H2O)2] · 5H2O.A chloroacid of rhenium(III), H3O[Re3Cl10(H2O)2] · 5H2O, was obtained at room temperature from a saturated solution of “ReCl3 · 2H2O” with an excess of NaCl in concentrated hydrochloric acid. The crystal structure (tetragonal, P41212 (Nr. 92); a = 1 150.9(2) pm; c = 1 592.2(6) pm; Z = 4; R = 0.086; Rw = 0.066) has been determined from four-circle diffractometer data. The structure contains isolated cluster anions, [Re3Cl3i,bCl6o,tCli,t (H2O)2i,t]-, which are enclosed by a cage of water molecules. These building units are connected with each other through a “strong” hydrogen-bonding system.
    Notes: Die Chlorosäure H3O[Re3Cl10(H2O)2] · 5H2O kristallisiert aus einer mit NaCl und „ReCl3 · 2H2O“ gesättigten Lösung in konz. Salzsäure bei Raumtemperatur aus. Die Kristallstruktur wurde aus Vierkreis-Diffraktometerdaten bestimmt: tetragonal, P41212 (Nr. 92); a = 1 150,9(2) pm; c = 1 592,2(6) pm; Z = 4; R = 0,086; Rw = 0,066. In der Struktur liegen isolierte, anionische, trimere Einheiten [Re3Cl3i,bCl6o,tCli,t(H2O)2i,t]- vor, welche über „starke“ Wasserstoffbrückenbindungen „käfigartig“ mit Wassermolekülen umgeben und durch diese Hydrathülle miteinander vernetzt sind.
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  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 718-726 
    ISSN: 0044-2313
    Keywords: Organoindium fluorides ; organoindium fluoride cesium fluoride complexes ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Insertion of Metal Fluorides in Organoindium Fluorides.The reaction of i-Pr2InCl (1) with CsF in acetonitrile at room temperature yields [(i-Pr2InF)5(CsF · 2 MeCN)] ([2 · 2 MeCN]). {[(MesInF2)10MgF2] · 5 toluene} ({3 · 5 toluene}) can be isolated as a by-product in the reaction of Mes3In with BF3 · OEt2 in the presence of MgBrCl. [2 · 2 MeCN] and {3 · 5 toluene} were characterized by NMR spectroscopy as well as by X-ray structure determinations. [2 · 2 MeCN] forms infinite double chains of (i-Pr2InF)5-blocks and CsF-units. The coordination sphere of the cesium atom consists of three fluorine atoms and the nitrogen atoms of three acetonitrile molecules, which wrap the metal atom in a strongly distorted octahedral fashion. One of the acetonitrile molecules in [2 · 2 MeCN] has a μ2-bridging function. This results in the formation of four membered Cs2N2-rings.In {3 · 5 toluene}, ten molecules of MesInF2 are forming a cage in which a linear MgF2-unit is inserted.
    Notes: Die Reaktion von i-Pr2InCl (1) mit CsF in Acetonitril bei Raumtemperatur führt zu [(i-Pr2InF)5(CsF · 2 MeCN)] ([2 · 2 MeCN]).{[(MesInF2)10MgF2] · 5 Toluol} ({3 · 5 Toluol}) kann als Nebenprodukt bei der Umsetzung von Mes3In mit BF3 · OEt2 in der Gegenwart von MgBrCl erhalten werden. [2 · 2 MeCN] und {3 · 5 Toluol} wurden mittels NMR-Methoden sowie durch Röntgenstrukturanalysen charakterisiert. [2 · 2 MeCN] bildet unendliche Doppelstränge aus (i-Pr2InF)5-Blöcken und CsF-Einheiten. Die Koordinationssphäre des Cs-Atoms besteht aus drei F-Atomen und den N-Atomen von drei Acetonitril-Molekülen, was zu einer stark verzerrt oktaedrischen Umgebung des Metallatoms führt. Eines der Acetonitril-Moleküle in [2 · 2 MeCN] hat eine μ2-verbrückende Funktion, woraus sich die Ausbildung von Cs2N2-Vierringen ergibt.In {3 · 5 Toluol} wird ein Käfig aus zehn MesInF2-Einheiten geformt, in welchem eine lineare MgF2-Einheit eingelagert ist.
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  • 43
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 727-730 
    ISSN: 0044-2313
    Keywords: Antimonytriiodide complex with trithiacyclononane ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of SbI3 · 9S3 (9S3 = 1.4.7-Trithiacyclononane).SbI3 forms a 1:1 adduct with 1.4.7-trithiacyclononane. The crystal structure exhibits discrete complexes with a distorted octahedral coordination of antimony(III). In comparison with molecular SbI3 the Sb—I distances are elongated from 271.9 to 290.4 pm (mean). The mean value of the Sb—S distances is 287.5 pm. The planes through iodine and sulfur atoms, respectively, are nearly coplanar. There is no significant stereochemical influence of the Sb(III) lone pair.
    Notes: SbI3 bildet ein 1:1-Addukt mit 1,4,7-Trithiacyclononan. Die Kristallstruktur enthält diskrete Komplexe mit verzerrt oktaedrischer Koordination von Antimon(III). Im Vergleich zum molekularen SbI3 ist der Sb—I-Abstand von 271,9 auf 290,4 pm aufgeweitet. Der mittlere Sb—S-Abstand beträgt 287,5 pm. Die Ebenen durch die drei Iod- und drei Schwefelatome sind nahezu koplanar. Ein signifikanter stereochemischer Einfluß des nichtbindenden Elektronenpaares von Sb(III) ist nicht zu erkennen.
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  • 44
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 741-747 
    ISSN: 0044-2313
    Keywords: Gadolinium iodide carbide, Gd3I3C ; preparation ; X-ray single crystal investigation ; crystal structure ; condensed cluster ; double chain of condensed octahedra ; electrical resistivity ; magnetic susceptibility ; antiferromagnetic order ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Properties of Gd3I3C.The compound Gd3I3C is prepared by reaction of Gd, GdI3 and C (2:1:1 mole) at 1 250 K in sealed Ta tubes. It is obtained as bronze-coloured needles which are air and moisture sensitive. The structure of Gd3I3C contains twin chains of C centered Gd6 octahedra surrounded by I atoms capping all free edges like in the M6X12 cluster. The one-dimensional units are oriented along [010] and linked according to (GdGd1/3Gd2/2Gd2/3C)2I2iI4/2i-iI2/2i-aI2/2a-i. Gd3I3C is metallic in the temperature range 300 K ≥ T ≥ 120 K, between 120 and 15 K the electrical resistance increases by 6 orders of magnitude. At high temperatures the susceptibility follows the Curie-Weiß law with a paramagnetic Curie temperature θ ≈ - 340 K. Two local maxima in the susceptibility at 100 K and 25 K indicate successive formation of antiferromagnetically ordered structures.
    Notes: Gd3I3C wird durch Reaktion von Gd, GdI3 und C (Molverhältnis 2:1:1) bei 1 250 K im verschlossenen Ta-Tiegel erhalten. Es bildet metallisch glänzende, bronzefarbene Nadeln, die gegen Luft und Feuchtigkeit empfindlich sind. Die Struktur von Gd3I3C enthält durch einzelne C-Atome zentrierte Gd6-Oktaeder, die zu Doppelketten kondensiert sind und von den Iod-Atomen über allen freien Kanten nach Art des M6X12-Clusters koordiniert werden. Diese eindimensionalen Einheiten verlaufen längs [010] und sind untereinander nach dem Schema (GdGd1/3Gd2/2Gd2/3C)2I2iI4/2i-iI2/2i-aI2/2a-i verknüpft. Gd3I3C besitzt im Temperaturbereich 300 K ≥ T ≥ 120 K metallisches Verhalten, zwischen 120 und 15 K steigt der elektrische Widerstand um 6 Größenordnungen an. Die magnetische Suszeptibilität läßt sich bei hohen Temperaturen durch das Curie-Weiß-Gesetz mit einer paramagnetischen Curie-Temperatur von θ ≈ - 340 K beschreiben. Zwei lokale Maxima der Suszeptibilität bei 100 K und 25 K weisen auf sukzessive Ausbildung antiferromagnetischer Ordnungsstrukturen hin.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 761-765 
    ISSN: 0044-2313
    Keywords: Synthesis ; crystal structure ; neodymium ; ternary ammonium nitrate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (NH4)6Nd(NO3)9, A Ternary Ammonium-Rich Lanthanide Nitrate with Lonesome Nitrate Ions: (NH4)6[Nd(NO3)6](NO3)3.Single crystals of the ternary ammonium neodymium nitrate (NH4)6Nd(NO3)9 are obtained from a solution of Nd2O3 in a melt of NH4NO3. In the crystal structure (monoclinic, C 2/c, Z = 4, a = 1 775.1(4), b = 912.7(3), c = 2 072.3(5) pm; β = 125.56(1)°; R = 0.059, Rw = 0.036) the Nd3+ ion is surrounded by six bidentate nitrate ligands so that anionic units [Nd(NO3)6]3- are formed. The units are isolated, but they are incorporated in layers parallel to (010). The structure is held together by a network of hydrogen bonds, built up by NH4+ and NO3- ions lying between the layers. Due to the structure, the compound may be described as a double salt like (NH4)3[Nd(NO3)6] · 3 NH4NO3 or, better, as (NH4)6[Nd(NO3)6](NO3)3.
    Notes: Einkristalle des ternären Ammonium-neodymnitrates (NH4)6Nd(NO3)9 erhält man aus der Lösung von Nd2O3 in einer Schmelze von NH4NO3. Die Röntgenstrukturanalyse von (NH4)6Nd(NO3)9 (monoklin, C 2/c, Z = 4; a = 1 775,1(4); b = 912,7(3); c = 2 072,3(5) pm; β = 125,56(1)°; R = 0,059; Rw = 0,036) zeigt, daß Nd3+ von sechs zweizähnigen Nitratliganden in der anionischen Einheit [Nd(NO3)6]3- umgeben ist. Diese isolierten Einheiten sind in Schichten parallel (010) angeordnet. Durch die zwischen den Schichten liegenden NH4+- und NO3--Ionen wird ein Netzwerk von Wasserstoffbrückenbindungen gebildet, das für den Zusammenhalt der Struktur sorgt. Auf Grund des Aufbaus muß die Verbindung nach Art eines Doppelsalzes als (NH4)3[Nd(NO3)6] · 3 NH4NO3 bzw. besser gemäß (NH4)6[Nd(NO3)6](NO3)3 formuliert werden.
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  • 46
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    Zeitschrift für anorganische Chemie 619 (1993), S. 753-760 
    ISSN: 0044-2313
    Keywords: Metal bis(acetylacetonate) complexes ; binuclear complexes ; ligand exchange reactions ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Exchange of Metal Ions in the System Acetylacetonate/Halide/Tetrahydrofuran.As bifunctional Lewis bases metal bis(acetyl-acetonates) react with zinc(II) chloride under formation of binuclear complexes (THF)2M(acac)2ZnCl2 (M = Ni, Co, Mg). The octahedral and the tetrahedral centre of these compounds are connected by tridentate oxygen atoms of the two acetylacetonato ligands which are simultaneously part of a four-membered ring MOZnO. The addition is combined with a deformation of the octahedral centre, as a prerequisite of a closest package of the atoms within the MOZnO ring.With mercury(II) chloride the metal bis(acetylacetonates) react as tetrafunctional Lewis bases. In the trinuclear complexes (THF)2M(acac)2(HgCl2)2 (M = Co, Ni, Mg) the interaction between the three coordination centres is weak. No structural change of the octahedral centre (THF)2M(acac)2 is found, but the HgCl2 group diverge slightly from linearity.A ligand exchange was observed in the following cases: (a)Reaction of vanadium(III) chloride with Co(acac)2 under formation of [(THF)2V(acac)2][(THF)CoCl3] (transition of the acetylacetonato ligands to the higher valent central atom).(b)Reaction of magnesium halides with M(acac)2 and formation of (THF)3Mg(acac)2MX2(c)Formation von (THF)3Co(acac)(μ - C1)ZnC12 (V) by the reaction of Zn(acac)2 with cobalt(l1) chlorideIn the complex V the octahedral ccntrc of cobalt(II) is connected with the tetrahedral centre of zinc(I1) by tridentate oxygen atom of the acetylacetonato ligand and a chloro bridge (formation of the four-membered CoClZnO cycle with a closest package of the atoms).A driving force for reaction c is the formation of the stable tetrahedral OZnCI3 group. Important for the li- gand exchange according to c is the stability of the octa- hcdral MgO6 moiety and the easy formation of the tetra- hedral MO2X2 group with a transition metal ion.(THF)3Co(acac)(μ-CI)(HgCl2) (VI) is isoslruclural with V. But there is a marked diffcrence between the bond angles of the tetrahedral central atom including the termi- nal chloro ligands (120.7° for V; 143.7° for VI).The crystal structure of (THF)3Co(acac)(μ-CI)ZnCl2 (V) was determined by X-ray diffraction: monoclinic; space group P2,/n; Z = 4; a = 1 177.4(5); b = 1628.9(4); c = 1284.2(6) pm; β = 99.54(4)°; R = 6.71 % for 2160 observed reflections.
    Notes: Metall-bis(acetylacetonate) fungieren in THF gegenüber Zink(II)-chlorid als bifunktionelle Lewis-Basen und bilden binukleare Komplexe (THF)2M(acac)2ZnCl2 (M = Co, Ni, Mg). Ein oktaedrisches und ein tetraedrisches Zentrum sind über zwei dreibindige Sauerstoffatome der Acetylacetonatliganden miteinander verknüpft (Bildung eines viergliedrigen MOZnO-Rings). Die Addition ist mit einer Deformation des oktaedrischen Zentrums verbunden, die eine dichte Packung der vier Atome des MOZnO-Ringes ermöglicht.Gegenüber Quecksilber(II)-chlorid fungieren die Metall-bis(acetylacetonate) als tetrafunktionelle Lewis-Basen. In den trinuklearen Komplexen (THF)2M(acac)2(HgCl2)2 (M = Co, Ni, Mg) bleibt die Wechselwirkung zwischen den drei Koordinationszentren gering; das oktaedrische Zentrum wird strukturell nicht verändert, die beiden HgCl2-Bausteine weichen nur gering von der Linearität ab.Ein Ligandenaustausch wurde in folgenden Fällen beobachtet: (a)Umsetzung von Vanadium(III)-chlorid mit Co(acac)2 unter Bildung von [(THF)2V(acac)2][(THF)CoCl3] (übergang der Acetylacetonatliganden auf das höherwertige Zentralatom).(b)Umsetzung von Magnesiumhalogeniden mit M(acac)2 unter Bildung von (THF)2Mg(acac)2MX2(c)Bildung von (THF)3Co(acac) (μ - Cl)ZnCl2 (V) aus Zn(acac)2 und Cobalt(II)-chloridIm Komplex V ist das oktaedrische Zentrum am Cobalt über ein dreibindiges Sauerstoffatom des Acetylacetonatoliganden und eine Chlorobrücke mit dem tetraedrischen Zentrum am Zink verknüpft (Bildung eines viergliedrigen CoClZnO-Ringes mit dichtester Packung der Atome).Wesentliche Triebkraft für die Umsetzung gemäß c ist die Bildung der stabilen OZnCl3-Gruppierung. Für den Ligandenaustausch gemäß b ist die Stabilität der oktaedrischen MgO6-Gruppierung und die leichte Bildung der teraedrischen Baugruppe MO2X2 bei den übergangsmetallen maßgebend. (THF)3Co(acac)(μ - Cl)HgCl2 (VI) ist isostrukturell mit V. Deutlich verschieden sind allerdings die Valenzwinkel am tetraedrischen Zentralatom, in die die terminalen Chloroliganden einbezogen sind (120,7° für V; 143,7° für VI).Die Kristallstruktur von (THF)3Co(acac)(μ - Cl)ZnCl2 (V) wurde durch Röntgenbeugung bestimmt: monoklin, Raumgruppe P21/n, Z = 4; a = 1 177,4(5); b = 1 628,9(4); c = 1 284,2(6) pm; β = 99,54(4)°; R = 6,71% für 2 160 beobachtete Reflexe.
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  • 47
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 766-770 
    ISSN: 0044-2313
    Keywords: Mixed alkali orthoarsenate, NaLi2[AsO4] ; crystal structure ; MAPLE calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Alkali Oxoarsenates(V): NaLi2[AsO4]  -  A New Type of Formula [1].By heating of well ground mixtures of the binary oxides As2O3, Na2O, and Li2O2, molar ratio As:Na:Li = 1.0:1.0:2.0, in a well closed Ni tube (650°C, 21 d) colourless single crystals of NaLi2[AsO4] were obtained for the first time. The new orthoarsenate(V) crystallizes orthorhombic (space group P mn21-C2v7, No. 31) with Z = 2. The structure determination showed that it is isostructural to βII-Li3[VO4] and that means the Li3[PO4]-type. The lattice constants a = 702.9(2) pm, b = 520.5(1) pm, c = 505.4(2) pm were taken from Guinier-Simon powder data. The structure was determined by four-circle diffractometer data [Philips PW 1 100, AgKα, 679 independent out of 2 373 Io(hkl), R = 3.03%, Rw = 2.29%; parameter see text]. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.
    Notes: Zur Synthese von NaLi2[AsO4] wurden innige Gemenge der binären Ausgangskomponenten As2O3, Na2O und Li2O2 im Molverhältnis As:Na:Li = 1,0:1,0:2,0 in einer fest verschlossenen Ni-Bombe, diese in einer Ampulle aus Supremax-Glas eingeschmolzen, bei 650°C 21 Tage getempert. NaLi2[AsO4] fiel in Form plättchenförmiger, farbloser Einkristalle an. Das neue Orthoarsenat kristallisiert orthorhombisch (Raumgruppe P mn21-C2v7, Nr. 31) mit Z = 2. Die Strukturaufklärung ergab Isotypie zu βII-Li3[VO4] mit a = 702,9(2) pm, b = 520,5(1) pm, c = 505,4(2) pm (Guinier-Simon-Daten). Die Struktur wurde über Vierkreisdiffraktometerdaten [Philips PW 1 100, AgKα, 679 symmetrieunabhängige aus 2 373 Io(hkl), R = 3,03%, Rw = 2,29%; Parameter siehe Text] bestimmt. Der Madelunganteil der Gitterenergie, MAPLE, und Effektive Koordinationszahlen, ECoN, diese über fiktive Ionenradien, MEFIR, werden berechnet und diskutiert.
