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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 597 (1991), S. 51-59 
    ISSN: 0044-2313
    Keywords: Pentastrontium-trifluoride-{di-μ-fluoro-bis[tetrafluoroferrate(III)]}-hemafluoroferrate(III), Sr5F3[Fe2F10][FeF6] ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dinuclear Anion Groups [Fe2F10]4- in the Crystal Structure of Sr5Fe3F19At single crystals of Sr5Fe3F19 a X-ray structure determination in the tetragonal space group 14/m was performed (a = 1429.4(3), c = 730.7(3) pm; Z = 4. wR = 0.019 for 502 independent reflections). Within the structure there are isolated, but disordered dimeric anion groups of edge-sharing octahedra [Fe2F10]4- (average Fe—F = 193.3 pm, Fe—Fe = 319.1 pm). They are embedded in a framework of strontium ions (C.N. 8-10) and single FeF63- octahedra (Fe—F = 191.0 resp. 192.7 pm, if corrected for thermal motion). The strong relations to the crystal structure of BaTiF5 and to further related fluoride compounds are discussed.
    Notes: An Einkristallen von Sr5Fe3F19 wurde eine röntgenographische Strukturbestimmung in der tetragonalen Raumgruppe 14/m durchgeführt (a = 1429,4(3), c = 730,7(3) pm; Z = 4. wR = 0,019 für 502 unabhängige Reflexe). In der Struktur treten isolierte, aber fehlgeordnete dimere Aniongruppen kantenverknüpfter Oktaeder [Fe2F10]4- auf (Mittelwert Fe—F = 193,3 pm, Fe—Fe = 319,1 pm). Sie sind eingebettet in ein Gerüst von Strontiumionen (KZ 8-10) und FeF63--Einzeloktaedern (Fe—F = 191,0 bzw. 192,7 pm, wenn für die thermische Schwingung korrigiert wird). Die engen Beziehungen zur Kristallstruktur von BaTiF5 und zu weiteren verwandten Fluorverbindungen werden diskutiert.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1686-1691 
    ISSN: 0044-2313
    Keywords: Sodium scandium fluoride ; cryolite structure ; tolerance factor ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Cryolite Structure of Na3ScF6 and the Tilting of Octahedra in Isostructural Sodium Hexafluorometallates Na3MF6X-ray studies at single crystals of Na3ScF6 confirmed the monoclinic cryolite type structure of this compound: a = 559.5, b = 580.2, c = 811.6 pm, β = 90.72°, Z = 2, space group P21/n; R1 = 0.021 for 512 symmetry independent reflections. The octahedra of [ScF6] (average Sc—F = 200.7 pm), as well as those of [NaF6] (Na1—F = 229.1 pm) linked to them, are titled by about 20° with respect to the axes of the perovskite-like pseudocell. This tilting of octahedra is discussed in comparison with other cryolites and with orthorhombic perovskites NaMF3; there results a correlation between tilt angle and tolerance factor t ˜ 0.88 of these compounds, the [NaF8] coordination of which invariably exhibits a constant mean value of Na2—F = 231.5 ± 1 pm for the four shortest distances.
    Notes: Eine röntgenographische Untersuchung an Einkristallen von Na3ScF6 bestätigte die monokline Kryolithstruktur dieser Verbindung: a = 559,5, b = 580,2, c = 811,6 pm, β = 90,72°, Z = 2, Raumgruppe P21/n; R1 = 0,021 für 512 symmetrie-unabhängige Reflexe. Die [ScF6]-Oktaeder (Mittelwert Sc—F = 200,7 pm) sind ebenso wie die mit ihnen verknüpften [NaF6]-Oktaeder (Na1—F = 229,1 pm) um etwa 20° gegen die Richtungen der perowskitartigen Pseudozelle gekippt. Diese Oktaederkippung wird im Vergleich mit anderen Kryolithen und mit den orthorhombischen Perowskiten NaMF3 diskutiert; dabei ergibt sich ein Zusammenhang zwischen Kippungswinkel und Toleranzfaktor t 〈 0,88 für diese Verbindungen, in deren [NaF8]-Koordination sich einheitlich ein konstanter Mittelwert von Na2—F = 231,5 ± 1 pm für die vier kürzesten Abstände zeigt.
