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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 1 (1995), S. 389-393 
    ISSN: 0947-6539
    Keywords: crystal structure ; differential thermal analysis ; nitrogen oxides ; phase transitions ; twinning ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of N2O3 and N2O4 have been prepared from measured volumes of NO and O2. Phase relationships in the system N2O3/N2O4, which depend on the composition of the samples and on the temperature, were studied by the Guinier technique and differential thermal analysis. Single crystals of phases A and B of N2O3 were grown in situ on a diffractometer and studied at temperatures between -107 and -170°C by X-ray diffraction. The structure analysis of A-N2O3 (tetragonal, space group I41/a, T = -170°C, a = 1625.57 (16), c = 880.49(13) pm, Z = 32, R1 = 0.051 for 1030 unique reflections) is hampered by twinning and additional disorder of one of two crystallographically independent molecules. B-N2O3 is nicely ordered with one molecule in the asymmetric unit (orthorhombic, space group P212121, T = -160°C, a = 506.86(4), b = 647.96(5), c = 863.26(6) pm, Z = 4, R1 = 0.023 for 1352 unique reflections). The most interesting features of the N2O3 molecule are its planarity and the extraordinarily long N—N bond (189.0(1) pm).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 20 (1981), S. 1-22 
    ISSN: 0570-0833
    Keywords: Cluster compounds ; Lanthanides ; Metal-metal interactions ; Solid-state reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemistry of metals in low valence states is marked by the frequent occurrence of metal clusters, which are easily recognizable when they occur as molecular units. Many metal-rich compounds of transition metals with p-elements (3rd to the 6th main groups) are closely related to the corresponding halides, since they are built up from metal clusters of the same type. The clusters are however, linked together (condensed) by metal-metal bonds. This principle of construction holds particularly well in the case of the novel reduced halides of the lanthanoids.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Gadolinium Iodide Carbide Nitride ; Gadolinium Bromide Carbide Nitride ; Yttrium Iodide Carbide Nitride ; Lanthanum Iodide Carbide Nitride ; preparation ; X-ray single crystal structure investigation ; crystal structure ; condensed cluster ; chain of condensed octahedra and double tetrahedra ; C—C single bond ; Gd6(C2) octahedron ; Gd6N2 double tetrahedron ; Y10(C2)2 double octahedron ; Y6N2 double tetrahedron ; α-Gd4I6CN, β-Gd4I6CN, Y6I9C2N, α-Gd4Br6CN, α-La4I6CN ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gd4I6CN: A Carbide Nitride with Chains of Gd6(C2) Octahedra and Gd6N2 Double TetrahedraThe compound α-Gd4I6CN is prepared by reaction of Gd, GdI3, C, and GdN (1:2:1:1 mole ratio) at 1 170 K in sealed Ta tubes. It is obtained as brown red, transparent needles which are air and moisture sensitive. The structure of α-Gd4I6CN contains Gd6 octahedra centered by C2 groups and double tetrahedra centered by N atoms. The units are alternatingly connected via common edges to form chains (Gd2Gd4/2C2) (Gd2/2Gd2/2N)2 parallel [001]. The linear chains are surrounded by I atoms above all free edges of the metal polyhedra and linked according to (Gd2Gd4/2C2) (Gd2Gd4/2N2)I4/2I8I2 in the a - b plane.We also found β-Gd4I6CN, which is formed in a monotropic transition from the α-form. In the structure the chains of Gd octahedra and tetrahedra as described for α-Gd4I6CN are more densely packed.The structure of Y6I9C2N is composed by chains of pairs of Y-octahedra and Y-tetrahedra, respectively. The octahedra are centered by C2 groups, the tetrahedra by N-atoms.We also synthesized the compounds Gd4Br6CN und La4I6CN by tempering at 1 220 K. They are isotypic with α-Gd4I6CN.