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  • 48
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 775-778 
    ISSN: 0044-2313
    Keywords: Nitrido complex of tungsten ; synthesis ; IR-spectrum ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2].The title compound has been prepared by the reaction of CuCl with WNCl3 in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH3CN)4]+ ions, which are arranged to form strands, and of anions [W4N4Cl14(CH3CN)2]2-, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W≡N—W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.
    Notes: Die Titelverbindung wird durch Umsetzung von Kupfer(I)chlorid mit WNCl3 in Acetonitril in Form roter feuchtigkeitsempfindlicher Kristalle gewonnen. Sie wird durch das IR-Spektrum und eine röntgenographische Strukturanalyse charakterisiert. Raumgruppe I2/a, Z = 4, 2 027 beobachtete unabhängige Reflexe, R = 4,9%. Gitterkonstanten bei -80°C: a = 2 527,0; b = 971,9; c = 2 137,5 pm; β = 106,01°. Die Verbindung besteht aus [Cu(CH3CN)4]+-Ionen, die zu Strängen angeordnet sind, und Anionen [W4N4Cl14(CH3CN)2]2-, in denen die Wolframatome an den Ecken eines Quadrats angeordnet sind und über lineare W≡N—W-Brücken verknüpft sind. Zwei der Wolframatome haben je vier Chloratome als terminale Liganden, die beiden anderen je drei Chloratome und je ein N-Atom eines Acetonitrilmoleküls als terminale Liganden.
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  • 49
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 786-790 
    ISSN: 0044-2313
    Keywords: Bis(N,N-diethyl-N′-benzoylselenoureato)-zinc(II) ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of Bis(N,N-Diethyl-N′-benzoylselenoureato)zinc(II).Zn(C12H15N2OSe)2 crystallizes in the acentric orthorhombic space group Pca21. The cell parameters are a = 16.914(5), b = 13.492(4), c = 11.705(5) Å and Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 7,05%. ZnII is coordinated to two N,N-Diethyl-N′-benzoylselenoureato molecules, which are bidentately coordinated through their oxygen and selenium atoms to form a distorted tetrahedron. The Zn—Se bond lenghts are 2.394(3) and 2.369(4) Å, the Zn—O bond lengths are 1.971(11) and 1.974(12) Å.
    Notes: Zn(C12H15N2OSe)2 kristallisiert in der azentrischen orthorhombischen Raumgruppe Pca21 mit den Gitterkonstanten a = 16,914(5), b = 13,492(4), c = 11,705(5) Å, Z = 4. Die Struktur wurde mit Patterson und Direkten Methoden gelöst und bis zu einem R-Wert von 7,05% verfeinert. Zink bildet mit dem Liganden N,N-Diethyl-N′-benzoylselenoharnstoff einen bidental koordinierten Komplex, in dem zwei Ligandmoleküle über Selen und Sauerstoff in Form eines verzerrten Tetraeders an das Zentralatom gebunden sind. Die Zn—Se-Abstände betragen 2,394(3) und 2,369(4) Å, die Zn—O-Abstände 1,971(11) und 1,974(12) Å.
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  • 50
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 791-795 
    ISSN: 0044-2313
    Keywords: Bis(N,N-Diethyl-N′-benzoylselenoureato)-cadmium(II) ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of Bis(N,N-Diethyl-N′-benzoylselenoureato)cadmium(II).Cd(C12H15N2OSe)2 exists in a dimeric oxygen bridged form and crystallized in the monoclinic space group P21/n. The cell parameters are a = 12.506(3), b = 11.563(2), c = 18.924(4) Å, β = 91.59(3)°, Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 6.58%. Cadmium is coordinated by 3 oxygen and 2 selenium atoms and exhibits the unusual coordination number 5. The coordination polyhedron is a distorted trigonal bipyramid, to bipyramids are connected by a common edge. The Cd—Se bond lengths are 2.591(1) and 2.565(1) Å, the Cd—O bond lengths are 2.263(6), 2.272(5) und 2.438(5) Å.
    Notes: Cd(C12H15N2OSe)2 liegt als sauerstoff-verbrücktes Dimer vor und kristallisiert in der monoklinen Raumgruppe P21/n mit den Gitterkonstanten a = 12,506(3), b = 11,563(2), c = 18,924(4) Å, β = 91,59(3)°, Z = 4. Die Struktur wurde mit Patterson und Direkten Methoden gelöst und bis zu einem R-Wert von 6,58% verfeinert. Die Cadmiumatome sind von jeweils 3 Sauerstoff- und 2 Selenatomen koordiniert und besitzen die ungewöhnliche Koordinationszahl 5. Das Koordinationspolyeder ist eine verzerrte trigonale Bipyramide, zwei Bipyramiden sind über eine gemeinsame Kante miteinander verknüpft. Die Cd—Se Abstände betragen 2,591(1) und 2,565(1) Å, die Cd—O Abstände 2,263(6), 2,272(5) und 2,438(5) Å.
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  • 51
    ISSN: 0044-2313
    Keywords: Molybdenum / tungsten complexes ; pyridinium molybdenum / tungsten tetrabromine complexes ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kristallstruktur von trans-pyH[MoBr4py2] und die Reaktivität von trans-pyH[MBr4py2] (M = Mo, W; py = Pyridin) gegenüber Stickstoff-Liganden und zur Oxidation mit Brom.Die Kristallstruktur von trans-pyH[MoBr4py2] wurde bestimmt: orthorhombisch, Pnma (No. 62), a = 16,197(3), b = 13,995(3), c = 8,615(1) Å, Z = 4, Dgemess. = 2,20(3), Dröntg. = 2,23 g/cm3, V = 1953(1) Å3. R1, Rw = 0,057 and 0,053. Trans-[MoBr4py2]-, mit der gestaffelten Konformation der Pyridin-Liganden in der Spiegelebene. Mo—Br- und Mo—N(Pyridin)-Abstände sind 2,593(1), 2,573(1), 2,227(8) und 2,213(7) Å. Die Kationen befinden sich in den Symmetriezentren.Das Kation in trans-pyH[MBr4py2] ist ersetzbar; trans-NH4[MBr4py2] · H2O, Cs[MBr4py2], LH[MBr4py2] (M = Mo, W; L = 4-Methylpyridin, 4-pic; 2,2′-Bipyridyl, bipy) wurden dargestellt. Die Molybdän- und Wolfram-Verbindungen analoger Zusammensetzung sind isostrukturell. Alle Stoffe reagieren mit Pyridin und 4-Methyl-pyridin zu trans-MBr3L3 und im Fall des Molybdäns auch zu trans-MoBr3py2(4-pic). Brom oxidiert trans-MI[MBr4py2] zu trans-MBr4py2.
    Notes: The crystal structure of trans-pyH[MoBr4py2] has been determined: orthorhombic, Pnma (No. 62), a = 16.197(3), b = 13.995(3), c = 8.615(1) Å, Z = 4, Dc = 2.23, Do = 2.20(3) g/cm3, V = 1 953(1) Å3. R1, Rw = 0.057 and 0.053. Trans-[MoBr4py2]- anions with staggered conformation of pyridine rings are located on the mirror planes. Mo—Br, Mo—N(pyridine) distances are 2.593(1), 2.573(1), 2.227(8) and 2.213(7) Å. Cations are located on the symmetry centers.The cation in trans-pyH[MBr4py2] can be replaced. Trans-NH4[MBr4py2] · H2O, Cs[MBr4py2], LH[MBr4py2] (M = Mo, W; L = 4-methylpyridine, 4-pic; 2,2′-bipyridyl, bipy) were prepared. The compounds of molybdenum and tungsten with the same chemical composition are isostructural. All compounds react with pyridine and 4-methylpyridine. The products are trans-MBr3L3, and in the case of molybdenum, also trans-MoBr3py2(4-pic). Bromine oxidizes trans-MI[MBr4py2] to trans-MBr4py2.
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  • 52
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    Zeitschrift für anorganische Chemie 619 (1993), S. 811-818 
    ISSN: 0044-2313
    Keywords: Alkali metal digermanate ; preparation ; crystal structure ; MAPLE calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chains consisting of Rings: K5{Li[Ge2O7]}  -  the First ‘Litho-Digermanate’By heating of a well-ground mixture of the binary oxides KO0.55, Li2O and GeO2 (K: Li: Ge = 6.1 : 2.2 : 2; Ni-tube; 600°C; 49 d) we obtained for the first time single crystals of K5{Li[Ge2O7]}. This ‘lithodigermanate’ represents a completely new type of structure: monoclinic, space group P21/c, a = 624.9(2) pm, b = 1586.6(8) pm; c = 1058.3(6) pm and β = 109.38(4)°; Guinier-Simon data, Z = 4. The structure was solved by four-circle diffractometer data [Siemens AED II, Mo—Kα; 2872 Io(hkl); R = 4.5%, Rw = 3.3%], parameters see text. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, these calculated via Mean Fictive Ionic Radii, MEFIR, as well as charge distribution CHARDI, are calculated and discussed.
    Notes: Durch Tempern inniger Gemenge der binären Oxide KO0,55, Li2O und GeO2 (K: Li: Ge = 6,1: 2,2: 2; Ni-Bömbchen; 600°C; 49 d) wurden erstmals Kristalle von K5{Li[Ge2O7]} erhalten. Das „Litho-Digermanat“ repräsentiert einen völlig neuen Strukturtyp, der „Ketten aus Ringen {Li[Ge2O7]5}“ enthält (monoklin, Raumgruppe P21/c mit a = 624,9(2) pm, b = 1 586,6(8) pm; c = 1058,3(6) pm und β = 109,38(4)°; Guinier-Simon Daten, Z = 4). Die Struktur wurde mittels Vierkreisdiffraktometerdaten [Siemens AED II; Mo—Kα; 2872 Io(hkl); R = 4,5%; Rw = 3,3%] bestimmt, Parameter siehe Text. Der Madelunganteil der Gitternergie, MAPLE, und Effektive Koordinationszahlen, ECoN, diese über Mittlere Fiktive Ionenradien, MEFIR, sowie die Ladungsverteilung CHARDI werden berechnet und diskutiert.
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  • 53
    ISSN: 0044-2313
    Keywords: Tetrabariumtriphosphide, Ba4P3 ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 58. Tetrabariumtriphosphide, Ba4P3: Preparation and Crystal StructureBa4P3 is obtained from the elements in the molar ratio 4:3 or by reaction of Ba3P2 and Ba5P4 in the molar ratio 1:1 (steel ampoules with inner corundum crucibles; 1 490 K). The greyish black, easily hydrolysing compound crystallizes in a new structure type oP56. The structure shows two crystallographically independent dumbbells P24- (d(P—P) = 225 and 232 pm) and isolated ions P3- corresponding to (Ba2+)8(P24-)4(P3-)4. The partial structure of the Ba atoms forms a complex network of trigonal prisms with tetrahedral and square pyramidal holes, as well as polyhedra with 14 faces (CN 10) which are icosahedron derivatives. The P3- anions center trigonal prisms and the 14 face polyhedron. The P-atoms of the P24- dumbbells center neighboring trigonal prisms with common square faces. (Pbam (no. 55); a = 1 325.4(2) pm, b = 1 256.2(2) pm, c = 1 127.3 pm; Z = 8).
    Notes: Ba4P3 erhält man aus den Elementen im Molverhältnis 4:3 oder durch Umsetzung von Ba3P2 und Ba5P4 im Molverhältnis 1:1 (Korundinnentiegel; Stahlampullen; 1 490 K). Die grauschwarze, hydrolyseempfindliche Verbindung kristallisiert in einem neuen Strukturtyp oP56 mit zwei kristallographisch unabhängigen P24--Hanteln (d(P—P) = 225 und 232 pm und isolierten P3--Anionen entsprechend (Ba2+)8(P24-)(P3-)4. Die Partialstruktur der Ba-Atome bildet ein komplexes Netz trigonaler Prismen mit tetraedrischen und quadratisch-pyramidalen Lücken, sowie einem 14-Flächner (CN 10), der sich vom Ikosaeder ableitet. Die P3--Anionen zentrieren trigonale Prismen und den 14-Flächner, die Atome der P24--Hanteln jeweils benachbarte trigonale Prismen mit gemeinsamer Vierecksfläche. (Pbam (Nr. 55); a = 1 325,4(2) pm, b = 1 256,2(2) pm, c = 1 127,3(2) pm; Z = 8).
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  • 54
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    Zeitschrift für anorganische Chemie 619 (1993), S. 849-852 
    ISSN: 0044-2313
    Keywords: Bis(pyridin)bis(trifluoromethyl)zinc ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structure of Bis(pyridine)bis(trifluoromethyl)zincBis(pyridin)bis(trifluoromethyl)zinc 1 has been isolated and characterized by means of single-crystal X-ray diffraction techniques. The title compound represents the first structure determination of a fully fluorinated alkylzinc compound (monoclinic, space group P21/c, Z = 4, a = 8.856(3), b = 18.158(3), c = 8.979(3) Å, β = 98.14(2)°, R = 0.054, Rw = 0.035). The zinc atom is in a distorted tetrahedral environment. The molecular structure of [ClZn(CCl2CF3) η2O]2 2 was solved, but is not included in a structural comparison due to crystallographic disorder.
    Notes: Der Pyridin-Komplex 1 von Bis(trifluoromethyl)zink wurde durch Einkristall-Röntgenstrukturanalyse charakterisiert. Die Titelverbindung repräsentiert die erste Struktur eines vollfluorierten Zinkalkyls (monoklin, Raumgruppe P21/c, Z = 4, a = 8,856(3), b = 18,158(3), c = 8,979(3) Å, β = 98,14(2)°, R = 0,054, Rw = 0,035). Das Zinkatom ist verzerrt tetraedrisch koordiniert. Die Kristall- und Molekülstruktur der zweikernigen Zinkverbindung [ClZn(CCl2CF3) η2O]2 2 wurde bestimmt, kann aber wegen kristallographischer Fehlordnung nicht einem Strukturvergleich unterzogen werden.
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  • 55
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    Zeitschrift für anorganische Chemie 619 (1993), S. 859-864 
    ISSN: 0044-2313
    Keywords: 2,2-Bis(diisopropoxyphosphonyl)propyl methyltin dibromide ; synthesis ; crystal structure ; n.m.r. data ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Molecular Structure of 2,2-Bis(diisopropoxyphosphonyl)propyl Methyltin DibromideBy methylation of Me3SnCH2CH[P(O)(OPr-i)2]2 with NaH/MeI Me3SnCH2C(Me)[P(O)(OPr-i)2]2 (1) is obtained, which is converted by bromine into the dibromide MeBr2SnCH2C(Me)[P(O)(OPr-i)2]2 (2). An X-ray crystal structure analysis shows 2 to be monomeric. The tin atom is situated in the centre of a distorted octahedron, in which the functional substituent is intramolecular coordinated as tridentate ligand in a facial mode. The two organo groups are arranged in trans-position (C—Sn—C 155.1°), whereas the oxygen and bromine atoms are orientated cis to each other. The six-membered ring of the bicyclic molecular fragment of 2 which results from the coordination of the functional organo group to the tin atom shows a boat-conformation, whereas the two five-membered rings exist in twist-conformations. Multinuclear n.m.r. and i.r. data show that 2 retains its solid state structure also in nonpolar solvents.
    Notes: Durch Methylierung von Me3SnCH2CH[P(O)(OPr-i)2]2 mittels NaH/MeI erhält man Me3SnCH2C(Me)[P(O)(OPr-i)2]2 (1), das mit Brom in das Dibromid MeBr2SnCH2C(Me)[P(O)(OPr-i)2]2 (2) überführt wird. Nach der Röntgenkristallstrukturanalyse ist 2 im Festkörper monomer. Das Zinnatom befindet sich im Zentrum eines verzerrten Oktaeders, in dem der funktionelle Substituent intramolekular als tridentater Ligand in facialer Anordnung koordiniert ist. Die beiden Organoreste sind trans-ständig angeordnet (C—Sn—C 155,1°), während sich die Sauerstoff- und Bromatome in cis-Anordnung zueinander befinden. Der Sechsring des aus der Koordination des funktionellen Organorestes am Zinnatom resultierenden bicyclischen Molekülfragmentes von 2 weist Wannenkonformation auf, während die beiden Fünfringe in Twist-Konformationen vorliegen. Multikern-NMR- und IR-Daten belegen, daß 2 seine Festkörperstruktur auch in unpolaren Lösungsmitteln beibehält.
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  • 56
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 885-888 
    ISSN: 0044-2313
    Keywords: Organodilithium phosphides ; organolithium phosphide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Characterization of Organodilithium Phosphides. The Crystal Structure of [Li(THF)(TMEDA)P(H)Mes]t-BuPH2 and MesPH2 can be reacted with two equivalents n-BuLi at R. T. in Et2O/n-hexane to yield the corresponding organodilithium phosphides t-BuPLi2 (1) and MesPLi2 (2). 1 and 2 can be isolated solvent-free as bright orange-yellow solids. 1 and 2 were characterized by NMR, IR, and RE spectra. When MesPH2 is treated with one equivalent of n-BuLi, MesP(H)Li is crystallizing as [Li(THF)(TMEDA)P(H)Mes] (3) from THF/TMEDA/n-pentane in the space group P21/n with a = 893.41(6), b = 1 734.7(1), c = 1 391.1(1) pm and β = 90.613(6)°.
    Notes: t-BuPH2 und MesPH2 werden bei Zimmertemperatur in Et2O/n-Hexan mit zwei äquivalenten n-BuLi zu den entsprechenden Organodilithiumphosphiden t-BuPLi2 (1) und MesPLi2 (2) umgesetzt. 1 und 2 können lösungsmittelfrei als leuchtend orange-gelbe Festkörper isoliert werden. 1 und 2 wurden mittels NMR-, IR- und RE-Spektren charakterisiert. Wird MesPH2 mit nur einem äquivalent n-BuLi behandelt, kristallisiert MesP(H)Li in Form von [Li(THF)(TMEDA)P(H)Mes] (3) aus THF/TMEDA/n-Pentan in der Raumgruppe P21/n mit a = 893,41(6), b = 1 734,7(1), c = 1 391,1(1) pm und β = 90,613(6)°.