    Additional Material: 4 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1692-1697 
    ISSN: 0044-2313
    Keywords: Sodium copper scandium fluoride ; sodium zinc aluminium fluoride ; weberite structure ; crystal structure determination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structures of the Weberites Na2CuScF7 and Na2ZnAlF7At single crystals of the orthorhombic weberites Na2CuScF7 (Pmnb, Z = 4) and Na2ZnAlF7 (Imma, Z = 4) X-ray structure determinations were performed. Na2CuScF7 (Na2ZnAlF7): a = 726.0 (709.2), b = 1053.4 (1009.2), c = 765.8 (733.7) pm; R1 = 0.030 (0.042) for 887 (363) observed and independent reflections. The resulting average distances of the octahedrally coordinated metal atoms are: Cu—F = 200.7 pm, Sc—F = 201.7 pm; Zn—F = 198.8 pm, Al—F = 180.1 pm. Some structural relations and the variation in the bridge angles of the corner-sharing octahedra are discussed.
    Notes: An Einkristallen der orthorhombischen Weberite Na2CuScF7 (Pmnb, Z = 4) und Na2ZnAlF7 (Imma, Z = 4) wurden röntgenographische Strukturbestimmungen durchgeführt. Na2CuScF7 (Na2ZnAlF7): a = 726,0 (709,2), b = 1053,4 (1009,2), c = 765,8 (733,7) pm; R1 = 0,030 (0,042) für 887 (363) beobachtete und unabhängige Reflexe. Die resultierenden mittleren Abstände für die oktaedrisch koordinierten Metallatome sind: Cu—F = 200,7 pm, Sc—F = 201,7 pm; Zn—F = 198,8 pm, Al—F = 180,1 pm. Die Stukturverhältnisse und die Unterschiede in den Brückenwinkeln der eckenverknüpften Oktaeder werden diskutiert.
    Additional Material: 1 Ill.
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  • 14
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tetragonal Fluoroperovskites AM0,75 □ 0,25F3 Deficient in Cations: K4MnIIM2IIIF12 and Ba2Cs2Cu3F12By heating 2KMnF3 + K2MnF6 and BaF2, CsF + CuF2 respectively, the isostructural tetragonal compounds K4Mn3F12 (a = 832.2, c = 1643.0 pm) and Ba2Cs2Cu3F12 (a = 854.1, c = 1704.1 pm) were prepared. They crystallize in a cation-deficient perovskite structure exhibiting ordering of octahedral vacancies. Single crystal structures determinations in the space group I41/amd, Z = 4, yielded the following average distances within the octahedra, which are Jahn-Teller distorted for MnIII and CuII:MnII—F = 208.3 pm, MnIII—F = 4 × 183.0/2 × 209.7 pm; Cu—F = 190.7/227.1 and 190.6/236.4 pm, respectively. The results are discussed in comparison with related compounds.
    Notes: Durch Erhitzen von 2KMnF3 + K2MnF6 bzw. von BaF2, CsF und CuF2 wurden die isostrukturellen tetragonalen Verbindungen K4Mn3F12 (a = 832,2, c = 1643,0 pm) bzw. Ba2Cs2Cu3F12 (a = 854,1, c = 1704,1 pm) hergestellt. Sie kristallisieren in einer kationendefizitären Perowskitstruktur mit geordneter Verteilung der zu einem Viertel unbesetzten Oktaederlücken. Die Einkristallstrukturbestimmungen in der Raumgruppe I41/amd, Z = 4, ergaben folgende mittlere Abstände in den für MnIII and CuII Jahn-Teller-verzerrten Oktaedern: MnII - F = 208,3 pm, MnIII—F = 4 × 183,0/2 × 209,7 pm; Cu—F = 190,7/227,1 bzw. 190,6/236,4 pm. Die Resultate werden im Vergleich mit verwandten Verbindungen diskutiert.