    Notes: α-Gd4I6CN wird durch Reaktion von Gd, GdI3, C und GdN (Molverhältnis 1:2:1:1) bei 1 170 K im verschlossenen Ta-Tiegel erhalten. Es bildet braunrot durchscheinende Nadeln, die gegen Luft und Feuchtigkeit empfindlich sind. Die Struktur von α-Gd4I6CN enthält durch C2-Einheiten zentrierte Gd6-Oktaeder und Doppel aus N zentrierten Tetraedern, Gd6N2. Abwechselnd sind Oktaeder und Tetraederdoppel über gemeinsame Kanten zu Ketten (Gd2Gd4/2C2) (Gd2/2Gd2/2N)2 verknüpft, die parallel [001] ausgerichtet sind. Diese eindimensionalen Einheiten sind über allen freien Kanten durch Iodatome koordiniert und untereinander nach dem Schema (Gd2Gd4/2C2) · (Gd2Gd4/2N2)I4/2I8I2 in der a - b-Ebene verknüpft.Daneben existiert noch ein β-Gd4I6CN, das sich monotrop aus der α-Form bei 1 300 K bildet. Dessen Struktur zeichnet sich durch eine dichtere Packung der für die α-Form beschriebenen Gd-Oktaeder-Tetraederketten aus.In der Struktur von Y6I9C2N sind die Ketten aus Doppeln sowohl C2-zentrierter Oktaeder als auch N-zentrierter Tetraeder der Y-Atome aufgebaut.Weiter erhielten wir die mit α-Gd4I6CN isotypen Verbindungen Gd4Br6CN und La4I6CN durch Tempern der Ausgangsverbindungen bei 1 220 K.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 649-654 
    ISSN: 0044-2313
    Keywords: Cerium Nitride Iodide ; preparation ; X-ray single crystal investigation ; crystal structure ; condensed cluster ; chain of condensed Ce tetrahedra around N ; Ce triangles around N ; magnetic properties ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Crystal Structure, and Magnetic Properties of Ce15N7I24The compound Ce15N7I24 is prepared by reaction of CeI3 and CeN (8:7 mole) at 1050 K in sealed Ta tubes. It is obtained as red, transparent needles which are air and moisture sensitive. The structure of Ce15N7I24 contains two crystallographically different types of N atoms. The one type of N is tetrahedrally coordinated by Ce atoms. The Ce4N tetrahedra are condensed via opposite edges to form chains. The other type of N has a triangular environment of Ce atoms. Ce15N7I24 is paramagnetic with an effective magnetic moment of 2,55 μB.
    Notes: Ce15N7I24 wird durch Reaktion von CeI3 und CeN (Molverhältnis 8:7) bei 1050 K im verschlossenen Ta-Tiegel erhalten. Es bildet rot durchscheinende Nadeln, die gegen Luft und Feuchtigkeit empfindlich sind. In der Struktur von Ce15N7I24 liegen zwei kristallchemisch unterschiedliche N-Atome vor. Die eine Sorte wird von den Ce-Atomen tetraedrisch koordiniert. Die Ce4N-Tetraeder sind über gemeinsame Kanten zu Ketten verknüpft. Die andere Sorte befindet sich im Mittelpunkt eines von Ce-Atomen aufgespannten Dreiecks. Die Ce3N-Dreiecke sind über I-Atome mit benachbarten Dreiecken und Tetraederketten verknüpft. Ce15N7I24 ist paramagnetisch mit einem effektiven magnetischen Moment von 2,55 μB.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1501-1507 
    ISSN: 0044-2313
    Keywords: Gadolinium carbide chloride ; gadolinium carbide bromide ; terbium carbide bromide ; crystal structure ; Gd—Gd bonds, electrical conductivity ; antiferromagnetism ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Gadolinium Carbide Halides, Gd4C2X3 (X = Cl, Br)The compounds Gd4C2X3 (X = Cl, Br) and Tb4C2Br3 have been prepared by reaction of the metals (RE), REX3, and C in sealed Ta capsules at 1 100° and 1 300°C, respectively. Monophasic samples of Gd4C2Br3 and Tb4C2Br3 were obtained by reacting stoichiometric mixtures of the starting materials for five days. The needle shaped crystals are bronze-coloured and sensitive to air and moisture. Gd4C2X3 crystallizes in the space group Pnma (No. 62) with lattice constants a = 1 059.6(4), b = 368.4(1), c = 1 962.7(8) pm (Gd4C2Cl3), a = 1 084.4(1), b = 373.0(1), c = 2 036.1(1) pm (Gd4C2Br3). According to Guinier photographs, Tb4C2Br3 is isotypic (a = 1 074.3(2), b = 370.6(1), c = 2 019.4(1) pm).In the crystal structure C is octahedrally coordinated by Gd. The Gd6 octahedra are linked via common edges to form corrugated layers. The X-anions coordinate all free edges and corners of these layers and connect them via Xi—Xi contacts parallel [001].Gd4C2Br3 shows metallic conductivity. The magnetic susceptibility follows at high temperatures a Curie Weiss law with an effective moment of 7.95 μB. At temperatures below 50 K antiferromagnetic order is observed.