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  • 57
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1419-1425 
    ISSN: 0044-2313
    Keywords: Lithium permanganate, Li[MnO4] ; preparation ; crystal structure ; neutron powder data ; MAPLE calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Coordination Number 4 or 6 for Lithium?: The Crystal Structure of Lithium Permanganate, Li[MnO4]Waterless 7Li[MnO4] was obtained by dehydration of 7Li[MnO4] · 3 D2O at 60°C above P4O10 in vacuum as violet powder.The structure determination by neutron diffraction measurements via pulsed polychromatic neutron source [time-of-flight powder diffractometer; profile-R-value = 2.1%, Bragg-R-value = 7.4%] confirms the space group Cmcm with a = 551.402(8), b = 839.754(15), c = 635.911(10) pm (Z = 4); parameters see text. The crystal structure of Li[MnO4] corresponds to the CrVO4-type with coordination number 6 for lithium and 4 for manganese.The Madelung Part of Lattice Energie, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution were calculated and discussed.
    Notes: Durch Trocknung von 7Li[MnO4] · 3 D2O bei 60°C über P4O10 im Vakuum wurde wasserfreies 7Li[MnO4] als violettes Pulver erhalten.Die Strukturaufklärung mittels Neutronenbeugungsmessungen im gepulsten polychromatischen Neutronenstrahl [Flugzeitdiffraktometer; Profil-R-Wert = 2,1%, Bragg-R-Wert = 7,4%] belegt die Raumgruppe Cmcm mit a = 551,402(8), b = 839,754(15), c = 635,911(10)pm (Z = 4); Parameter siehe Text. Die Kristallstruktur von Li[MnO4] entspricht dem CrVO4-Typ mit der Koordinationszahl 6 für Lithium und 4 für Mangan.Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECoN und die Ladungsverteilung wurden berechnet und diskutiert.
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  • 58
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1426-1430 
    ISSN: 0044-2313
    Keywords: Manganese fluorides ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Crystal Structure of MnF3 and MnPtF6Single crystal investigations of MnF3 (rubyred) confirmed the crystal structure based on powder data [2]: monoclinic, space group C 2/c-C2h6 (No. 15) with a = 892.02 pm, b = 504.72 pm, c = 1 347.48 pm, β = 92.64° with Z = 12.The corresponding determination of the crystal structure of MnPtF6, yellow, confirmed the unit cell [3] with a = 510.47 pm, c = 1 421.0 pm and γ = 120°, Z = 3 space group R 3-C3i2 (No. 148).For both compounds detailed parameters respectively interatomic distances have been obtained.
    Notes: Einkristalluntersuchungen an MnF3 (rubinrot) bestätigen den aus Pulverdaten [2] abgeleiteten Strukturvorschlag: monoklin, Raumgruppe C 2/c-C2h6 (Nr. 15) mit a = 892,02 pm, b = 504,72 pm, c = 1 347,48 pm, β = 92,64° mit Z = 12 (Vierkreisdiffraktometerdaten).Entsprechende Einkristalluntersuchungen an MnPtF6, hellgelb, bestätigen auch hier die Abmessungen der Elementarzelle [3] mit a = 510,47 pm, c = 1 421,0 pm und γ = 120°, Z = 3 in der Raumgruppe R °3-C3i2 (Nr. 148). Für beide Verbindungen konnten damit genaue Parameter bzw. interatomare Abstände ermittelt werden.
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  • 59
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1446-1454 
    ISSN: 0044-2313
    Keywords: Silver bismuthate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ag3BiO3 and Ag5BiO4,the first Silver Oxobismuthates(III)Applying high oxygen pressures (100 MPa) Ag3BiO3 and Ag5BiO4 were prepared for the first time by reacting the binary components Ag2O and Bi2O3 at temperatures between 770 and 800 K. Single crystals of both compounds were grown hydrothermally from Ag2O and Bi2O3 at 620 K and at oxygen pressures of 10 MPa. The crystal structure determination (Ag3BiO3: I41, a = 14.1924(1), c = 8.7997(1) Å, Z = 16, 1 729 diffractometer data, Rw = 0.057; Ag5BiO4: P21/n, a = 5.855(1), b = 8.984(1), c = 12.457(1) Å, β = 91.49(1)Å, Z = 4, 2716 diffractometer data, Rw = 0.036) shows that in Ag5BiO4 bismuth approximately has a square pyramidal coordination by five oxygen atoms. Two such pyramids share an edge thus forming ‘isolated’ Bi2O810- anions. In Ag3BiO3 the same groups are linked by the terminal oxygen atoms to form a three dimensional network. In both structures the cation arrangements form variants of the Laves-phases MgCu2 with silver occupying the copper positions. The Mg positions are ordered occupied by bismuth and silver.
    Notes: Ag3BiO3 und Ag5BiO4 wurden durch Festkörperreaktion aus den binären Komponenten Ag2O und Bi2O3 bei Temperaturen zwischen 770 und 800 K und Sauerstoffdrücken von 100 MPa erstmals dargestellt. Einkristalle von beiden Verbindungen konnten durch Hydrothermalreaktion zwischen Ag2O und Bi2O3 bei 620 K unter einem Sauerstoffdruck von 10 MPa dargestellt werden. Nach den Ergebnissen der Röntgenstrukturanalyse (Ag3BiO3: I41, a = 14,1924(1), c = 8,7997(1) Å, Z = 16, 1 729 Diffraktometerdaten, Rw = 0,057; Ag5BiO4: P21/n, a = 5,855(1), b = 8,984(1), c = 12,457(1) Å, β = 91,49(1)Å, Z = 4, 2716 Diffraktometerdaten, Rw = 0,036) liegt in Ag5BiO4 eine transständige Verknüpfung von quadratisch-pyramidal mit Sauerstoff koordinierten BiO5-Baueinheiten zu dimeren, ‘isolierten’, Bi2O810--Gruppen vor. In Ag3BiO3 findet man die gleichen Bi2O8-Baugruppen, die hier jedoch dreidimensional über die terminalen Sauerstoffatome verknüpft sind. In beiden Verbindungen sind die Kationen analog zur Laves-Phase MgCu2 angeordnet mit gemischter Besetzung der Mg-Position durch Silber und Bismut sowie Besetzung der Cu-Positionen ausschließlich durch Silber.
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  • 60
    ISSN: 0044-2313
    Keywords: Disulfonyl amines ; silver(I) 1,1,3,3-tetraoxo-1,3,2-benzodithiazolide ; aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) ; crystal structure ; thermal analysis ; calorimetry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XLII. An Aquasilver(I) Complex with an Ag(m̈-H2O)2Ag Structural Unit: Characterization of Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) by X-Ray Diffractometry and Thermal AnalysisThe title compound C6H4(SO2)2NAg · H2O, where C6H4(SO2)2Nº is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space group C2/m with (at -95°C) a = 1 129,7(3), b = 1 196.1(3), c = 810.7(2) pm, β = 124.25(2)°, V = 0.9055 nm3, Z = 4, Dx = 2.524 Mg m-3. The crystal packing consists of [Ag(m̈-H2O)2Ag{m̈-C6H4(SO2)2N}2]n bands with crystallographic mirror symmetry, associated into layers by H-bonds with O(W) - O(S) 289.7 pm. The Ag(m̈-H2O)2Ag moiety forms a planar four-membered ring with Ag—O(W)—Ag 97.3°, O(W)—Ag—O(W) 82.7° and Ag°Ag 372.1 pm. In the Ag{C6H4(SO2)2N}2Ag′ unit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bonded to Ag and O,O-chelated to Ag′, the other N-bonded to Ag′ and O,O-chelated to Ag. The silver atoms are (O4N)-pentacoordinate, with nitrogen in the apical position of a distorted square pyramid [Ag—N 223.6, Ag—O(W) 247.8, Ag—O(S) 259.4 pm]. The thermochemical behaviour of the hydrate was investigated by thermal analysis and calorimetry. Water is only released at temperatures above 220°C. The dehydration enthalpy at 298 K is + 13.9 kJ mol-1.
    Notes: Die Titelverbindung C6H4(SO2)2NAg · H2O, mit C6H4(SO2)2N- = Anion des 1,2-Benzoldisulfonsäureimids, kristallisiert in der monoklinen Raumgruppe C2/m mit (bei -95°C) a = 1 129,7(3), b = 1 196,1(3), c = 810,7(2) pm, β = 124,25(2)°, V = 0,9055 nm3, Z = 4, Dx = 2,524 Mg m-3. Die Kristallpackung besteht aus Strängen des Typs [Ag(m̈-H2O)2Ag{m̈-C6H4(SO2)2N}2]n mit kristallographischer Spiegelsymmetrie, die über H-Brücken mit O(W)…O(S) 289,7 pm zu Schichten assoziiert sind. Die Ag(m̈—H2O)2Ag-Einheit bildet einen planaren Vierring mit Ag - O(W) - Ag 97,3°, O(W) - Ag - O(W) 82,7° und Ag…Ag 372,1 pm. In der Ag{m̈—C6H4(SO2)2N}2Ag′-Einheit wirken die Anionen als dreizähnige (N, 1-O, 3-O)-Liganden, und zwar das eine als N-Donor gegenüber Ag und als O,O-Chelatligand gegenüber Ag′, das andere umgekehrt als N-Donor gegenüber Ag′ und als O,O-Chelatligand gegenüber Ag. Die Silberatome sind (O4N)-pentakoordiniert mit dem Stickstoffatom am Scheitelpunkt einer verzerrten quadratischen Pyramide [Ag—N 223,6, Ag—O(W) 247,8, Ag—O(S) 259,4 pm]. Das thermochemische Verhalten des Hydrats wurde mit thermoanalytischen und kalorimetrischen Methoden untersucht. Das Wasser wird erst bei Temperaturen oberhalb 220°C abgegeben. Die Dehydratationsenthalpie bei 298 K beträgt + 13,9 kJ mol-1.
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  • 61
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1526-1529 
    ISSN: 0044-2313
    Keywords: Octameric titanium imide chloride, [Ti(NSiMe3)Cl2]8 ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe3)Cl2]8The reaction of TiCl4 with N(SiMe3)3 in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe3)Cl2]8 (1). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl2-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe3)Cl2]n. Above 250°C 1 decomposes under separation of Me3SiCl affording TiNCl.
    Notes: TiCl4 reagiert in zugeschmolzenen Glasampullen mit N(SiMe3)3 zum Titanimidchlorid [Ti(NSiMe3)Cl2]8 (1). Es kristallisiert monoklin in der Raumgruppe C2/c mit a = 2 704,5(4), b = 1 303,9(1), c = 2 205,4(2) pm, β = 112,78(1)°, Z = 4. In 1 sind sechs Titanatome über Chloro- und Trimethylsilylimido-Brücken zu einer Ringstruktur verknüpft. Zusätzlich sind zwei TiCl2-Gruppen über zwei Imidobrücken an dß Ring gebunden. Durch Tempern bei 250°C wird 1 in das isomere Polymer [Ti(NSiMe3)Cl2]n umgewandelt. Oberhalb 250°C zersetzt sich 1 unter Abspaltung von Me3SiCl zu TiNCl.
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  • 62
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1004-1006 
    ISSN: 0044-2313
    Keywords: Alkaline-Earth ; palladium ; oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On an Alkaline-Earth Oxopalladate containing Pd6O12 Rings: CaBa2Pd3O6CaBa2Pd3O6 was prepared for the first time and investigated by X-ray single crystal technique. It is isotypic to NaBa2Cu3O6 and crystallizes with orthorhombic symmetry, space group D2h23-Fmmm, a = 8.717, b = 11.47, c = 14.933 Å; Z = 2. Typical features of the crystal structure are edge connected square planar PdO4 polygones, forming isolated Pd6O12 rings.
    Notes: CaBa2Pd3O6 wurde erstmals dargestellt und röntgenographisch an Einkristallen untersucht. Es ist isotyp mit NaBa2Cu3O6 und kristallisiert mit orthorhombischer Symmetrie, Raumgruppe D2h23-Fmmm, a = 8,717, b = 11,47, c = 14,933 Å; Z = 2. Charakteristische Strukturmerkmale sind kantenverknüpfte planare PdO4-Polygone, die isolierte Pd6O12-Ringe ausbilden.
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  • 63
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1012-1016 
    ISSN: 0044-2313
    Keywords: Zwitterionic λ5-organofluorosilicate ; pentacoordinate silicon ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal and Molecular Structure of Tetrafluoro[2-(pyrrolidinio)ethyl]silicateThe zwitterionic tetrafluoro[2-(pyrrolidinio)ethyl]silicate (4) was synthesized by reaction of trimethoxy(2-pyrrolidinoethyl)silane (5) with hydrogen fluoride in ethanol/hydrofluoric acid at 0°C. The crystal and molecular structure of 4 was studied at -100°C by single-crystal X-ray diffraction. In addition, 4 was characterized by solution-state NMR studies (CD3CN: 1H, 13C).
    Notes: Das zwitterionische Tetrafluoro[2-(pyrrolidinio)ethyl]silicat (4) wurde durch Reaktion von Trimethoxy(2-pyrrolidinoethyl)silan (5) mit Fluorwasserstoff in einem Ethanol/Flußsäure-Gemisch bei 0°C synthetisiert. Die Kristall- und Molekülstruktur von 4 wurde bei - 100°C mittels einer Einkristall-Röntgenstrukturanalyse untersucht. Außerdem wurde 4 durch NMR-Untersuchungen in Lösung charakterisiert (CD3CN: 1H, 13C).
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  • 64
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1017-1022 
    ISSN: 0044-2313
    Keywords: Thallium perrhenate ; room-temperature modification ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Kristallstruktur von β-ThalliumperrhenatDie Raumtemperaturmodifikation von Thalliumperrhenat, β-TlReO4, wurde durch Röntgenbeugung an Einkristallen untersucht. β-TlReO4 kristallisiert in der monoklinen Raumgruppe P1121/a mit a = 5,636(1), b = 17,428(3), c = 13,353(3) Å, γ = 89,86(2)° und Z = 12. Die Strukturverfeinerung endete bei R = 0,063 (wR = 0,053), wobei 2 020 absorptionskorrigierte Reflexdaten verwendet wurden. β-TlReO4 läßt sich als eine Verwachsung von β-CsReO4- und Scheelit-Einheiten auf Elementarzellniveau beschreiben.Die Struktur von β-TlReO4, besteht aus isolierten ReO4-Tetraedern, die durch TlO8- und TlO9-Polyeder miteinander verknüpft sind. Auf der Basis gruppentheoretischer Überlegungen werden die strukturellen Beziehungen zwischen β-TlReO4, β-CsReO4, α-CsReO4 und Scheelit-Typ diskutiert.
    Notes: β-TlReO4, the room temperature modification of thallium perrhenate, has been investigated by means of single crystal X-ray diffraction. It crystallizes in the monoclinic space group P1121/a with a = 5.636(1), b = 17.428(3), c = 13.353(3) Å, γ = 89.86(2)° and Z = 12. The structure has been refined to R = 0.063 (wR = 0.053) using 2 020 absorption-corrected reflections. The title compound can be described as an intergrowth of β-CsReO4 and scheelite type blocks at unit cell level. The structure of β-TlReO4 consists of isolated ReO4 tetrahedra linked together by TlO8 and TlO9 polyhedra. Based upon group theoretical considerations the structural relationships between β-TlReO4, β-CsReO4, α-CsReO4 and scheelite type are discussed.
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  • 65
    ISSN: 0044-2313
    Keywords: Tris[(trialkylphosphine)gold(I)]oxonium salts ; tris[(triphenylphosphine)gold(I)]sulfonium salts ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Tris[(trialkylphosphine)gold(I)]oxonium Tetrafluoroborates and Tris[(triphenylphosphine)gold(I)]sulfonium Tetrafluoroborate[Et3PAu]+BF4-, obtained from Et3PAuCl and AgBF4 in tetrahydrofuran, reacts with KOH (molar ratio 3:1) to give the oxonium salt [(Et3P)Au]3O+BF4- (1). The homologous [t(Bu3P)Au]3O+BF4- (2) is generated similarly from tBu3PAuCl and Ag2O in the presence of NaBF4 in THF. The composition and identity of these two first tris[(trialkylphosphine)gold(I)]oxonium salts have been confirmed by analytical and spectroscopic data. The compounds are useful aurating agents. From the corresponding triphenylphosphine complex and (Me3Si)2S quantitative yields of the sulfonium salt [(Ph3P)Au]3S+BF4- (3) are obtained. Its crystal structure features monomeric cations, and in these small Au—S—Au angles indicate significant metal-metal bonding.
    Notes: Das durch Umsetzung von Et3PAuCl mit AgBF4 entstehende [Et3PAu]+BF4- ergibt mit KOH (Molverhältnis 3:1) in Tetrahydrofuran das Oxonium-Salz [(Et3P)Au]3O+BF4- (1). Ähnlich entsteht aus Bu3PAuCl und Ag2O in Gegenwart von NaBF4 in THF das homologe [(tBu3P)Au]3O+BF4- (2). Diese beiden ersten Tris[(trialkylphosphan)gold(I)]oxonium-Salze wurden durch analytische und spektroskopische Daten in ihrer Zusammensetzung und Identität gesichert. Sie sind wichtige Aurierungsreagentien. Aus dem zugehörigen Triphenylphosphan-Komplex entsteht mit (Me3Si)2S quantitativ das Sulfonium-Salz [(Ph3P)Au]3S+BF4- (3). Seine Kristallstrukturanalyse zeigt monomere Trigoldsulfonium-Kationen mit steiler SAu3-Pyramide. Kurze Au … Au-Abstände und kleine Au—S—Au-Winkel deuten signifikante Au  -  Au-Wechselwirkungen an.
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  • 66
    ISSN: 0044-2313
    Keywords: monoplatinum nonagold cluster cluster ; monoplatinum dicobalt cluster ; monoplatinum tetragold cluster ; [(Ph3PAu)6(AuCl)3Pt(CO)] ; [(dppe)PtCo2(CO)7] ; [(Ph3PAu)4Pt(dppe)](PF6)2 ; synthesis ; photolysis of azido complexes ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] and [(Ph3PAu)4Pt(dppe)](PF6)2Photolysis of a mixture of Ph3PAuN3, Ph3PAuCl and (Ph3P)2Pt(N3)2 in THF yields after chromatographic separation with CH2Cl2/EtOH as eluens the cluster [(Ph3PAu)6(AuCl)3Pt(CO)] (1). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N3)2 with Co2(CO)8 in THF one m̈2-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo2(CO)7] (2) crystallizes monoclinically in the space group P21/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph3PAuN3 affords the clusters [(Ph3PAu)4Pt(dppe)]2+ (3), and [(Ph3PAu)6AuCo2(CO)6]+. 3 crystallizes with PF6- as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au4Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.