    Additional Material: 3 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 406 (1974), S. 38-44 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation of Quaternary Fluorides LiMIIMIIIF6. Some Compounds of the BaLiCrF6 TypeSome monoclinically crystallizing compounds BaLiMIIIF6 (MIII = Al, Ga, Cr, V, Fe, Ti) are reported. Part of the lithium, which is tetrahedrally coordinated in the BaLiCrF6-type structures, could be replaced by Co(II) ions in solid solutions BaLiGaF6/KCoGaF6. The reflectance spectrum of tetrahedral CoF42- is given.
    Notes: Es wird über eine Reihe monoklin kristallisierender Verbindungen der Zusammensetzung BaLiMIIIF6 (MIII = Al, Ga, Cr, V, Fe, Ti) berichtet. Das in den Strukturen vom BaLiCrF6-Typ tetraedrisch koordiniert vorliegende Lithium ließ sich in Mischkristallen BaLiGaF6/KCoGaF6 partiell durch Co(II)-Ionen ersetzen. Das Reflexionsspektrum von tetraedrischem CoF42- wird mitgeteilt.
    Additional Material: 1 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 487 (1982), S. 75-84 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Relations of Distances and Coordination in the Layer Structures of the Ternary Fluorides K2MF4 and K3M2F7 (MII = Mg, Mn, Co=Zn)Results of X-ray single crystal structure refinements of the compounds K2MF4 (M = Mg, Mn, Co, Ni) and K3M2F7 (M = Mn, Co, Ni), all crystallizing in the tetragonal space group I4/mmm of the K2NiF4 and Sr3Ti2O7 type, resp., are reported. The distances obtained are discussed, including data of the compounds with M = Cu, Zn. The influence of the KF9 coordination is made responsible for the fact, that the octahedral MF6 dimensions are much the same as in the corresponding perovskites KMF3. The shortest K—F distance of this KF9 group, occuring in both layer structure types, decreases against lattice widening from 263.4 pm (K2MgF4) to 258.0 pm (K2MnF4). The charge ratio calculated from the KF9 coordination for the unlike bonded anions leads to a better balanced charge distribution in the K2MF4 type, as is obtained by applying Pauling's rules.
    Notes: Ergebnisse röntgenographischer Einkristallstrukturverfeinerungen an den im K2NiF4- bzw. Sr3Ti2O7-Typ kristallisierenden Verbindungen K2MF4 (M = Mg, Mn, Co, Ni) und K3M2F7 (M = Mn, Co, Ni), die alle der tetragonalen Raumgruppe I4/mmm angehören, werden mitgeteilt. Die resultierenden Abstandsdaten werden unter Einbeziehung der Verbindungen mit M = Cu, Zn diskutiert. Die weitgehend den zugehörigen Perowskiten KMF3 entsprechenden Abstandsverhältnisse in den MF6-Oktaedern werden dem Einfluß der KF9-Koordination zugeschrieben, deren kürzester Abstand K—F in beiden Schichtstrukturtypen entgegen der Gitteraufweitung von 263,4 pm (K2MgF4) auf 258,0 pm (K2MnF4) abnimmt. Das aus der KF9-Koordination berechnete Ladungsverhältnis der ungleich gebundenen Anionen führt zu einer ausgeglicheneren Ladungsbilanz für den K2MF4-Typ, als die Anwendung der Paulingschen Regeln.
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  • 17
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Single Crystal Structure Determinations of the Cubic High Pressure Elpasolites Rb2LiFeF6 and Cs2NaFeF6: Pressure-Distance Paradox without Change of Coordination NumberAt single crystals of metastable high pressure phases of Rb2LiFeF6 (a = 824.4 pm) and Cs2NaFeF6 (a = 873,9 pm) the parameters of the cubic elpasolite structure (Fm3m, Z = 4) were determined by X-ray methods. Compared to the 12L-structures of the normal pressure phases (R3m, hex. Z = 6) only the distances within the 12-coordination, Rb—F = 291.7 resp. Cs—F = 309.9 pm, are compressed by 2-3%. However, the octahedral distances Fe—F = 194.6 pm and Li—F = 217.6 pm resp. Fe—F = 194.9 pm and Na—F = 242.0 pm, are enlarged by 1-4%, though there was no increase in coordination number. This paradoxical behaviour is discussed. Difference Fourier syntheses reveal disorder only for the lithium positions in Rb2LiFeF6, which are 30 pm off-center, corresponding to a splitting of distances Li—F into 188, 247 and 4 × 220 pm.