    Notes: Die Verbindungen Gd4C2X3 (X = Cl, Br) und Tb4C2Br3 werden durch fünftägiges Tempern von Metall, Trihalogenid und C in verschweißten Ta-Kapseln bei Temperaturen zwischen 1 100° und 1 300°C dargestellt. Die Kristalle bilden bronzefarbene Nadeln und sind gegen Luft und Feuchtigkeit mäßig empfindlich. Es liegt die Raumgruppe Pnma (Nr. 62) vor mit den Gitterkonstanten a = 1 059,6(4), b = 368,4(1), c = 1 962,7(8) pm (Gd4C2Cl3), a = 1 084,4(1), b = 373,0(1), c = 2 036,1(1) pm (Gd4C2Br3). Nach Guinier-Aufnahmen ist Tb4C2Br3 isotyp (a = 1 074,3(2), b = 370,6(1), c = 2 019,4(1) pm).In der Kristallstruktur ist C oktaedrisch von Gd koordiniert. Die Gd6-Oktaeder sind über gemeinsame Kanten kondensiert und bilden gewellte Schichten. Die X-Anionen koordinieren alle freien Ecken und Kanten dieser Schichten und verknüpfen sie parallel [001] über Xi—Xi-Kontakte.Gd4C2Br3 zeigt metallisches Verhalten. Die Hochtemperatursuszeptibilität befolgt ein Curie-Weiss-Gesetz mit einem magnetischen Moment von 7,95 μB. Bei Temperaturen unterhalb 50 K findet man langreichweitige antiferromagnetische Ordnung.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 49-63 
    ISSN: 0044-2313
    Keywords: Oxomolybdates ; cluster ; crystal structure ; HRTEM ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of PbMo5O8; a reduced Oxomolybdate with Mo10O28 Double OctahedraThe crystal structure of the new phase PbMo5O8 contains oligometric Mo clusters which consist of two edge-sharing Mo6 octahedra connected according to Mo10O6iO4/2i-iO16/2i-a. The compound is isotypic with LaMo5O8. Isolated, divalent Pb atoms are located in the “channels” of the monoclinic structure (a = 999.3(2) pm, b = 924.7(1) pm, c = 753.6(2) pm, β = 109.39(2)°, P21/a. Compared to the compound In 11Mo40O62 the Mo—O distances (average 206 pm) and the Mo—Mo distances within the octahedral units (average 275 pm) are slightly decreased by 1 and 4 pm, respectively. The very short Mo—Mo distances (278 pm) between the cluster units which are not observed in In11Mo40O62 (320 pm) are due to excess electrons in these inter-cluster bonds which would otherwise occupy antibonding cluster states.
    Notes: Mit der neuen Phase PbMo5O8 wurde ein weiteres Beispiel für oligomere Mo-Cluster aus zwei kantenverknüpften Mo6-Oktaedern gefunden, die nach Mo10O6iO4/2i-iO16sol;2i-a verknüpft sind. Die Verbindung ist isotyp zu LaMo5O8. In den „Kanälen“ der monoklinen Struktur a = 999,3(2) pm, b = 924,7(1) pm, c = 753,6(2) pm, β = 109,39(2)°, P21/a) findet man isolierte, zweiwertige Pb-Atome. Gegenüber der Verbindung In11Mo40O62 sind die Mo—O-Abstände mit durchschnittlich 206 pm nur gering um 1 pm und die Mo—Mo-Abstände innerhalb der oktaedrischen Baueinheiten mit durchschnittlich 275 pm ebenfalls nur schwach um 4 pm verkürzt. Allerdings findet man mit 278 pm sehr kurze Mo—Mo-Abstände zwischen den Clustereinheiten, die so nicht bei In11Mo40O62 (320 pm) beobachtet werden können. An diesen inter-Cluster-Bindungen sind überschüssige Elektronen beteiligt, die andernfalls antibindende Clusterzustände besetzen würden.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 36 (1997), S. 1788-1806 
    ISSN: 0570-0833
    Keywords: band structure ; carbides ; cuprates ; lanthanoids ; superconductivity ; Electronic structure ; Carbides ; Cuprates ; Lanthanides ; Superconductors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The microscopic theory of superconductivity worked out by Bardeen, Cooper, and Schrieffer led to a fundamental understanding of the phenomenon. However, this theory does not provide a materials aspect. Starting from the special situation of chemical bonding in carbides and carbide halides of the rare earth metals a general view of the origin of superconductivity is developed, based on a tendency for (pairwise) localization of conduction electrons. This approach is tested in terms of special features in the electronic band structure and compared with existing physical models of electron pairing in real space. Its applicability to high-temperature superconductors discovered during the last decade is discussed.
    Additional Material: 26 Ill.
    Type of Medium: Electronic Resource
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