    Notes: Die Photolyse einer Mischung von Ph3PAuN3, Ph3PAuCl und (Ph3P)2Pt(N3)2 in THF ergibt nach chromatographischer Reinigung mit CH2Cl2/EtOH als Eluens den Cluster [(Ph3PAu)6(AuCl)3Pt(CO)] (1). Er kristallisiert triklin in der Raumgruppe P1 mit den Gitterkonstanten: a = 2 139,3(4), b = 2 457,1(4), c = 2 561,9(1) pm, α = 79,74(9)°, β = 80,06(6)°, γ = 66,05(5)°, Z = 4. Die neun Goldatome bilden ein Ikosaederfragment, in dessen Zentrum sich das Pt-Atom befindet. Bei der Photolyse einer Mischung von (dppe)Pt(N3)2 mit Co2(CO)8 in THF wird ein m̈2-CO-Ligand des Cobaltcarbonyls durch eine (dppe)Pt-Gruppe substituiert. Der resultierende Cluster [(dppe)PtCo2(CO)7] (2) kristallisiert monoklin mit der Raumgruppe P21/n und a = 1 303,9(3), b = 1 768,1(8), c = 1 461,4(4) pm, β = 102,81(1)°, Z = 4. Die Photolyse von 2 mit überschüssigem Ph3PAuN3 führt auf die Cluster [(Ph3PAu)4Pt(dppe)]2+ (3) und [(Ph3PAu)6AuCo2(CO)6]+. 3 kristallisiert als PF6- -Salz in der triklinen Raumgruppe P1 mit a = 1 369,1(4), b = 1 505,0(4), c = 2 773,0(8) pm, α = 84,74(1)°, β = 87,37(2)°, γ = 65,94(2)°, Z = 2. Das Au4Pt-Gerüst von 3 bildet eine trigonale Bipyramide mit dem Pt-Atom in äquatorialer Position.
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  • 67
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1603-1608 
    ISSN: 0044-2313
    Keywords: Lanthanum acetate ; ammonium lanthanum acetate ; synthesis ; crystal structure ; thermal behaviour ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anhydrous Lanthanum Acetate, La(CH3COO)3, and its Precursor, ·NH4)3[La(CH3COO)6] · 1/2 H2O: Synthesis, Structures, Thermal BehaviourSingle crystals of (NH4)3[La(CH3COO)6] · ½ H2O are obtained by refluxing La2O3in (CH3COO)3 · 1.5 H2O with an excess of NH4CH3COO in methanol. The crystal structure (trigonal, R3, Z = 6, a = 1 365.0(3) pm, c = 2 360(1) pm, R = 0.088, Rw = 0.061 exhibits the coordination number of nine for La3+, which is surrounded by three chelating-type bidentate and three unidentate acetate groups. Characteristic are monomeric units of [La(CH3COO)6]3- which are connected to a three-dimensional network by hydrogen bonds with the NH4+ ions. Thermal decomposition consists of four steps with La(CH3COO)3, La2(CO3)3 and La2O2CO3 as intermediates and La2O3 as the final Product. Single crystals of La(CH3COO)3 are obtained from La2O3 in a melt of NH4CH3COO (molar ratio 1:12) in a sealed glass ampoule. The crystal structure (trigonal, R3, Z = 18, a = 2 203.0(5) pm; c = 987.1(3) pm, R = 0.027, Rw = 0.023) shows the coordination number of ten for La3+. These are three-dimensionally connected by oxygen atoms of the acetate groups with two tetradentate double-bridging and one Z,Z-type-bridging bidentate acetate group.
    Notes: (NH4)3[La(CH3COO)6] · 1/2 H2O erhält man in Form von Einkristallen durch Erhitzen von La2O3 bzw. La(CH3COO)3 · 1,5 H2O mit einem Überschuß von Ammoniumacetat in Methanol. Die Röntgenstrukturanalyse (trigonal, R3, Z = 6, a = 1 365,0(3) pm, a = 2 360(1) pm, R = 0,088, Rw = 0,061 zeigt, daß La3+ von jeweils drei „chelating-type bidentate“- bzw. „unidentate“-Acetatgruppen umgeben ist (Koordinationszahl neun). Die Kristallstruktur wird von monomeren anionischen Baueinheiten [La(CH3COO)6]3- bestimmt, welche über Wasserstoffbrückenbindungen mit den NH4+-Ionen zu einer dreidimensionalen Struktur verknüpft sind. Der thermische Abbau verläuft in vier Stufen über La(CH3COO)3, La2(CO3)3 und La2O2CO3 zu La2O3. Einkristalle von La(CH3COO)3 erhält man aus einer Schmelze von La2O3 in NH4CH3COO (molares Verhältnis 1:12) in einer abgeschmolzenen Glasampulle. Die Röntgenstrukturanalyse (trigonal, R3, Z = 18, a = 2 203,0(5) pm; c = 987,1(3) pm, R = 0,027, Rw = 0,023) ergibt für La3+ die Koordinationszahl zehn. Die La3+-Ionen sind dreidimensional über die Sauerstoffatome der Acetatgruppen verknüpft, Pro La3+ zwei „tetradentate double-bridging“-Acetatgruppen und eine „Z,Z-type-bridging bidentate“-Acetatgruppe.
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  • 68
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1633-1638 
    ISSN: 0044-2313
    Keywords: Cesium cyclooctaphosphate octahydrate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of Cs8P8O24 · 8H2OCs8P8O24 · 8H2O was obtained from Na8P8O24 · 6H2O by cation exchange. Crystal growth was achieved by applying gel techniques (agar agar). The crystal structure (P1; a = 766.6(8); b = 1 156.9(9); c = 1 163.4(9) pm; α = 100,2(1)°; β = 106.5(2)°; γ = 92.2(1)°; Z = 1; 4 099 unique diffractometer data; R = 0.051; R(w) = 0.037) contains cyclo-octaphosphate anions with point symmetry C2h. The cesium atoms are coordinated irregularily by eight and ten oxygen atoms, respectively. The threedimensional linkage of the P8O248--rings is established via bonds to cesium atoms and hydrogen bonds Provided by H2O molecules.
    Notes: Cs8P8O24 · 8H2O wurde durch Kationenaustausch aus dem entsprechenden Natriumsalz gewonnen. Die Kristallzüchtung erfolgte diffusionskontrolliert (Agar-Agar-Gel). Die Kristallstruktur (P1; a = 766,6(8); b = 1 156,9(9); c = 1 163,4(9) pm; α = 100,2(1)°; β = 106,5(2)°; γ = 92,2(1)°; Z = 1; 4 099 unabhängige Reflexe; R = 0,051; R(w) = 0,037) enthält cyclo-Octaphosphatanionen mit der Punktsymmetrie C2h. Caesium ist unspezifisch mit 8 bzw. 10 Sauerstoffatomen koordiniert. Die dreidimensionale Verknüpfung der Ringe erfolgt über Koordination an Caesium und über Wasserstoffbrückenbindungen ausgehend vom Kristallwasser.
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  • 69
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1147-1153 
    ISSN: 0044-2313
    Keywords: O,O′,O″,O‴-tetraphenyl μ-imido-dithiodiphosphate ; N-(O,O′-diphenylthiophosphoryl)-O″,O‴-diphenylthiophosphorimidate ; Bis(O,O′,O″,O‴-tetraphenyl μ-imido-dithiodiphosphato) palladium chelate ; Bis[N-O,O′-diphenylthiophosphoryl-O″,O‴-diphenylthiophosphorimidato] palladium chelate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Der Tetraphenylester der μ-Imido-dithiodiphosphorsäure und sein Palladiumkomplex  -  KristallstrukturenDie Darstellung der Verbindung [(C6H5O2PS]2NH (SS) und ihres Palladiumkomplexes [Pd{C6H5O)2P(S)NP(S)(OC6H5) 2}2] (PDSS) wird beschrieben. Die Verbindungen werden elementaranalytisch, durch NMR- und Massenspektrometrie sowie mittels Röntgen-Kristallstrukturanalyse charakterisiert. Die Struktur von SS enthält zwei unabhängige Moleküle in einer asymmetrischen Einheit, die über N … H … S Wasserstoffbrücken zu Dimeren verbunden sind. SS ist eine Br⊘nsted-Säure, die mit PdII zu einem neutralen Chelatkomplex reagiert. Die Struktur von PDSS besteht aus isolierten Molekülen mit dem Pd-Atom als Symmetriezentrum. Das Pd ist an 4 S-Atome in einer verzerrt quadratisch-planaren Anordnung mit einem mittleren Abstand Pd—S von 2,345(6) Å und Winkel S—Pd—S von 98,29(4)° gebunden.
    Notes: The preparations of [(C6H5O)2PS]2NH (SS) and its Pd complex [Pd{C6H5O2P(S)NP(S)(OC6H5) 2}2] (PDSS) are described. The compounds were characterized by elemental analysis, NMR, and mass spectra and X-ray structure analysis. The structure of SS contains two independent molecules in an asymmetric unit which are joined into dimers via N … H … S hydrogen bonds. SS is a Br⊘nsted acid And reacts with PdII to a neutral chelate complex. The structure of PDSS is composed of isolated molecules with Pd atom in the center of symmetry. The Pd atom is coordinated by 4 S atoms in a distorted square-planar arrangement with average distance Pd—S 2.345(6) Å and an angle S—Pd—S 98.29(4)°.
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  • 70
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1132-1136 
    ISSN: 0044-2313
    Keywords: Hexamolybdotellurate(VI) ; crystal structure ; hydrogen bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Über das Protonenakzeptorverhalten von [TeMo6O24]6- in Na4(NH4)2[TeMo6O24] · 16H2OFarblose Einkristalle von Na4(NH4)2[TeMo6O24] · 16H2O wurden in wäßriger Lösung gezüchtet (Raumgruppe P1, a = 1 075,3(1), b = 1 074,2(1), c = 1 089,8(1) pm, = 96,259(9), β = 118,556(7), γ = 113,355(8)°, Z = 1, 295 K, 311 Parameter, 3 689 Reflexe, Rg = 0,0197). Es liegen zwei kristallographisch unabhängige Na+ Kationen vor. Na(1) ist oktaedrisch von vier Wassermolekülen und zwei Sauerstoffatomen des zentrosymmetrischen [TeMo6O24]6--Anions umgeben. Na(2) ist in stark verzerrt trigonal-bipyramidaler Weise von fünf Wassermolekülen koordiniert. Je zwei dieser Na(H2O)5+-Bipyramiden sind mit zwei NH4+-Kationen über Wasserstoffbrückenbindungen zu zentrosymmetrischen kationischen Clustern verknüpft. Mit Ausnahme von O(10) wirken alle Sauerstoffatome des [TeMo6O24]6--Anions ungeachtet ihrer unterschiedlichen Bindigkeit bezüglich Mo bzw. Te als annähernd gleichwertige Protonenakzeptoren in Wasserstoffbrückenbindungen zu den NH4+-Kationen und den Kristallwassermolekülen.
    Notes: Colourless triclinic single crystals of Na4(NH4)2[TeMo6O24] · 16H2O were grown in aqueous solution (space group P1, a = 1 075.3(1), b = 1 074.2(1), c = 1 089.8(1) pm, = 96.259(9), β = 118.556(7), γ = 113.355(8)°, Z = 1, 295 K, 311 parameters, 3 689 reflections, Rg = 0.0197). There are two crystallographically independent Na+ cations. Na(1) is coordinated octahedrally by four water molecules and two oxygen atoms of the centrosymmetric [TeMo6O24]6- anion. Na(2) is bound to five water molecules in a considerably distorted trigonally bipyramidal fashion. These bipyramids are linked with NH4+ by hydrogen bonds to yield centrosymmetric cluster cations consisting of two NH4+ and two Na(H2O)5+ each. Hydrogen bonds envolving all except one (O(10)) of the oxygen atoms of the [TeMo6O24]6- anion as almost equivalent proton acceptors regardless of their bonding mode to Te and Mo, respectively, establish further connections to NH4+ and the water of crystallization.
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  • 71
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1137-1146 
    ISSN: 0044-2313
    Keywords: Molybdotellurate(VI) ; crystal structure ; differential thermal analysis ; hydrogen bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Wasserreiche Molybdotellurate: Darstellung und Kristallstruktur von Li6[TeMo6O24] · 18 H2O und Li6[TeMo6O24] · Te(OH)6 · 18 H2OLi6[TeMo6O24] · 18 H2O kristallisiert in der triklinen Raumgruppe P1 (a = 1 041,7(1), b = 1 058,6(1), c = 1 070,8(1) pm, α = 61,08(1), β = 60,44(1), γ = 73,95(1)°. Die Einkristallröntgenstrukturanalyse (Z = 1, 295 K, 317 Parameter, 3 973 Reflexe, Rg = 0,0250) zeigte, daß eine verzweigte, unendliche Kette aus kantenverknüpften Li-Koordinationspolyedern das markante Strukturmerkmal dieser Verbindung ist. Eines der vier kristallographisch unabhängigen Li+-Kationen ist oktaedrisch koordiniert. Bei den übrigen Li+-Kationen liegt verzerrt trigonal-bipyramidale Koordination vor. Lediglich drei kristallographisch unabhängige Sauerstoffatome (O(9), O(10), O(12)) des zentrosymmetrischen [TeMo6O24]6--Anions sind an Li+ koordiniert. Die übrigen Positionen in den Li+-Koordinationssphären sind durch Wassermoleküle besetzt. Die Sauerstoffatome des [TeMo6O24]6--Anions treten in intermolekularen Wasserstoffbrückenbindungen ungeachtet ihrer unterschiedlichen Bindigkeit bezüglich Mo und Te als annähernd gleichwertige Protonenakzeptoren auf.Li6[TeMo6O24] · Te(OH)6 · 18 H2O kristallisiert in der monoklinen Raumgruppe P21/n mit Z = 4, a = 994,1(3), b = 2 344,8(10), c = 1 764,9(4) pm und β = 91,36(4)°. Die Einkristallröntgenstrukturbestimmung mit 627 Parametern und 5900 Reflexen (295 K) konvergierte bei Rg = 0,0324. Es liegen sechs kristallographisch unabhängige Li+-Kationen vor. Die Koordinationspolyeder von Li(1), Li(2), Li(3) und Li(4) sind über gemeinsame Kanten zu einem achtgliedrigen, zentrosymmetrischen Strang verknüpft. Die Koordinationspolyeder von Li(5) und Li(6) sind über eine gemeinsame Ecke zu Zweiergruppen verbunden. Sämtliche Sauerstoffatome des eingeschlossenen Te(OH)6-Moleküls, aber nur drei Sauerstoffatome (0(13), 0(18), O(23)) des [TeMo6024]6--Anions, welches hier über keine kristallographische Symmetrie verfügt, sind an Li+ koordiniert. Die Sauerstoffatome des Anions treten in Wasserstoffbrückenbindungen von überwiegend mittlerer Stärke als Protonenakzeptoren auf. Kurze intermolekulare Wasserstoffbrückenbindungen verbinden die [TeMo6O24]6--Anionen mit den Te(OH)6-Molekülen zu unendlichen Ketten.
    Notes: Li6[TeMo6O24] · 18 H2O is triclinic (space group P1, a = 1 041.7(1), b = 1 058.6(1), c = 1 070.8(1) pm, α = 61.08(1), β = 60.44(1), γ = 73.95(1)°). Single crystal X-ray structure analysis (Z = 1, 295 K, 317 parameters, 3 973 reflections, Rg = 0.0250) revealed an infinite branched chain of edge-sharing Li coordination polyhedra to be the prominent structural feature. One of the four crystallographically independent Li+ is coordinated octahedrally. The coordination polyhedra of the remaining Li+ are distorted trigonal bipyramids. Only three unique oxygen atoms (O(9), O(10), O(12)) of the centrosymmetric [TeMo6O24]6- anion are bound to Li+. The further positions in the coordination spheres of the Li+ are occupied by water molecules. Intermolecular hydrogen bonds involve mainly oxygen atoms of the [TeMo6O24]6- anion as nearly equivalent proton acceptors without regard to their different bonding modes to Te and Mo, respectively.Li6[TeMo6O24] · Te(OH)6 · 18 H2O crystallizes monoclinically in space group P21/n with Z = 4, a = 994.1(3), b = 2 344.8(10), c = 1 764.9(4) pm, and β = 91.36(4)°. Single crystal structure analysis with least squares refinement of 627 parameters (5 900 reflections, 295 K) converged to Rg = 0.0324. There are six unique Li+ cations. The coordination polyhedra of Li(1), Li(2), Li(3), and Li(4) are linked by common edges to yield an eight membered centrosymmetric strand. The coordination polyhedra of the remaining two Li+ sites (Li(5), Li(6)) are connected to a dimeric unit via a common corner. All oxygen atoms of the Te(OH)6 molecule are involved in the coordination of Li+. However, only three oxygen atoms (O(13), O(18), O(23)) of the [TeMo6O24]6- anion which lacks crystallographic symmetry are involved in the coordination of Li+. The oxygen atoms of the anion act as proton acceptors in hydrogen bonds of predominantly medium strength. Te(OH)6 molecules and [TeMo6O24]6- anions connected by strong hydrogen bonds form an infinite chain.
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  • 72
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1155-1160 
    ISSN: 0044-2313
    Keywords: Tin tetrathalliumtritelluride ; lead tetrathalliumtritelluride ; preparation ; crystal structure ; Cr5B3 type ; In5Bi3 type ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Crystal Structure of SnTl4Te3 and PbTl4Te3.We describe the synthesis and crystal structure of two ternary derivatives MTl4Te3 of the parent phase Tl5Te3. Both the derivatives, SnTl4Te3 and PbTl4Te3, crystallize with the In5Bi3 type of structure: space group I4/mcm, Z = 4. The cell constants of SnTl4Te3(PbTl4Te3) are as follows: a = 8.819(2) Å (8.841(2)Å), c = 13.013(3) Å (13.056(3) Å), c/a = 1.47 (1.48). Short M—Te distances of 3.25 Å (3.26 Å) are obtained in ∞1[MTe2/2] chains, which run along [001]. The M atoms are further surrounded by additional tellurium atoms in such a way that octahedra occur, which share common vertices to build up a three dimensional infinite network ∞3[MTe6/2]. The remaining thallium atoms span cubes around the octahedra: ∞3[MTe6/2]Tl8/2 = MTl4Te3.An alternative structure description takes into account bent fragments Tl2Te with Tl—Te distances of 3.15 Å (3.17 Å) as the constitutional elements of M-centered, slightly distorted rhombic dodecahedra as the only polyhedra of the structure. Along [001] they share common vertices, whereas in the tetragonal a-a-plane they are interconnected via common faces.