    Notes: An Einkristallen der metastabilen Hochdruckphasen von Rb2LiFeF6 (a = 824,4 pm) und Cs2NaFeF6 (a = 873,9 pm) wurden röntgenographisch die Parameter der kubischen Elpasolithstruktur (Fm3m, Z = 4) bestimmt. Gegenüber den 12 L-Strukturen der Normaldruckphasen (R3m, hex. Z = 6) sind nur die Abstandswerte in der Zwölferkoordination, Rb—F = 291,7 bzw. Cs—F = 309,9 pm, um 2-3% verkleinert. Aber für die oktaedrischen Abstände Fe—F = 194,6 pm und Li—F = 217,6 pm bzw. Fe—F = 194,9 pm und Na—F = 242,0 pm ergeben sich Aufweitungen von 1-4%, obwohl keine Erhöhung der Koordinationszahl stattgefunden hat. Dieses paradoxe Verhalten wird diskutiert. Nur für die Lithiumpositionen in Rb2LiFeF6 zeigen Differenzfouriersynthesen eine Fehlordnung, die einer Li-Auslenkung von 30 pm aus dem Oktaederzentrum und einer Li—F-Abstandsaufspaltung in 188, 247 und 4 × 220 pm entspricht.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 418 (1975), S. 193-207 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: High Pressure Syntheses and Transformations of Hexagonal Elpasolithes A2IBIMIIIF6Hexagonal-rhombohedrally in the structure type of Cs2NaCrF6 crystallizing elpasolithes Rb2LiMF6 and Cs2NaMF6 (MIII = Al, Ga, V, Cr, Fe) were transformed to cubic modifications (K2NaAlF6 type) by high pressure application (15-100 kbar). In addition intermediate high pressure phases with the hexagonal structure of high temperature K2LiAlF6 could be obtained in some cases. The lattice constants of these compounds are reported, as well as those of hexagonal elpasolithes Tl2LiMF6 and Cs2LiMF6 which only form, if they are synthesized under pressure. The results are discussed in connection with the Goldschmidt tolerance factor t′ = √2(rA + rF)/(rB + rM + 2rF) of the elpasolithes mentioned.
    Notes: Von hexagonal-rhomboedrisch im Cs2NaCrF6-Typ kristallisierenden Elpasolithen Rb2LiMF6 und Cs2NaMF6 (MIII = Al, Ga, V, Cr, Fe) konnten durch Hochdruckanwendung (15-100 kbar) kubische Modifikationen (K2NaAlF6-Typ) erhalten werden. Als intermediäre Hochdruckphasen ließen sich in einigen Fällen außerdem Modifikationen mit der hexagonalen Struktur von Hochtemperatur-K2LiAlF6 fassen. Die Gitterkonstanten dieser Verbindungen werden mitgeteilt, ebenso wie diejenigen neuer hexagonaler Elpasolithe Tl2LiMF6 und Cs2LiMF6, die sich nur bilden, wenn die Synthese unter Druck erfolgt. Die Ergebnisse werden im Zusammenhang mit dem Goldschmidtschen Toleranzfaktor t′ = √2(rA + rF)/(rB + rM + 2rF) der genannten Elpasolithe diskutiert.