    Notes: Die Darstellung und die Kristallstruktur der zwei ternären Abkömmlinge SnTl4Te3 und PbTl4Te3 werden beschrieben. Beide kristallisieren isotyp zu ihrer Mutterphase Tl5Te3 im In5Bi3-Typ, der seinerseits eine isopuntale Unterfamilie des Cr5B3-Typs bildet. Die Raumgruppe ist I4/mcm, die Zahl der Formeleinheiten beträgt 4. Die Gitterkonstanten für SnTl4Te3(PbTl4Te3) lauten a = 8,819(2) Å (8,841(2) Å), c = 13,013(3) Å (13,056(3) Å), das c/a-Verhältnis beträgt 1,47 (1,48).In zwei Fragmenten des dreidimensionalen Verbandes treten kurze M—Te—Abstände auf (M = Sn, Pb, Tl). Je nachdem, welchem Fragment man mehr Aufmerksamkeit schenkt, sind zwei alternative, aber gleichwertige Strukturbeschreibungen möglich: Die erstere lehnt sich an die bei der Mutterphase Tl5Te3 gewählte an und betont die kurzen Sn—Te— bzw. Pb—Te—Abstände in den parallel zur [001]-Richtung verlaufenden linearen Ketten ∞1[MTe2/2](Sn—Te: 3,25 Å, Pb—Te: 3,26 Å). Die M-Atome der Ketten werden durch weitere Tellur-Atome zu einem allseits spitzenverknüpften Oktaederverband ∞1[MTe6/2] komplettiert. Die Oktaeder werden würfelförmig von den Thallium-Atomen umgeben: ∞3[MTe6/2]Tl8/2 = MTl4Te3.De zweite betont die gewinkelten Fragmente Tl2Te(Tl—Te in SnTl4Te3: 3,15 Å, Tl—Te in PbTl4Te3: 3,16 Å). Die Tl2Te-Fragmente sind Teile verzerrter Tl2Te2-Rhomben. Diese Rhomben bauen M-zentrierte Rhombendodekaeder auf (M = Sn, Pb), die das einzige zum Strukturaufbau nötige Polyeder sind.
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1177-1182 
    ISSN: 0044-2313
    Keywords: 3, 5-Dimethyl-4-oxo-4-phenoxy-1 λ4-thia-2, 3,-5, 6-tetraaza-4λ5-phosphacyclohexane-2, 6-dicarbonic acid diethylester ; 3, 5-Dimethyl-4-phenoxy-4-thioxo-1λ4-thia-2, 3, 5, 6-tetraaza-4λ5-phosphacyclohexane-2, 6-dicarbonic acid diethylester ; crystal structure ; NMR spectra ; twist-boat conformation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphorus(V)-Hydrazine-Sulfur(IV) Heterocycles with Twist-Boat Conformation.Unlike the corresponding unsubstituted compounds N-ethoxycarbonyl-substituted dihydrazidophosphoric acid derivatives do not react with thionylchloride under redoxdecomposition but yield sulfur containing sixmembered rings. In solution (NMR spectra) as well as in the crystal (X-ray structure analysis) the rings adopt unusual twist-boat conformations. Due to the rather bulky substituents high energies of interconversion between enantiomeric twist-forms are found: 75 ± 2 kJ/mol.
    Notes: N-ethoxycarbonyl-substituierte Dihydrazidoderivate der Phosphorsäure reagieren mit Thionylchlorid nicht wie die entsprechenden unsubstituierten Verbindungen unter Redoxzersetzung sondern unter Bildung schwefelhaltiger Sechsringe. Die Ringe liegen sowohl in Lösung (NMR-Spektren) als auch im Kristall (Röntgenstrukturanalyse) in einer ungewöhnlichen Twist-Boot-Konformation vor. Bedingt durch die sperrigen Substituenten ergeben sich hohe Aktivierungsenergien für die Interkonversion der enantiomeren Twistkonformationen von 75 ± 2 kJ/mol.
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1771-1776 
    ISSN: 0044-2313
    Keywords: Lanthanides ; nitride sulfides ; La3NS3 ; Ce3NS3 ; Pr3NS3 ; Nd3NS3 ; Sm3NS3 ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: M3NS3, the First Nitride Sulfides of the Lanthanides (M = La—Nd, Sm).The oxidation of the “light” lanthanides (M = La—Nd, Sm) with equimolar amounts of sulfur in the presence of NaN3 as nitrogen source results in the formation of the first lanthanide nitride sulfides: M3NS3 (evacuated silica vessels, some NaCl as flux, 850°C, 7 d). NaCl is afterwards removed from the not moisture sensitive crude product (faint- or orange-yellow to amber-co- loured transparent needles, oftenly intergrown to feltlike bunches) upon rinsing with water.The crystal structure was determined from X-ray single crystal data for the example of Sm3NS3 (orthorhombic, Pnma (no. 62), a = 1 201.18(7), b = 394.32(3), c = 1 285.27(6) pm, Z = 4, R = 0.027, Rw = 0.024), and M3NS3 (M = La—Nd) proved to be isostructural from Guinier powder data. There are three crystallographically different M3+ cations in six- (1 X) and sevenfold (2 X) coordination of the N3- and S2- anions. [(N3-)(M3+)4] tetrahedra connected via two corners forming linear chains ∞1[N(M1)1/1(M2)1/1(M3)2/2] 6+ build up the main structural feature. Arranged in the manner of a closest packing of rods, they are held together by three crystallographically different S2- which take care for charge neutrality and three-dimensional interconnection.
    Notes: Die Oxidation der “leichten” Lanthanide (M = La—Nd, Sm) mit äquimolaren Mengen an Schwefel in Gegenwart von NaN3 als Stickstoff-Quelle liefert die ersten Nitridsulfide der Lanthanide: M3NS3 (evakuierte Quarzampullen, etwas NaCl als Flußmittel, 850°C, 7 d). NaCl wird anschließend mit Wasser aus dem hydrolyse-unempfindlichen Rohprodukt (sehr feine, blaß- bzw. orange-gelbe bis bernsteinfarbene, transparente Nadeln, oft zu filzartigen Büscheln verwachsen) her- ausgelöst.Die Kristallstruktur wurde über Einkristalldaten am Beispiel von Sm3NS3 (orthorhombisch, Pnma (Nr. 62); a = 1 201,18(7), b = 394,32(3), c = 1 285,27(6) pm, Z = 4, R = 0,027, Rw = 0,024) bestimmt. Alle dargestellten Nitridsulfide (M3NS3, M = La—Nd) sind nach Guinier-Pulveraufnahmen isotyp. In der Struktur liegen drei kristallographisch unterschiedliche M3+-Kationen in sechs (1 X) bzw. siebenfacher (2 X) Koordination der Anionen (N3- und S2-) vor. [(N3-)(M3+)4]-Tetraeder, über zwei Ecken zu linearen Ketten ∞1[N(M1)1/1(M2)1/1(M3)2/2]6+ verknüpft, bilden das strukturelle Hauptmerkmal. Nach Art einer dichtesten “Stabpackung” gebündelt, werden diese durch drei kristallographisch unterschiedliche S2- zusammengehalten, die für Ladungsausgleich und dreidimensionale Vernetzung sorgen.
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  • 75
    ISSN: 0044-2313
    Keywords: Di(phthalocyaninato(1-))praseodymium(III)-polyhalides ; crystal structure ; uv-vis-nir spectra ; mir spectra ; resonance Raman spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of Tetragonal α-Di(phthalocyaninato(1-))praseodymium(III)-polyhalides; Crystal Structure of α-[Pr(Pc-)2]Br1.5Brown red di(phthalocyaninato(1-))-praseodym(III)-polyhalides [Pr(Pc-)2]Xy (X = Br, I) of variable composition (1 ≤ y ≤ 2.5) are formed by (electro)chemical oxidation of [Pr(Pc2-)2]-. The thermical decomposition of these polyhalides at 250°C yields partially oxidized, green α-[PrPc-Pc2-]. Due to strong spin-spin coupling of the phthalocyanin-π-radicals only PrIII contributes to the magnetic moment of ca. 3.0 B.M. for all complexes. Green metallic prisms of [Pr(Pc-)2]Br1.5 crystallize in the tetragonal α-modification: space group P4/nnc with a = 19.634(5) Å, c = 6.485(2) Å; Z = 2. In the sandwich complex PrIII is eightfold coordinated by the isoindoline N-atoms of the two staggered (41°), nearly planar Pc-- ligands. The quasi-onedimensional character of the structure along [001] is due to the infinite columns of Pc- ligands. The superperiod along [001] is a consequence of the distribution of the Pr atoms onto two incompletely filled crystallographic positions at a distance of c/2 and the disordered chains of the bromine atoms extending in the same direction. Powder diffractograms of Pr(Pc )2Br2, [Pr(Pc-)2]I2 und [PrPc Pc2-] confirm the tetragonal α-modification of these complexes, too. The content of tribromide correlates with the population of the Pr(2)-site. In the UV-VIS-NTR absorption spectrum of a thin film of Pr(Pc )2Br, the intense bands at 13.9 and 19.5 kK are assigned to the B and Q transition, respectively. The D band at 9. kK is characteristic for isolated dimeric Pc--π-radicals. Due to increasing electron delocalisation as a result of the growing columns the D band is shifted to lower energy appearing successively at 6.05 and 3.3 kK. The mir and resonance Raman (RR) spectra of α-[Pr(Pr-)2]Xy, (X = Br, I) show the well known diagnostic bands for Pc--π-radicals. Thc RR spectrum of the polyiodide is dominated by the overtone progression of the totally symmetric (I-I) stretching vibration of the triiodide at 108cm-1. The FT-Raman spectra are also marked by the totally symmetric stretching vibration of the polyhalides (Br3 : 145cm 1; 13-:105cm-1; I5- 151 cm-1).
    Notes: Braunrote Di(phthalocyaninato(1-))-praseodym(III)-polyhalogenide [Pr(Pc-)2]Xy (X = Br, I) variabler Zusammensetzung (1 ≤ y ≤ 2,5) bilden sich bei der (elektro)chemischen Oxydation von [Pr(Pc2-)2]-. Die thermische Zersetzung der Polyhalogenide bei 250°C liefert partiell oxydiertes, grünes α-[PrPc-Pc2-]. Wegen der starken Spin-Spin-Kopplung der Phthalocyanin-π-Radikale reduziert sich das magnetische Moment für alle Komplexe auf den Beitrag des PrIII-Kations von ca. 3,0 B.M. Grün metallisch glänzende Nadeln von [Pr(Pc-)2]Br1,5 kristallisieren in der tetragonalen α-Modifikation: Raumgruppe P4/nnc mit a = 19,634(5) Å, c = 6,485(2) Å; Z = 2. In dem Sandwich-Komplex ist PrIII von den Isoindol-N-Atomen der beiden fast planaren, um 41° gegeneinander gedrehten Pc--Liganden achtfach-koordiniert. Die stapelförmige Anordnung der Pc--Liganden bedingen den quasi-eindimensionalen Charakter der Struktur längs [001]. Die Überperiode längs [001] ist eine Folge der Verteilung der Pr-Atome auf zwei unvollständig besetzte kristallographische Positionen im Abstand von c/2 und der in gleicher Richtung verlaufenden ungeordneten Ketten der Bromatome. Die Pulverdiffraktogramme von [Pr(Pc-)2]Br2, [Pr(Pc-)2]I2 und [PrPc-Pc2-] bestätigen die tetragonale α-Modifikation auch für diese Komplexe. Der Tribromid-Gehalt korreliert mit der Besetzung der Pr(2)-Lage. Im UV-VIS-NIR-Absorptionsspektrum eines Dünnfilms von [Pr(Pc-)2]Bry wird die intensive Bande bei 13,9 kK dem B-, die bei 19,5 kK dem Q-Übergang zugeordnet. Die für isolierte dimere Pc--π-Radikale charakteristische D-Bande liegt bei 9,1 kK. Sie verschiebt sich mit zunehmender Elektronendelokalisierung aufgrund wachsender Stapel bathochrom, wobei sie sukzessive bei 6,05, dann 3,3 kK auftritt. Die MIR- und Resonanz-Raman(RR)-Spektren von α-[Pr(Pc-)2]Xy, (X = Br, I) zeigen die für Pc--π-Radikale bekannten diagnostischen Banden. Im RR-Spektrum des Polyiodids dominiert die Obertonprogression der totalsymmetrischen (I - I)-Valenzschwingung des Triiodids (108 cm-1). Die FT-Raman-Spektren sind ebenfalls von der totalsymmetrischen Valenzschwingung des Polyhalogenids geprägt (Br3-: 145 cm-1; I3-: 105 cm-1; I5-: 151 cm-1).
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  • 76
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1283-1286 
    ISSN: 0044-2313
    Keywords: Alumothiosilicate ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Growth and Structure of the Alumothiosilicate Mn1.84Al0.16Si0.84Al0.16S4Single Crystals of the alumothiosilicate Mn1.84Al0.16Si0.84Al0.16S4 were grown by chemical transport reaction. The compound represents the first example of this type of silicate. The crystals were characterized by electron microprobe analyses and X-ray methods. The compound crystallizes in the olivine type structure, space group Pnma, a = 1 266.9(2), b = 739.6(3), c = 592.8(1) pm. The mean bond lengths are very similar to those in Mn2SiS4. That part of aluminum which is situated at the octahedral sites is not equally distributed amongst both types of octahedral positions but is enriched on the smaller and more symmetric M(1) position.
    Notes: Durch Chemische Transportreaktion gelang die Züchtung von Einkristallen der Verbindung Mn1,84Al0,16Si0,84Al0,16S4, einem Alumothiosilicat; sie stellt das erste Beispiel für ein derartiges Silicat dar. Die Charakterisierung erfolgte mit der Elektronenstrahlmikrosonde sowie mit Röntgenmethoden. Die Verbindung besitzt Olivinstruktur, Raumgruppe Pnma, a = 1 266,9(2), b = 739,6(3), c = 592,8(1) pm. Die mittleren Bindungslängen sind mit denen in Mn2SiS4 vergleichbar. Der Anteil des Aluminiums auf den Oktaederplätzen ist nicht statistisch auf die beiden kristallographisch unterschiedlichen Plätze verteilt, sondern es findet eine Anreicherung auf der kleineren und höhersymmetrischen M(1)-Position statt.
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  • 77
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1738-1742 
    ISSN: 0044-2313
    Keywords: Strontium, osmium, oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New Mixed Valenced Oxoosmate(VI, VII): Sr11Os26+Os27+O24.Single crystals of Sr11Os26+Os27+O24 were prepared in closed silver bombs using SrO, osmium and an extend of KO2. It crystallizes with monoclinic symmetry, space group C2h6-I12/a1 a = 11.703; b = 16.058; c = 11.696 Å; β = 90.03°; Z = 4. Sr11Os26+Os27+O24 shows a new crystal structure characterized by a [Sr11O24]26- network and incorporated Os6+ and Os7+ ions. Calculations of the coulombterm of lattice energy shows an orderer distribution of the two oxidation states of osmium.
    Notes: Einkristalle von Sr11Os26+Os27+O24 wurden in geschlossenen Silberbömbchen aus SrO, Osmium und einem überschuß von KO2 erhalten. Diese Substanz kristallisiert monoklin, Raumgruppe C2h6-I12/a1 mit a = 11,703; b = 16,058; c = 11,696 Å; β = 90,03°; Z = 4. Sie zeigt eine neue Kristallstruktur, die durch ein [Sr11O24]26--Gerüst mit eingelagerten Os6+ und Os7+-Ionen ausgezeichnet ist. Berechnungen des Coulombterm der Gitterenergie führen zu einer geordneten Verteilung der zwei Valenzen des Osmiums.
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  • 78
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1939-1944 
    ISSN: 0044-2313
    Keywords: Acetamidinium hexafluorometallates: preparation ; crystal structure ; thermal decomposition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Acetamidiniumhexafluorometallates of Aluminium, Gallium, Indium, Vanadium, Chromium, Manganese, Iron and CobaltThe title compounds were crystallized from F-containing aqueous solutions of their hexafluoro-metallate acids by adding acetamidine. Their unit cells were determined and the thermal decomposition was investigated thermoanalytically. The crystal structure of [CH3C(NH2)2]3AlF6 was determined: Space group P41212/P43212, a = 8,987(1), c = 17,894(3) Å, R = 0,054. The unit cell parameters: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm GaF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,078(1),}\,{\rm c}\,{\rm = }\,{\rm 18,104(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm InF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,277(1),}\,{\rm c}\,{\rm = }\,{\rm 18,545(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm VF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,1201(6),}\,{\rm c}\,{\rm = }\,{\rm 18,2197(6)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm CrF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,089(1),}\,{\rm c}\,{\rm = }\,{\rm 18,132(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm MnF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,109(2),}\,{\rm c}\,{\rm = }\,{\rm 18,241(3)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm FeF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,122(2),}\,{\rm c}\,{\rm = }\,{\rm 18,189(6)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm CoF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,084(1),}\,{\rm c}\,{\rm = }\,{\rm 18,130(4)}\,{\rm {\AA}}} \hfill \\ \end{array} $$\end{document}.
    Notes: Die Titelverbindungen wurden aus den HF enthaltenden, wäßrigen Lösungen der jeweiligen Hexafluorometallatsäuren nach Zugabe von Acetamidin auskristallisiert, ihre Gitterkonstanten bestimmt und der Abbau thermoanalytisch verfolgt.Vom [CH3C(NH2)2]3AlF6 wurde die Kristallstruktur bestimmt: Raumgruppe P41212/P43212, a = 8,987(1), c = 17,894(3) Å, R = 0,054.\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm GaF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,078(1),}\,{\rm c}\,{\rm = }\,{\rm 18,104(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm InF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,277(1),}\,{\rm c}\,{\rm = }\,{\rm 18,545(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm VF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,1201(6),}\,{\rm c}\,{\rm = }\,{\rm 18,2197(6)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm CrF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,089(1),}\,{\rm c}\,{\rm = }\,{\rm 18,132(2)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm MnF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,109(2),}\,{\rm c}\,{\rm = }\,{\rm 18,241(3)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm FeF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,122(2),}\,{\rm c}\,{\rm = }\,{\rm 18,189(6)}\,{\rm {\AA};}} \hfill \\ {{\rm [CH}_{\rm 3} {\rm C(NH}_{\rm 2})_2]_3 {\rm CoF}_{\rm 6} :\,{\rm a}\,{\rm = }\,{\rm 9,084(1),}\,{\rm c}\,{\rm = }\,{\rm 18,130(4)}\,{\rm {\AA}}} \hfill \\ \end{array} $$\end{document}.
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  • 79
    ISSN: 0044-2313
    Keywords: Organylphosphine monosulfides ; organylphosphine monoselenides ; (1-hydroxyalkyl)-organyl-phosphine sulfides ; (1-hydroxyalkyl)-organyl-phosphine selenides ; bis(1-hydroxy-alkyl)-organyl-phosphine sulfides ; (1-hydroxy-1-methyl-ethyl)-phenyl-phosphine sulfide ; crystal structure ; hydrogen bonds ; 31P CP/MAS NMR ; quantumchemical calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation into Sulfides and Selenides of Primary Phosphines  -  The (1-Hydroxyalkyl)-organyl-phosphine Sulfides and Selenides, New Classes of CompoundsPrimary phosphines react with S8 and Se8, respectively, forming organylphosphine monosulfides, and monoselenides, respectively, RP(X)H2 (X = S, Se) which are well characterized by 31P NMR spectroscopy. Organylphosphine monosulfides are detected in the reaction mixture of primary phosphines with 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides, too. The reaction of primary phosphines with sulfur or selenium proceeds in presence of most of the ketones without formation of any side product. The (1-hydroxyalkyl)-organyl-phosphine sulfides and selenides, respectively, RP(X)(H)C(OH)R1R2, are yielded generally in crystalline form. The X-ray crystal structure analysis of the (1-hydroxy-1-methyl-ethyl)-phenyl-phosphane sulfide (R = Ph, R1 = R2 = Me) has shown that in the crystal the molecules are chained via intermolecular O—H … S hydrogen bridging bonds (O … S = 328 pm). Aldehydes react with primary phosphines and sulfur forming bis(1-hydroxyalkyl)-phenyl-phosphine sulfides, RP(S)[CH(OH)R1]2. 1H, 13C, and 31P NMR spectroscopic investigations allow to detect and to identify stereoisomers in some cases. Quantumchemical calculations reflect correctly which of the carbonyl compounds are able to react with the organylphosphine monosulfide formed as intermediate.
    Notes: Primäre Phosphane reagieren mit S8 oder Se8 und bilden neben einer großen Anzahl von Nebenprodukten Organylphosphanmonosulfide bzw. -selenide, RP(X)H2 (X = S, Se), die 31P-NMR- spektroskopisch charakterisiert werden können. Die Bildung von Organylphosphanmonosulfiden ist auch bei der Umsetzung primärer Phosphane mit 2,4-Diaryl-1,3,2,4-dithiadiphosphetan-2,4-disulfid nachweisbar. Praktisch ohne Nebenprodukte verläuft die Reaktion primärer Phosphane mit Schwefel oder Selen und einer Reihe von Ketonen. Es entstehen die meist kristallinen (1-Hydroxyalkyl)-organyl-phosphansulfide bzw. -selenide, RP(X)(H)C(OH)R1R2. Die Röntgen-Kristallstrukturanalyse des (1-Hydroxy-1-methyl-ethyl)-phenyl-phosphansulfids (R = Ph, R1 = R2 = Me) ergab, daß im Kristall intermolekulare O—H … S-Wasserstoffbrückenbindungen (O … S = 328 pm) zu einer kettenförmigen Anordnung der Moleküle führen. Aldehyde reagieren mit Phenylphosphan und Schwefel zu Bis(1-hydroxyalkyl)-phenyl-phosphansulfiden, C6H5P(S)[CH(OH)R1]2. 1H—, 13C— und 31P-NMR-Untersuchungen gestatten den Nachweis und die Zuordnung von auftretenden Stereoisomeren. Quantenchemische Berechnungen spiegeln richtig wider, welche Carbonylverbindungen in der Lage sind, mit dem intermediär gebildeten Phosphansulfid zu reagieren und welche nicht.
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  • 80
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 2015-2020 
    ISSN: 0044-2313
    Keywords: Cluster compounds ; technetium ; rhenium ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Isolated [M6S14] Units in Ternary Sulfides of Technetium and RheniumWe have successfully prepared the ternary sulfides Rb10Tc6S14, Cs10Tc6S14, Rb10Re6S14, and Cs10Re6S14 by heating alkali carbonate with elemental technetium or rhenium in a hydrogen stream charged with sulfur.Structural investigations on single crystals revealed that these compounds crystallize in the space group Fm3m. [M6S14] cluster units (M \documentclass{article}\pagestyle{empty}\begin{document}$ \hat = $\end{document} Tc, Re) are found as the characteristic structural features, in which regular M6 octahedra are coordinated by sulfur atoms over their eight faces and six vertices. Other than in the case of the previously investigated ternary technetium and rhenium chalcogenides, these units are not linked to one another, but occur as isolated complex anions which form a cubic close packed array. The alkali ions, whose sites are partly statistically occupied, are found on the corners, the edges and the longer face diagonals of a rhombic dodecahedron surrounding each of these units. The dodecahedra share all their faces with one another.The diamagnetic behaviour which was measured on Cs10Tc6S14 in the temperature range from 10 to 295 K is in accordance with a 24-electron-configuration of the regular M6 octahedra.
    Notes: Durch Schmelzreaktionen von Alkalicarbonat mit elementarem Technetium oder Rhenium in einem mit Schwefel beladenen Wasserstoffstrom gelang die Darstellung der ternären Sulfide Rb10Tc6S14, Cs10Tc6S14, Rb10Re6S14 und Cs10Re6S14.Strukturuntersuchungen an Einkristallen ergaben, daß diese Verbindungen isotyp in der Raumgruppe Fm3m kristallisieren. Als charakteristische Strukturelemente treten [M6S14]-Baueinheiten (M \documentclass{article}\pagestyle{empty}\begin{document}$ \hat = $\end{document} Tc, Re) auf, in denen die unverzerrten M6-Oktaeder über den acht Flächen und sechs Ecken von Schwefelatomen koordiniert sind. Diese Einheiten sind, anders als bei den bisher untersuchten ternären Technetium- und Rheniumchalcogeniden, nicht untereinander verknüpft, sondern liegen als isolierte komplexe Anionen vor, die sich entsprechend einer kubisch dichten Kugelpackung anordnen. Die Alkalimetallionen befinden sich mit teilweise statistischer Besetzung ihrer Punktlagen auf den Ecken, den Kanten und den längeren Flächendiagonalen eines jede dieser Einheiten umgebenden Rhombendodekaeders. Die Dodekaeder sind untereinander allseitig flächenverknüpft.Der an Cs10Tc6S14 im Temperaturbereich zwischen 10 und 295 K gemessene Diamagnetismus stimmt mit der Annahme einer 24-Elektronenkonfiguration der regulären M6-Oktaeder überein.
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  • 81
    ISSN: 0044-2313
    Keywords: Cyclopentadienyl molybdenum(V) and (III) complexes ; diphenylphosphido bridged complex ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Cyclopentadienyl Substituted Molybdenum(V) Tetrachlorides with LiPH(2,4,6-Bu3tC6H2) and KPPh2(Dioxane)2. Crystal Structures of [Cp0Mo(μ—Cl)2]2 and [Cp20Mo2(μ—Cl)3(μ—PPh2)] (Cp0 = C5Me4Et)The reaction of [Cp0Mo(CO)3]2 (Cp0 = C5Me4Et) and [Cp′Mo(CO)3]2 (Cp′ = C5H4Me) with PCl5 in CH3CN furnishes the Mo(V) complexes Cp0MoCl4(CH3CN) 1 and Cp′MoCl4(CH3CN) 2 in good yields. While 1 and 2 are reduced by LiPH(2,4,6-Bu3tC6H2) to the Mo(III) complexes [Cp0Mo(μ—Cl)2]2 3 and [Cp′Mo(μ—Cl)2]2 4, the reaction of 1 with KPPh2(dioxane)2 yields the reduction/substitution product [Cp20Mo2(μ—Cl)3(μ—PPh)] 5 in low yield. 1-4 were characterized spectroscopically (i.r., mass, 3 and 4 also n.m.r.). An X-ray crystal structure determination was carried out on 3 and 5. 3 crystallizes in the triclinic space group P1 (No. 2) with a = 8.278(4), b = 12.508(7), c = 12.826(7) Å, α = 86.78(5), β = 81.55(2), γ = 75.65(4)°, V = 1 272.4 Å3 and two formula units in the unit cell (data collection at - 67°C, 4 255 independent observed reflections, R = 2.9%); 5 crystallizes in the triclinic space group P1 (No. 2) with a = 11.536(8), b = 12.307(9), c = 13.157(9) Å, α = 91.41(6), β = 100.42(5), γ = 112.26(6)°, V = 1 688.7 Å3 and two formula units in the unit cell (data collection at - 60°C, 6 147 independent observed reflections, R = 4.9%). The crystal structure of 3 shows the presence of centrosymmetric dimeric molecules with four bridging chloro ligands. In 5, two Mo atoms are bridged by three chloro ligands and one PPh2 ligand. The Mo—Mo bond length in 3 and 5 (2.600(2), 2.596(2) Å and 2.6388(8) Å) is in agreement with a Mo—Mo bond.
    Notes: Durch die Umsetzung von [Cp0Mo(CO)3]2 (Cp0 = C5Me4Et) und [Cp′Mo(CO)3]2 (Cp′ = C5H4Me) mit PCl5 in CH3CN sind die Mo(V)-Komplexe Cp0MoCl4(CH3CN) 1 und Cp′MoCl4(CH3CN) 2 in guten Ausbeuten zugänglich. 1 und 2 werden durch LiPH(2,4,6-Bu3tC6H2) zu den Mo(III)-Komplexen [Cp0Mo(μ—Cl)2]2 3 und [Cp′Mo(μ—Cl)2]2 4 reduziert. Hingegen fällt bei der Umsetzung von 1 mit KPPh2(Dioxan)2 [Cp20Mo2(μ—Cl)3(μ—PPh2)] 5, das durch Reduktion und Substitution gebildet wird, in geringer Ausbeute an. 1-4 wurden IR-spektroskopisch und massenspektrometrisch, 3 und 4 auch NMR-spektroskopisch charakterisiert. An 3 und 5 wurden Röntgenstrukturanalysen durchgeführt. 3 kristallisiert triklin in der Raumgruppe P1 (Nr. 2) mit a = 8,278(4), b = 12,508(7), c = 12,826(7) Å, α = 86,78(5), β = 81,55(2), γ = 75,65(4)°, V = 1 272,4 Å3 und zwei Formeleinheiten pro Elementarzelle (Meßtemperatur - 67°C, 4 255 unabhängige, beobachtete Reflexe, R = 2,9%); 5 kristallisiert triklin in der Raumgruppe P1 (Nr. 2) mit a = 11,536(8), b = 12,307(9), c = 13,157(9) Å, α = 91,41(6), β = 100,42(5), γ = 112,26(6)°, V = 1 688,7 Å3 und zwei Formeleinheiten pro Elementarzelle (Meßtemperatur - 60°C, 6 147 unabhängige, beobachtete Reflexe, R = 4,9%). In 3 liegen zentrosymmetrische dimere Moleküle mit vier verbrückenden Chloroliganden vor. In 5 sind zwei Mo-Atome durch drei Chloroliganden und einen PPh2-Liganden verbrückt. Der Mo—Mo-Bindungsabstand in 3 und 5 (2,600(2), 2,596(2) Å und 2,6388(8) Å) weist auf das Vorliegen einer Mo—Mo-Bindung hin.
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  • 82
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 281-286 
    ISSN: 0044-2313
    Keywords: Tetraphosphorus hexaoxide disulfide and trisulfide ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Improved Syntheses, Crystal Growth, and Crystal Structure Determination of P4O6S2 and P4O6S3Syntheses and single crystal growths of the title compounds are described. Both compounds crystallize in the space group P21/c (P4O6S2: a = 11.293(4); b = 6.457(3); c = 11.588(4) Å; β = 90.29(2)°, 2 450 diffractometer data, Rw = 0.035/P4O6S3: a = 15.611(5); b = 8,303(3); c = 9.697(4) Å; β = 127.12(2)°, 2 481 diffractometer data, Rw = 0.034). The structural data for the series P4O6Sn (n = 1 - 4) thus completed are compared to their oxide analogues P4O6On (n = 1 - 4). The changes in the geometry of the P4O6-cage in course of its successive oxidation are discussed.
    Notes: Darstellung und Einkristallzucht der Titelverbindungen werden beschrieben. Beide Verbindungen kristallisieren in der Raumgruppe P21/c (P4O6S2: a = 11,293(4); b = 6,457(3); c = 11,588(4) Å; β = 90,29(2)°, 2 450 Diffraktometerdaten, Rw = 0,035/P4O6S3: a = 15,611(5); b = 8,303(3); c = 9.697(4) Å; β = 127,12(2)°, 2 481 Diffraktometerdaten, Rw = 0,034). Durch die neu gelösten Strukturen werden die Daten für das System P4O6Sn (n = 1 - 4) komplettiert und können mit denen der analog aufgebauten Oxide P4O6On (n = 1 - 4) verglichen werden. Die Veränderungen der Molekülgeometrie des zentralen P4O6-Käfigs im Zuge der schrittweisen Oxidation werden diskutiert.
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  • 83
    ISSN: 0044-2313
    Keywords: Lithium thioborates ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Li5B7S13 and Li9B19S33: Two Lithium Thioborates with Novel Highly Polymeric Anion NetworksLi5B7S13 (C2/c; a = 17.304(2) Å, b = 21.922(3) Å, c = 12.233(2) Å, β = 134.91(1)°; Z = 8) and Li9B19S33 (C2/c; a = 23.669(9) Å, b = 14.361(3) Å, c = 12.237(3) Å, β = 103.77(2)°; Z = 4) were prepared by reaction of stoichiometric amounts of lithium sulfide, boron, and sulfur at 750°C (Li5B7S13) and 700°C (Li9B19S33) with subsequent annealing. The crystal structures consist of interpenetrating, polymeric boron sulfur anion networks which are formed by corner-sharing of B4S10 and B10S20 units (Li5B7S13), or B19S36 units (Li9B19S33). The lithium cations are situated in between with a strong disorder in Li9B19S33.
    Notes: Li5B7S13 (C2/c; a = 17,304(2) Å, b = 21,922(3) Å, c = 12,233(2) Å, β = 134,91(1)°; Z = 8 und Li9B19S33 (C2/c; a = 23,669(9) Å, b = 14,361(3) Å, c = 12,237(3) Å, β = 103,77(2)°; Z = 4 wurden durch Reaktion von stöchiometrischen Mengen Lithiumsulfid, Bor und Schwefel bei 750°C (Li5B7S13) und 700°C (Li9B19S33) mit anschließendem Tempern dargestellt. Die Kristallstrukturen bestehen aus sich durchdringenden, polymeren Bor-Schwefel-Anionengerüsten, die durch Eckenverknüpfung von B4S10- und B10S20-Einheiten (Li5B7S13) bzw. B19S36-Einheiten (Li9B19S33) gebildet werden. Dazwischen befinden sich die Lithiumkationen, wobei bei Li9B19S33 eine starke Fehlordnung beobachtet wird.
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  • 84
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 517-520 
    ISSN: 0044-2313
    Keywords: Alkaline Earth ; ruthenium ; oxygen ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Novel Oxoruthenates of the 6 L-Perovskite Type: Ba3SrRu2-xTaxO9 (x = 0.8 and 1.4) with a Comment on Ba3CaRu2O9Single crystals of the phases Ba3SrRu2-xTaxO9 [(I): x = 0.8 and (II): x = 1.4] and the compound (III): Ba3CaRu2O9 were prepared by a BaCl2 flux and investigated by X-ray methods. (I)-(III) crystallizes with hexagonal symmetry space group P62c with lattice constants: (I) a = 6.003 Å; c = 15.227 Å; (II) a = 5.988 Å; c = 15.220 Å and (III) a = 5.891 Å; c = 14.571 Å. The crystal structures of these substances corresponds to the 6 layer perovskites with the stacking sequence (hcc)2. All of them show a so far not described slightly distorted oxygen framework caused by the Sr2+ and Ca2+ ions.
    Notes: Einkristalle der Phasen Ba2SrRu2-xTaxO9 [(I): x = 0,8 und (II): x = 1,4] sowie der Verbindung (III): Ba3CaRu2O9 wurden in einer BaCl2-Schmelze präpariert und mit Hilfe von Röntgenbeugungsmethoden untersucht. (I)-(III) kristallisieren in der hexagonalen Raumgruppe P62c mit den Gitterkonstanten: (I) a = 6,003 Å; c = 15,227 Å; (II) a = 5,988 Å; c = 15,220 Å und (III) a = 5,891 Å; c = 14,571 Å. Ihre Kristallstrukturen entsprechen den 6 L-Perowskiten mit der Stapelsequenz (hcc)2. Sie zeigen eine bislang noch nicht beschriebene leichte Verzerrung im Aufbau der Sauerstoffteilgitter, die auf die Sr2+ - bzw. Ca2+-Ionen zurückgeführt werden kann.
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  • 85
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 525-528 
    ISSN: 0044-2313
    Keywords: Barium-bismuth-oxovanadate ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ba2BiV3O11 containing Bismuth within closed CoordinationA new barium bismuth oxovanadate, Ba2BiV3O11, was prepared and investigated by X-Ray single crystal technique. It crystallizes with monoclinic symmetry space group C2h5 - P21/a, lattice constants a = 24.6473; b = 7.7347; c = 5.6375 Å, β = 103.16°; Z = 4. Octahedra arround Bi3+, tetrahedra and double tetrahedra arround V5+ form a tunnel structure. The tunnel positions are occupied by Ba(2).
    Notes: Ein neues Barium-Bismutoxovanadat, Ba2BiV3O11, wurde einkristallin dargestellt und röntgenographisch untersucht. Es kristallisiert monoklin, Raumgruppe C2h5 - P21/a, mit den Gitterkonstanten a = 24,6473; b = 7,7347; c = 5,6375 Å, β = 103,16°; Z = 4. Oktaeder um Bi3+, Tetraeder und Doppeltetraeder um V5+ vernetzen mit Ba(1) zu einer Tunnelstruktur. Ba(2) besetzt die Tunnelpositionen.