    Additional Material: 6 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 467 (1980), S. 187-196 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: X-Ray Studies on Titanium(III) Fluoro Compounds with Pyrochlore-related StructuresThe cubic compounds (a/pm) CsMIITiIIIF6, MII = Mg (1041.6), Ni (1043.9), Zn (1049.8), Co (1051.7), V (1052.6), Fe (1055.3), Mn (1064.9) and CsM0,5ITi1,5IIIF6, MI = K (1074.6), Rb (1080.6) were prepared. They crystallize in the modified pyrochlore structure of the RbNiCrF6 type, which is confirmed once more at single crystals of an oxide fluoride phase CsTi2X6 (X6 between O2F4 and O3F3): Space group Fd3m, a = 1028.8 pm, R = 2.6% (126 independent reflections). Further compounds CsM0,5ITi1,5IIIF6 according to their powder diagrams are orthorhombic (MI = NH4: a = 764.1, b = 767.5, c = 1087.5 pm) or monoclinic (Na: a = 737.0, b = 758.0, c = 1061.8 pm, β = 91.1°, Li: a = 1466, b = 1479, c = 1041 pm, β = 93.3°) with related, but not exactly know structures.
    Notes: Die kubischen verbindungen (a/pm) CsMIITiIIIF6, MII = Mg(1041,6), Ni(1043,9), Zn(1049,8), Co(1051,7), V(1052,6), Fe(1055,3), Mn(1064,9) und CsM0,5ITi1,5IIIF6, MI = K(1074,6), Rb(1080,6) wurden dargestellt. Sie kristallisieren in der modifizierten Pyrochlorstruktur des RbNiCrF6-Types, der an Einkristallen einer Oxidfluoridphase CsTi2X6 (X6 zwischen O2F4 und O3F3) erneut bestätigt wird: Raumgruppe Fd3m, a = 1028,8 pm, R = 2,6% (126 symmetrieunabhängige Reflexe). Weitere Verbindungen CsM0,5ITi1,5IIIF6 sind nach Pulveraufnahmen orthorhombisch (MI = NH4: a = 764,1, b = 767,5, c = 1087,5 pm) bzw. monoklin (Na: a = 737,0, b = 758,0, c = 1061,8 pm, β = 91,1°, Li: a = 1466, b = 1479, c = 1041 pm,β = 93,3°), mit verwandten, aber nicht genauer bekannten Strukturen.
    Additional Material: 5 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 491 (1982), S. 137-144 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of a High Temperature Modification of Barium-Zinc-Iron(III) Fluoride BaZnFeF7A metastable high temperature form of BaZnFeF7 prepared at 750°C crystallizes monoclinically (a = 560.3(1), b = 997,1(3), c = 958.4(4) pm, β = 92.80(4)°, Z = 4) in the same space group P21/c as the low temperature form. The X-ray structure determination (RG = 5.2— for 2426 independent reflections) showed analogy in the coordination behaviour of Zn2+ and Fe3+ cations, which occupy in an ordered way groups of two edgesharing octahedra, at each of which one ligand remains unbridged (mean distances Zn—F = 204.7 pm, Fe—F = 194.6 pm). The linking of double octahedra via corners to form a threedimensional framework involves strongly bent fluorine bridges (average Zn—F—Fe = 126.5°). Related structures are discussed.
    Notes: Eine bei 750°C in Einkristallen dargestellte metastabile Hochtemperatur-form von BaZnFeF7 kristallisiert monoklin (a = 560,3(1), b = 997,1(3), c = 958,4(4) pm, β = 92,80(4)°, Z = 4) in derselben Raumgruppe P21/c, wie die Tieftemperaturform. Die röntgenographische Strukturbestimmung (RG = 5,2 -  für 2 426 unabhängige Reflexe) ergab koordinationschemisch analoges Verhalten für Zn2+- und Fe3+-Kationen, die geordnet kantenverknüpfte Gruppen von zwei Oktaedern besetzen, an denen je ein Ligand unverbrückt bleibt (mittlere Abstände Zn—F = 204,7 pm, Fe—F = 194,6 pm). Die Eckenverknüpfung der Doppeloktaeder zu einer Raumnetzstruktur verläuft über stark gewinkelte Fluorbrücken (Mittel Zn—F—Fe = 126,5°). Verwandte Strukturen werden diskutiert.
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