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  • 86
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 534-536 
    ISSN: 0044-2313
    Keywords: Calcium ; iridium ; copper ; oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Ca3IrCuO6Single crystals of Ca3IrCuO6 were prepared by a flux technique and investigated by single crystal X-ray work. It crystallizes with monoclinic symmetry, space group C2h6 - C12/c1; a = 9.032, b = 9.295, c = 6.466 Å, β = 91.35°, Z = 4. Ca3IrCuO6 is isotypic to Sr3IrCuO6. The square planare CuO4 polygones show probably a slightly deficit accompanied by an adequate part of iridium in the oxydation state Ir5+.
    Notes: Einkristalle von Ca3IrCuO6 wurden mit Hilfe von Schmelzmitteln dargestellt und röntgenographisch untersucht. Es kristallisiert mit monokliner Symmetrie in der Raumgruppe C2h6 - C12/c1, mit a = 9,032, b = 9,295, c = 6,466 Å, β = 91,35°, Z = 4. Ca3IrCuO6 ist mit Sr3IrCuO6 isotyp. Die planaren CuO4-Baugruppen zeigen wahrscheinlich ein geringes Defizit an Cu2+, welches durch einen adäquaten Teil von Ir5+ kompensiert wird.
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  • 87
    ISSN: 0044-2313
    Keywords: Polysulfonyl amines ; silver(1) dimesylarnide ; tetrakis(dimesylamido)aquatetrasilver(l) ; crystal structure ; thermal analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag4(N)SO2CH3)2}4(H2O)] by X-Ray Diffraction and Thermal AnalysisThe title compound is obtained by crystallizing AgN(SO2CH3)2 from water at room temperature. Crystallographic data (at -95°C): Triclinic space group P1, a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm3, Z = 2, Dx = 2.608 Mg m-3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H2O)-Ag(3) … Ag(4) … Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) … Ag(4) 342.9, Ag(4) … Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) … O′(S) per repeating unit. Between the layers, a weak O(S) … Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) … O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO2,O(w)Ag(I), distorted trigonal bipyramid], 5[O4,O(w), trigonal bipyramid], and 2 + 1 (N2, li-near; plus a secondary Ag … 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO2CH3)2, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD).
    Notes: Die Titelverbindung entsteht durch Kristallisation von AgN(SO2CH3)2 aus Wasser bei Raumtemperatur. Kristallographische Daten (bei -95°C): Trikline Raumgruppe P1, a = 864,6(4), b = 1 211,2(5), c = 1 399,1(5) pm, α = 90,97(3), β = 90,90(3), γ = 98,25(4)°, V = 1,4496 nm3, Z = 2, Dx = 2,608 Mg m-3. Die vier unabhängigen Silberatome und das Wassermolekül bilden Zickzack-Ketten Ag(1)-Ag(2)-(μ-H2O)-Ag(3) … Ag(4) … Ag(1′) mit den Abständen Ag(1)-Ag(2) 309,7, Ag(2)-O(W) 241,8 O(W)-Ag(3) 241,4, Ag(3) … Ag(4) 342,9, Ag(4) … Ag(1′) 361,4 pm. Die Silberatome in der Kette werden durch die Dimesylamid-Anionen miteinander verklammert, die innerhalb der so resultierenden Stränge als dreizähnig-verbrückende (α-O, N, ω-O)-Liganden wirken. Die Stränge sind pro Repetiereinheit durch einen Kontakt O(S)-Ag′ (247 pm) und eine Wasserstoffbrücke O(W)-H(1) …O′(S) zu Schichten verknüpft. Zwischen den Schichten bestehen je Strang-Repetiereinheit eine schwache Wechselwirkung O(S) … Ag″ (271 pm) und eine Wasserstoffbrücke O(W)-H(2) … O″(S). Die Silberatome besitzen in der Reihenfolge Ag(1) bis Ag(4) die Koordinationszahl 5 [NO3Ag(2), verzerrt trigonal-bipyramidal], 5 [NO2O(W)Ag(1), verzerrt trigonal-bipyramidal], 5 [O4O(W), trigonal-bipyramidal], 2 + 1 (N2, linear; ein zusätzlicher Sekundärkontakt Ag … O). Die Dehydratation der Titelverbindung und eine fest-fest-Phasenumwandlung des wasserfreien AgN(SO2CH3)2 wurden durch Thermokonduktometrie sowie zeit- und temperaturaufgelöste Röntgendiffraktometrie (TXRD) quantitativ untersucht.
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  • 88
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1037-1046 
    ISSN: 0044-2313
    Keywords: Nickel ; chromium ; molybdenum ; penicillamine ; complexes ; synthesis ; crystal structure ; antidot ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Penicillamine Complexes of Nickel, Chromium, and Molybdenum  -  Structural Particularity and Biological/Medical RelevanceThe compounds Tl2[NiII(H2O)6][NiII(D-pen)(L-pen)]2[NiII(SCN)2(H2O)4] 1, Tl[NiII(D-pen)2H] · H2O 2, Tl[CrIII(D-pen)2] 3, and Na2[Mo2VO4(pen)2] · 3 CH3OH · 3 H2O 4 have been prepared by the reaction of nickel nitrate (for 1), nickel acetate (for 2), potassium chromate (for 3), and sodium molybdate (for 4) with D- and D, L-penicillamine, respectively. They were characterized by single-crystal X-ray structure analysis and other physical methods. Whereas penicillamine acts as a bidentate (N, S)-ligand in 1 and 2, CrIII (in 3), and MoV (in 4) are coordinated to the three ligand atoms N, O, and S. The presence of three different types of NiII-complexes a cationic, a neutral, and an anionic one in 1 is remarkable.For crystal data see Inhaltsübersicht.
    Notes: Die Verbindungen Tl2[NiII(H2O)6][NiII(D-Pen)(L-Pen)]2[NiII(SCN)2(H2O)4] 1, Tl[NiII(D-Pen)2H] · H2O 2, Tl[CrIII(D-Pen)2] 3 und Na2[Mo2VO4(Pen)2] · 3 CH3OH · 3 H2O 4 wurden durch Umsetzung von Nickelnitrat (für 1), Nickelacetat (für 2), Kaliumchromat (für 3) und Natriummolybdat (für 4) mit D- bzw. D, L-Penicillamin in wäßriger Lösung dargestellt und durch Einkristallstrukturanalyse und andere physikalische Methoden charakterisiert. Während in den Ni-Pen-Komplexen von 1 und 2 Penicillamin als zweizähniger Ligand (N, S) fungiert, sind CrIII in 3 und MoV in 4 über N, O und S koordiniert. Bemerkenswert ist, daß in 1 drei verschiedene Ni-Komplexe und zwar ein kationischer, ein neutraler und ein anionischer in einer Elementarzelle vorliegen.1: C2/m, a = 1 484,6(4), b = 1 358,7(4), c = 1 204,7(3) pm, β = 103,75(2)°, V = 2 360,4(11) ° 106 pm3, R = 0,042 für 1 633 unabhängige Reflexe (Fo〉 4,0σ(Fo)), Z = 2.2: C2, a = 2 279,9(7), b = 613,1(1), c = 1 275,2(3) pm, β = 110,94(2)°, V = 1 664,8(6) · 106 pm3, R = 0,056 für 1 413 unabhängige Reflexe (Fo〉 4,0σ(Fo)), Z = 4.3: C2, a = 2 054,0(3), b = 592,1(1), c = 606,7(1) pm, β = 92,89(1)°, V = 736,95(17) · 106 pm3, R = 0,028 für 862 unabhängige Reflexe (Fo〉 4,0σ(Fo)), Z = 2.4: P1, a = 996,2(4), b = 1 222,2(7), c = 1 395,3(7) pm, = 114,27(4), β = 104,55(4), γ = 95,63(4)°, V = 1 459,4(13) · 106 pm3, R = 0,072 für 3 763 unabhängige Reflexe (Fo〉 4,0σ(Fo)), Z = 2.
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  • 89
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    Zeitschrift für anorganische Chemie 619 (1993), S. 1073-1082 
    ISSN: 0044-2313
    Keywords: Bismuth arene π-complexes ; bismuth xylene complexes ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heavy Metal π-Complexes. IX. The Chain Polymers ∞1[(1,2- (CH3)2C6H4BiCl3)2], ∞1[(1,3- (CH3)2C6H4BiCl3)2] and ∞1[(1,4- (CH3)2C6H4BiCl3)2]In the crystal structures of the three solid state complexes (C6H4(CH3)2BiCl3 (C6H4(CH3)2 = o-xylene: 1, m-xylene: 2, p-xylene: 3) quasi-dimeric units of almost undistorted, arene coordinated BiCl3 fragments can be found that are further associated via additional Bi—Cl contacts to form one-dimensional polymeric chains. Whereas the chains of 2 and 3 are constituted by Bi2Cl2 four-membered rings only, further Cl-bridging in 1 leads to additional trigonal-bipyramidal arrangements with Bi atoms exhibiting coordination numbers of 3 + 3 + 1 and 3 + 2 + 1, respectively (prim. + sec. Cl contacts + arene). The arene-metal bonding is characterized by Bi-arene distances in the range from 297 - 306 pm, including ring slippages of 24 -41 pm and 73 pm with the Bi atoms being six and seven coordinated, respectively. The direction of this slipping with respect to the arene's methylation sites cannot be understood in terms of electronic influences but is shown to be caused by steric demands. The values IP1 of the arenes prove to determine the colours of the complexes.
    Notes: In den Festkörperstrukturen der drei Komplexe (C6H4(CH3)2)BiCl3 (C6H4(CH3)2 = o-Xylol: 1, m-Xylol: 2, p-Xylol: 3) findet man quasidimere Einheiten fast unverzerrter, arenkoordinierter BiCl3-Fragmente, die über zusätzliche Bi—Cl-Kontakte zu eindimensionalen polymeren Ketten assoziiert sind. Während die Ketten von 2 und 3 nur aus Bi2Cl2-Vierringsegmenten bestehen, führt eine weitere Verbrückung in 1 zusätzlich zu trigonal-bipyramidalen Anordnungen mit Bi-Atomen der Koordinationszahlen 3 + 3 + 1 bzw. 3 + 2 + 1 (prim. + sek. Cl-Kontakte + Aren). Die Bindung des Arens an das Metall ist durch Bi-Aren-Abstände zwischen 297 und 306 pm charakterisiert. Die „ring slippage“ beträgt 24-41 bzw. 73 pm bei den sechsfach bzw. siebenfach koordinierten Bi-Atomen. Die Richtung dieser Verschiebung in bezug auf die Lage der Methylgruppen des Arens kann nicht auf elektronischer Basis interpretiert werden, sondern ist sterisch verursacht. Für die Farbe der Komplexe erweist sich IP1 des Arens als bestimmend.
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  • 90
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1095-1097 
    ISSN: 0044-2313
    Keywords: Rubidium auride ; caesium auride ; preparation ; single-crystals ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Single-Crystal Growth and Structure Refinement of RbAu and CsAuSingle-crystals of RbAu and CsAu were obtained by the reaction of the alkalimetal azides with gold-powder at 400°C. The structures were determined from X-ray single-crystal diffraktometer data: space group Pm3m, Z = 1; RbAu, a = 4.098(1) Å, R/Rw(w = 1) = 0.011/0.011, N(Fo2) ≥ 3σ(Fo2) = 41 and N(var.) = 4; CsAu, a = 4.258(1) Å, R/Rw(w = 1) = 0.009/0.010, N(Fo2) ≥ 3σ(Fo2) = 34 and N(var.) = 4. Both compounds crystallize in the completely ordered CsCl-type with neglible deviations from the ideal 1:1-composition.
    Notes: Einkristalle von RbAu und CsAu wurden durch Reaktion der Alkalimetallazide mit Goldpulver bei 400°C erhalten. Die Strukturen wurden aus Einkristall-Röntgen-Diffraktometerdaten bestimmt: Raumgruppe Pm3m, Z = 1; RbAu, a = 4,098(1) Å, R/Rw(w = 1) = 0,011/0,011, Z(Fo2) ≥ 3σ(Fo2) = 41 und Z(Var.) = 4; CsAu, a = 4,258(1) Å, R/Rw(w = 1) = 0,009/0,010, Z(Fo2) ≥ 3σ(Fo2) = 34 und Z(Var.) = 4. Beide Verbindungen kristallisieren im vollständig geordneten CsCl-Typ mit vernachlässigbarer Abweichung von der idealen 1:1-Zusammensetzung.
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  • 91
    ISSN: 0044-2313
    Keywords: Tetramethylammonium alumosilicate hydrate ; crystal structure ; zeolite ; clathrate hydrate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Strukturelle Bindeglieder zwischen zeolithartigen und clathrathydratartigen Materialien: Synthese und Kristallstruktur von [N(CH3)4]6[AlxSi8-xO18-x(OH)2+x] · 44H2O (x = 3-4)Ein neues Tetramethylammoniumalumosilicat-Hydrat mit der ungefähren Zusammensetzung [NMe4]6[AlxSi8-xO18-x(OH)2+x] · 44H2O (x = 3-4) wurde mittels Röntgenpulverbeugung als eine Komponente eines mehrphasigen festen Gemisches erkannt, das bei Raumtemperatur aus einer wäßrigen NMe4OH—Al2O3—SiO2 Lösung kristallisierte. Große Kristalle der neuen Hydratphase konnten mechanisch aus dem Gemisch ausgelesen werden. Die Kristallstruktur wurde mit 1 196 unabhängigen MoKα-Beugungsdaten, gemessen bei 180 K, bestimmt: Tetragonales Kristallsystem; Zellkonstanten a = 16,181(4) und c = 17,450(4) Å; Raumgruppe P4/mnc mit Z = 2 Formeleinheiten pro Elementarzelle; R = 0,072. Die Wirt-Gast-Verbindung ist vom Typ eines polyedrischen Clathrats mit einem gemischten dreidimensionalen, (im wesentlichen) vierbindigen Netzwerk aus oligomeren Alumosilicat-Anionen [AlxSi8-xO18-x(OH)2+x]6- und H2O-Molekülen, die über Wasserstoffbrücken O—H … O miteinander verknüpft sind. Die Alumosilicat-Anionen besitzen würfelförmige (Doppelvierring-)Struktur. Orientierungsfehlgeordnete kationische Gastspezies NMe4+ befinden sich in den großen polyedrischen Hohlräumen, [4668] und [4151067], der Wirtstruktur; die kleinen [46] Käfige (d.h. die Doppelvierring-Anionen) und [4356] Käfige sind leer. Das Hydrat ist ein weiteres Glied in einer kürzlich aufgefundenen Serie von Clathraten mit gemischten tetraedrischen Netzwerken, wodurch strukturchemisch eine Verbindung zwischen zeolith- und clathrathydratartigen Wirt-Gast-Verbindungen hergestellt wird.
    Notes: A novel tetramethylammonium aluminosilicate hydrate with the approximate composition [NMe4]6[AlxSi8-xO18-x(OH)2+x] · 44H2O (x = 3-4) has been identified by powder X-ray diffraction as a component in a polyphasic solid mixture which crystallized at room temperature from an aqueous NMe4OH—Al2O3—SiO2 solution. Large crystals of the novel hydrate phase could be mechanically selected from that mixture. The crystal structure has been determined from 1 196 unique MoKα diffraction data measured at 180 K: Tetragonal crystal system, cell constants a = 16.181(4) and c = 17.450(4) Å, space group P4/mnc with Z = 2 formula units per unit cell, R = 0.072. The host-guest compound is of polyhedral clathrate type with a mixed three-dimensional, (mainly) four-connected network composed of oligomeric aluminosilicate anions [AlxSi8-xO18-x(OH)2+x]6- and H2O molecules linked via hydrogen bonds O—H … O. The aluminosilicate anions possess a cube-shaped (double four-ring) structure. Orientationally disordered cationic guest species NMe4+ are enclosed in the large [4668] and [4151067] polyhedral voids of the host framework; the small [46] cages (i.e. the double four-ring anions) and [4356] cages are empty. The hydrate is a further member in a recently discovered series of clathrates with mixed tetrahedral networks, which provides a structure-chemical link between zeolite- and clathrate hydrate-type host-guest compounds.
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  • 92
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1755-1758 
    ISSN: 0044-2313
    Keywords: Lead, rare earth, aluminium, oxide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Chemistry of the Lead Lanthanide Oxoaluminates. On Pb2HoAl3O8 and Pb2LuAl3O8.Single crystals of (I) Pb2HoAl3O8 and (II) Pb2LuAl3O8 were prepared by flux technique and investigated by X-ray methods. It crystallizes with cubic symmetry, space group Oh4-P42/n 3 2/m, (I): a = 9.4164(13) Å, (II): a = 9.3486(8) Å, Z = 4. The new structure type shows AlO4 tetrahedra, LnO8 hexagonal bipyramids and one sided coordinated Pb2+ within heterocubane units. The crystal chemical relationships to other lead oxides containing heterocubane Pb4O4 units are discussed.
    Notes: Mit Schmelzmitteltechnik wurden Einkristalle von (I) Pb2HoAl3O8 und (II) Pb2LuAl3O8 dargestellt. Die röntgenographische Untersuchung führte zu kubischer Symmetrie, Raumgruppe Oh4-P42/n 3 2/m, Zellabmessungen (I): a = 9,4164(13) Å, (II): a = 9,3486(8) Å, Z = 4. Der neue Strukturtyp zeigt AlO4-Tetraeder, hexagonale LnO8-Bipyramiden und einseitig koordinierte Pb2+-Ionen in Heterokubaneinheiten. Die kristallchemischen Beziehungen zu anderen Oxiden des Bleis mit Pb4O4-Baugruppen werden diskutiert.
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  • 93
    ISSN: 0044-2313
    Keywords: Complex compounds ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Crystal Structures and Spectroscopic Investigations of 3d-Transition Metal Complexes with Bicyclo[2.2.1]hept-5-ene-2-endo,3-cis-dicarboxylic Acid and N,N-Donor LigandsThe synthesis of coordination compounds of the general type [MLdam(H2O)3] · 2.5 H2O with M = Mn2+, Co2+, Ni2+; H2L = bicyclo[2.2.1]hept-5-ene-2-endo,3-cis-dicarboxylic acid and dam = 2,2′-dipyridyl, 1,10-phenanthroline has been described. The complexes have been characterized by elementary analysis, infrared and electronic spectra and magnetic susceptibility measurements.The results of X-ray crystal structure analyses of [MnLdipy(H2O)3] · 2.5 H2O (1 a) and [CoLdipy(H2O)3] · 2,5 H2O (1 b) show, that both compounds crystallize isotypically and prove the octahedral coordination of the metal atoms. The dicarboxylate anion is coordinated to the central atom by an O atom of only one carboxylate group, the other one is in the ionic state. One O atom of each carboxylate group makes an intramolecular hydrogen bond with a water molecule of the coordination sphere. The other crystal water molecules form a network of H bonds one with another and with the complex molecules, thus stabilizing the crystal packing.
    Notes: Die Synthese von Koordinationsverbindungen der allgemeinen Zusammensetzung [MLdam(H2O)3] · 2,5 H2O mit M = Mn2+, Co2+, Ni2+; H2L = Bicyclo[2.2.1]hept-5-en-2-endo,3-cis-dicarbonsäure und dam = 2,2′-Dipyridyl, 1,10-Phenanthrolin wird beschrieben. Die Komplexe werden durch quantitative Analysen, IR- und Elektronenspektren sowie Magnetmessungen charakterisiert.Die Ergebnisse der Röntgenkristallstrukturanalyse von [MnLdipy(H2O)3] · 2,5 H2O (1 a) und [CoLdipy(H2O)3] · 2,5 H2O (1 b) zeigen, daß beide Verbindungen isotyp kristallisieren und belegen die oktaedrische Koordination der Metallatome. Das Dicarboxylat-Anion ist mit nur einem O-Atom am Zentralatom gebunden, die zweite Carboxylatgruppe liegt ionisch vor. Je ein O-Atom jeder Carboxylatgruppe geht eine intramolekulare Wasserstoffbrückenbindung mit einem koordinativ gebundenem Wassermolekül ein. Die restlichen Kristallwassermoleküle bilden ein die Packung stabilisierendes Wasserstoffbrückennetz untereinander und mit den Komplexmolekülen.
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  • 94
    ISSN: 0044-2313
    Keywords: Rare earth oxychlorides and oxochlorotitanates ; preparation ; crystal structure ; chemical vapour transport ; electron microscopic investigation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Rare Earth Oxochlorotitanates LnTiO3Cl (Ln=Sm—Lu) - Preparation, Structure and Electron Microscopic InvestigationsAfter the preparation of SmTiO3Cl we made the attempt to prepare analogous compounds with the heavier rare earth elements.We present 2 methods to prepare powders of LnTiO3Cl (Ln = Sm—Lu) together with a new method to prepare the rare earth oxychlorides LnOCl (Ln = Tm—Lu). There will be also presented 2 methods to get single crystals of these compounds via chemical vapour transport.The new rare earth oxochlorotitanates LnTiO3Cl (Ln = Eu—Lu) are isotypic to SmTiO3Cl. They crystallize in the monoclinic space group: C2/m (No. 12). The lattice parameters (Å) are between a = 9.716(3), b = 3.942(2), c = 10.100(4) (SmTiO3Cl) and a = 9.748(1), b = 3.8454(5), c = 9.625(2) (LuTiO3Cl), Z = 4. We observed a permanent decay of the cell volume with the decay of the radii of the cations.The structure of EuTiO3Cl and DyTiO3Cl was refined to R = 3.4% and R = 5.8% respectively.The crystal structure which has a certain similarity to brannerite can be described in a simplified way by saying that the rare earth and chlorine particles are located between walls of Ti—O-double-octahedra.
    Notes: Anknüpfend an die Darstellung von SmTiO3Cl wurden weitere Verbindungen dieses Formeltyps mit den schwereren Seltenen Erden zugänglich. Eine neue Methode zur Darstellung von Seltenerd-Oxidchloriden LnOCl (Ln=Tm—Lu) sowie je 2 Wege zur Darstellung pulverförmiger Präparate LnTiO3Cl und zur Synthese von Einkristallen über den chemischen Transport werden vorgestellt.Die neuen, zu SmTiO3Cl isotypen, Oxochlorotitanate LnTiO3Cl (Ln = Eu—Lu) der Seltenen Erden kristallisieren monoklin: RG C2/m (No. 12). Die Gitterkonstanten (in Å) umfassen den Bereich von a = 9,716(3), b = 3,942(2), c = 10,100(4) (SmTiO3Cl) bis a = 9,748(1), b = 3,8454(5), c = 9,625(2) (LuTiO3Cl), Z = 4. Die Zellvolumina nehmen mit dem Kationenradius stetig ab. Die Struktur von EuTiO3Cl und DyTiO3Cl wurde bis zu R = 3,4% bzw. R = 5,8% verfeinert. In der mit dem Brannerittyp nahe verwandten Kristallstruktur erkennt man zwischen Wänden aus Ti - O-Doppeloktaedern angeordnete Seltenerd- und Chlorteilchen.
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  • 95
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1231-1236 
    ISSN: 0044-2313
    Keywords: Thallium(I) hexacyanoferrate(II) ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of Tl4Fe(CN)6Single crystals of Tl4Fe(CN)6 have been prepared for the first time and its crystal structure was determined. The pale yellow compound crystallizes in the triclinic space group P1 (No. 2) with the lattice parameters a = 726.6(1) pm, b = 797.4(8) pm, c = 1 336.0(1) pm, α = 104.7(9)°, β = 90.0(8)°, γ = 97.6(7)°, Z = 2 in a new structure type.
    Notes: Erstmals wurden Einkristalle von Tl4Fe(CN)6 dargestellt und deren Kristallstruktur gelöst. Die fahlgelbe Verbindung kristallisiert triklin, Raumgruppe P1 (No. 2), a = 726,6(1) pm, b = 797,4(8) pm, c = 1 336,0(1) pm, α = 104,7(9)°, β = 90,0(8)°, γ = 97,6(7)°, Z = 2 in einem neuen Strukturtyp.
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  • 96
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1237-1240 
    ISSN: 0044-2313
    Keywords: Synthesis ; crystal structure ; lanthanides ; ternary ammonium lanthanide nitrates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of the Ternary Ammonium Nitrates (NH4)2[M(NO3)5] (M = Tb—Lu, Y)Single crystals of the ternary ammonium nitrates (NH4)2[M(NO3)5] (M = Tb—Lu, Y) are obtained from the solution of the sesquioxides in a melt of NH4NO3 and sublimation of the excess NH4NO3. In the crystal structure of (NH4)2[Tm(NO3)5] (trigonal, P31, Z = 3; a = 1 123.76(8), c = 930.1(1) pm; R = 0.062; Rw = 0.034) Tm3+ is surrounded by five bidentate nitrate ligands. The isolated [Tm(NO3)5]2- groups are held together by ammonium ions.
    Notes: Einkristalle der ternären Ammoniumnitrate (NH4)2[M(NO3)5] (M = Tb—Lu, Y) erhält man durch Auflösen der Sesquioxide in einer Ammoniumnitrat-Schmelze und Entfernen des überschüssigen NH4NO3 durch Sublimation. Die Röntgenstrukturanalyse am Beispiel von (NH4)2[Tm(NO3)5] (trigonal, P31, Z = 3; a = 1 123,76(8), c = 930,1(1) pm; R = 0,062; Rw = 0,034) zeigt, daß Tm3+ von fünf zweizähnigen Nitratliganden umgeben ist. Die anionischen Baueinheiten [Tm(NO3)5]2- sind daher isoliert und werden nur durch die NH4+-Ionen zusammengehalten.
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  • 97
    ISSN: 0044-2313
    Keywords: Fluorometallates ; crystal structure ; hydrogen bonds ; phenylenediammonium salts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrogen Bonds in o- and m-Phenylenediammonium Aquapentafluoro Metallates(III) (MIII = Al, Cr, Fe)m- and o-Phenylenediammonium-[MIIIF5(H2O)] compounds of Al, Cr and Fe were synthesized and characterized by X-ray single crystal structure analysis. All structures are described in the space group P212121 (Z = 4). m-Ph(NH3)22+ (Ph(NH3)22+ = phenylenediammonium) compounds: Al: a = 6.489(2), b = 7.943(2), c = 18.204(2) Å, R/wR = 0.084/0.050 for 1 533 reflections; Cr: a = 6.571(2), b = 8.006(2), c = 18.456(3) Å, R/wR = 0.050/0.040 for 1 571 reflections; Fe: a = 6.608(2), b = 8.052(2), c = 18.424(4) Å, R/wR = 0.042/0.034 for 1 947 reflections. o-Ph(NH3)22+ compounds: Al: a = 6.580(2), b = 7.891(2), c = 18.319(5) Å, R/wR = 0.050/0.045 for 2 370 reflections; Cr: a = 6.642(2), b = 7.954(2), c = 18.484(4) Å, R/wR = 0.065/0.043 for 2 041 reflections; Fe: a = 6.693(2), b = 7.995(4), c = 18.529(7) Å, R/wR = 0.035/0.033 for 2 651 reflections. Isolated distorted octahedral [MIIIF5(H2O)]2- anions are connected by double O—H⃛F hydrogen bonds of alternating strength to form chains in the b direction. Those chains, packed in a pseudohexagonal way, are further linked by the ammonium functions of the phenylenediammonium cations to a 3 D hydrogen bond network.
    Notes: m- und o-Phenylendiammonium-[MIIIF5(H2O)]-Verbindungen von Al, Cr und Fe wurden synthetisiert und durch Röntgenstrukturbestimmungen an Einkristallen charakterisiert. Die Strukturen werden alle in der Raumgruppe P212121 (Z = 4) beschrieben. m-Ph(NH3)22+-Verbindungen (Ph(NH3)22+ = Phenylendiammonium): Al: a = 6,489(2), b = 7,943(2), c = 18,204(2) Å, R/wR = 0,084/0,050 für 1 533 Reflexe; Cr: a = 6,571(2), b = 8,006(2), c = 18,456(3) Å, R/wR = 0,050/0,040 für 1 571 Reflexe; Fe: a = 6,608(2), b = 8,052(2), c = 18,424(4) Å, R/wR = 0,042/0,034 für 1 947 Reflexe. o-Ph(NH3)22+-Verbindungen: Al: a = 6,580(2), b = 7,891(2), c = 18,319(5) Å, R/wR = 0,050/0,045 für 2 370 Reflexe; Cr: a = 6,642(2), b = 7,954(2), c = 18,484(4) Å, R/wR = 0,065/0,043 für 2 041 Reflexe; Fe: a = 6,693(2), b = 7,995(4), c = 18,529(7) Å, R/wR = 0,035/0,033 für 2 651 Reflexe. Isolierte verzerrt oktaedrische [MIIIF5(H2O)]2- Anionen werden durch doppelte O—H…F H-Brückenbindungen alternierender Stärke zu Ketten in b-Richtung verknüpft.Diese pseudohexagonal gepackten Ketten werden durch die Ammoniumfunktionen der Phenylendiammonium-Kationen über weitere H-Brücken dreidimensional vernetzt.
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  • 98
    ISSN: 0044-2313
    Keywords: Sodium aluminogermanate ; sodalite ; hydrogen dihydroxide anion ; crystal structure ; phase transition ; dynamical proton exchange ; MAS NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Natriumalumogermanat-Hydroxosodalithhydrat Na6+x[Al6Ge6O24](OH)x · nH2O (x ≈ 1,6, n ≈ 3,0): Synthese, Phasenumwandlungen und dynamische Fehlordnung des Hydrogendihydroxid-Anions,H3O2-,in der kubischen HochtemperaturformKristallines Natriumalumogermanat-Hydroxosodalithhydrat Na6+x[Al6Ge6O24](OH)x · nH2O mit x ≈ 1,6 und n ≈ 3,0 wurde durch Reaktion von Al2O3, GeO2 und NaOH-Lösung unter hydrothermalen Bedingungen hergestellt und mit Hilfe der Simultanthermoanalyse, Dynamischen Differenz-Kalorimetrie (DSC), Röntgen- und Neutronenbeugung sowie 1H- und 23Na-MAS-NMR- und IR-Spektroskopie charakterisiert. Die Verbindung durchläuft eine reversible strukturelle Phasenumwandlung bei Tc = 166 K (Heizmodus), die tatsächlich, wie in DSC-Messungen festgestellt wurde, als komplexe Zweistufentransformation abläuft. Struktur-
    Notes: Crystalline sodium aluminogermanate hydroxosodalite hydrate Na6+x[Al6Ge6O24](OH)x · nH2O with x ≈ 1.6 and n ≈ 3.0 has been synthesized by reacting Al2O3, GeO2 and NaOH solution under hydrothermal conditions, and characterized by means of simultaneous thermal analysis, differential scanning calorimetry, X-ray and neutron diffraction as well as 1H and 23Na MAS NMR and IR spectroscopy. The material undergoes a reversible structural phase transition at Tc = 166 K (heating mode), which is actually a complex two-step transformation as detected in DSC measurements. Structure refinements of the cubic high-temperature form (cell constant a = 9.034(2) Å, room temperature) with single-crystal X-ray and powder neutron diffraction data have not yielded overall satisfactory results, probably due to the solid-solution character of the hydrosodalite. The refinements nevertheless demonstrate that (i) the sodalite host framework is a strictly alternating array of corner-linked AlO4 and GeO4 tetrahedra, and (ii) most polyhedral [4668] cavities are occupied by four sodium cations and one orientationally disordered hydrogen dihydroxide anion, H3O2-, which possesses a strong central hydrogen bond. Variable-temperature 1H MAS NMR spectra unambiguously confirm the presence of H3O2- ions and, in addition, reveal a dynamical intraionic exchange between the central and terminal protons and a rotational diffusion of those anions to occur in the high-temperature form. The nature of the guest complexes filling the remaining cages could not be unambiguously determined. Results are compared with those obtained in recent studies on the related sodium aluminosilicate hydrosodalite system of the general formula Na6+x[Al6Si6O24] (OH)x · nH2O.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1897-1904 
    ISSN: 0044-2313
    Keywords: Mesityltrifluoro gallates ; mesitylbromo indates ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mesityltrifluoro Gallates. The Crystal Structures of Cs[MesGaF3] and K[MesInBr3]Mes3Ga reacts with GaBr3 in the ratio 1:2 in a commutation reaction to MesGaBr2 (1). 1 can be reacted with KF and CsF in MeCN to K[MesGaF3] (2) and Cs[MesGaF3] (3), respectively. K[MesInBr3] (4) was isolated when MesInBr2 was treated with KF in MeCN. The use of 15-crown-5 was leading to [K(15-crown-5)2][Mes2InBr2] (5) in a substituent exchange reaction. 1-5 were characterized by NMR-, IR- and MS-techniques. The solid state structures of 3 and 4 could be established by X-ray structure determinations. According to these determinations, a layer-type arrangement of the molecules is both structures in common. In the center of the layers, ionic interactions were formed, while the separation of the layers is caused by the bulky mesityl substituents.
    Notes: Mes3Ga reagiert mit GaBr3 im Verhält-nis 1:2 in einer Kommutierungsreaktion zu MesGaBr2 (1). 1 kann mit KF bzw. CsF in MeCN zu K[MesGaF3] (2) bzw. Cs[MesGaF3] (3) umgesetzt werden. Dagegen konnte bei der Reaktion von MesInBr2 mit KF in MeCN nur K[MesInBr3] (4) isoliert werden. Der Einsatz von 15-Krone-5 führt nach einer Substituentenaustauschreaktion zu [K(15-Krone-5)2][Mes2InBr2] (5). 1-5 wurden mittels NMR- und IR-Spektroskopie sowie Massenspektrometrie charakterisiert. Die Festkörperstrukturen von 3 und 4 konnten mit Röntgenstrukturanalysen aufgeklärt werden.Danach ist beiden Verbindungen ein schichtartiger Aufbau gemeinsam, wobei im Zentrum der Schichten die interionischen Wechselwirkungen ausgebildet werden. Die Separation der Schichten folgt aus der abschirmenden Wirkung der Mesitylgruppen an der Oberfläche der Schichten.
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  • 100
    ISSN: 0044-2313
    Keywords: Tellurium ; tungsten halides ; poly(heptatellurium(2+)chloride tetrachlorooxotungstate(1-)) ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reaction of Tellurium with Tungsten Halides: Synthesis and Crystal Structure of Te7WOCl5, a Compound with a Polymer Tellurium CationThe reaction of tellurium with WOCl4 in the presence of a large excess of WCl6 in a sealed evacuated glass ampoule at 150°C yields beside the main product Te8(WCl6)2 a small amount of Te7WOCl5. The crystal structure determination (orthorhombic space group Pcca, lattice parameters at 173 K: a = 2 596.5(9) pm, b = 810.0(3) pm, c = 775.7(2) pm) shows that Te7WOCl5 is built of one-dimensional band shaped polymeric tellurium cations, one-dimensional associated pyramidal WOCl4- anions and of isolated Cl- anions. Te7WOCl5 can thus be formulated as [Te72+]n [WOCl4-]n (Cl-). The structure is closely related but not isotypic to the bromine containing analogue Te7WOBr5. The difference between the two structures lies in different directions of the polar [WOX4-]n chains (X = Cl, Br). The strongly elongated thermal ellipsoid of one tellurium atom is shown to be caused by thermal vibration by determing the crystal structure of Te7WOCl5 at three different temperatures (223, 173 and 123 K). All displacement parameters of all atoms can be extrapolated to zero for 0 K.
    Notes: Die Reaktion von Tellur mit WOCl4 in Gegenwart eines großen Überschusses WCl6 in einer geschlossenen, evakuierten Glasampulle bei 150°C ergibt neben dem Hauptprodukt Te8(WCl6)2 eine geringe Ausbeute an Te7WOCl5. Die Kristallstrukturbestimmung (orthorhombische Raumgruppe Pcca, Gitterkonstanten bei 173 K: a = 2 596,5(9) pm, b = 810,0(3) pm, c = 775,7(2) pm) zeigt, daß Te7WOCl5 aus eindimensionalen, bandförmigen Tellur-Kationen, eindimensionalen Strängen assoziierter, pyramidaler WOCl4--Anionen und aus isolierten Cl--Anionen aufgebaut ist. Te7WOCl5 kann daher als [Te72+]n [WOCl4-]n (Cl-) formuliert werden. Die Struktur ist eng verwandt aber nicht isotyp zur Struktur des analogen, bromhaltigen Te7WOBr5. Der Unterschied zwischen den beiden Strukturen liegt in verschiedenen Richtungen der polaren [WOX4-]n-Ketten (X = Cl, Br). Die Bestimmung der Kristallstruktur von Te7WOCl5 bei drei verschiedenen Temperaturen (223, 173 und 123 K) zeigt, daß das stark anisotrope Schwingungs-ellipsoid eines Telluratoms durch thermische Schwingung verursacht wird, da die Auslenkungsparameter aller Atome der Struktur für 0 K auf Null extrapoliert werden können.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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