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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 863-866 
    ISSN: 0044-2313
    Keywords: CsNb3Br7S ; synthesis ; crystal structure ; bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CsNb3Br7S: Synthesis, Structure, and Bonding StatesThe reaction of NbBr5 with Nb, Cs and S in a sealed Nb container affords CsNb3Br7S at 800°C (3 days). Further on isotypic compounds of the general formula ANb3X7Ch with A = Rb, Cs; X = Cl, Br and Ch = S, Se are obtained. CsNb3Br7S crystallizes monoclinic (space group P21/a, Z = 2), with the lattice parameters a = 707.4(2), b = 1 888.4(4), c = 994.1(2) pm and β = 98.59(2)°. The crystal structure contains Nb3 clusters being linked by two additional Nb—Nb bonds to form infinite chains. Adjacent chains are bridged by Cs atoms in a cubeoctahedral coordination sphere of Br atoms. Similar with Nb3Br8 seven electrons occupy metal - metal bonding states.
    Notes: Bei der Reaktion von NbBr5 mit Nb, Cs und S bildet sich im verschweißten Niobrohr bei 800°C (3 Tage) CsNb3Br7S. Ferner wurden isotype Verbindungen der allgemeinen Zusammensetzung ANb3X7Ch mit A = Rb, Cs; X = Cl, Br und Ch = S, Se erhalten. CsNb3Br7S kristallisiert monoklin (Raumgruppe P21/a, Z = 2) mit den Gitterparametern a = 707,4(2), b = 1 888,4(4), c = 994,1(2) pm und β = 98,59(2)°. In der Kristallstruktur liegen Nb3-Cluster vor, die durch zwei zusätzliche Nb—Nb-Bindungen zu unendlichen Strängen verknüpft sind. Cs-Atome verbrücken benachbarte Stränge und besitzen eine kuboktaedrische Koordinationssphäre aus Br-Atomen. Wie in Nb3Br8 besetzen formal sieben Elektronen Metall - Metall-bindende Zustände.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 921-924 
    ISSN: 0044-2313
    Keywords: Niobium cluster azide ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Octahedral Niobium Cluster containing Six Terminal Azide Groups: The Structure of Rb4[Nb6Br12(N3)6](H2O)2Six terminal halide ligands of [Nb6Br12Br6]4- can be substituted in solution by azide ions. Single-crystals of Rb4[Nb6Br12(N3)6](H2O)2 were obtained during the evaporation of the water/methanol solvent, and structurally characterized by X-ray methods: Space group P21/c, Z = 2, a = 970.8(5) pm, b = 1525.4(7) pm, c = 1280.0(7) pm, β = 97.15(6)°. The [Nb6Br12(N3)6]4- ions contain six terminal azide groups at the corners of the octahedral niobium cluster (dNb-N = 227 pm). The [Nb6Br12(N3)6]4- ions are interconnected by Rb+ and H2O. Crystals of Rb4[Nb6Br12(N3)6](H2O)2 are explosive towards heat or mechanic pressure.
    Notes: Sechs terminal gebundene Halogenliganden von [Nb6Br12Br6]4- können in Lösung durch Azidionen ausgetauscht werden. Einkristalle von Rb4[Nb6Br12(N3)6](H2O)2 bildeten sich beim Eindunsten einer wäßrig-methanolischen Lösung und wurden röntgenographisch charakterisiert: Raumgruppe P21/c, Z = 2, a = 970,8(5) pm, b = 1525,4(7) pm, c = 1280,0(7) pm, β = 97,15(6)°. Die Struktur enthält [Nb6Br12(N3)6]4--Ionen in denen sechs terminale Azidgruppen an den Ecken des oktaedrischen Niobclusters (dNb-N = 227 pm) gebunden sind. In der Kristallstruktur liegen die [Nb6Br12(N3)6]4--Ionen verbrückt über Rb+ und H2O vor. Kristalle von Rb4[Nb6Br12(N3)6](H2O)2 reagieren auf Hitze oder mechanischen Druck explosiv.
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  • 3
    ISSN: 0044-2313
    Keywords: Niobium cluster thiocyanate ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thiocyanatverbindungen von [Nb6Cl12]2+: Die Struktur von A4[Nb6Cl12(NCS)6](H2O)4 (A = K, Rb, NH4)Neue Verbindungen der allgemeinen Zusammensetzung A4[Nb6Cl12(NCS)6](H2O)4 (A = K, Rb, NH4) wurden ausgehend von Nb6Cl14 und ASCN in wäßrigen Lösungen hergestellt. Röntgenstrukturbestimmungen wurden anhand von Einkristalldaten der drei Verbindungen durchgeführt. Die Verbindungen kristallisieren isotyp in der Raumgruppe P1 (Z = 1) mit den Gitterparametern: a = 877.9(3) pm, b = 1176.6(3) pm, c = 1187.0(3) pm, α = 114.29(1)°, β = 98.96(2)°, γ = 100.91(2)° für K4[Nb6Cl12(NCS)6](H2O)4 (1); a = 887.6(3) pm, b = 1184.0(4) pm, c = 1195.4(4) pm, α = 114.95(2)°, β = 98.84(2)°, γ = 101.31(2)° für Rb4[Nb6Cl12(NCS)6](H2O)4 (2) und a = 886.0(4) pm, b = 1181.1(6) pm, c = 1183.9(6) pm, α = 114.49(2)°, β = 99.48(3)°, γ = 101.53(1)° für (NH4)4[Nb6Cl12(NCS)6](H2O)4 (3). Jedes der zentrosymmetrischen [Nb6Cl12(NCS)6]4--Ionen der isotypen Verbindungen enthält sechs Thiocyanat-Einheiten, die über Stickstoffatome an die Ecken des oktaedrischen Niobclusters gebunden sind (dNb—N = 221.5(6)-224.3(6) pm, Bindungswinkel Nb—N—C 168.6(5)-176.4(6)°). Die [Nb6Cl12(NCS)6]4--Ionen sind über A—S- und A—Cl-Wechselwirkungen der A-Kationen miteinander verbrückt. Die Hälfte der Kationen sind über zwei kristallographische Positionen fehlgeordnet.
    Notes: New compounds of the general formula A4[Nb6Cl12(NCS)6](H2O)4 (A = K, Rb, NH4) were synthesized from Nb6Cl14 and ASCN in aqueous solutions. X-ray structure refinements were performed on single-crystal data of the three compounds. They are isotypic and crystallize with the space group P1 (Z = 1) and the lattice parameters: a = 877.9(3) pm, b = 1176.6(3) pm, c = 1187.0(3) pm, α = 114.29(1)°, β = 98.96(2)°, γ = 100.91(2)° for K4[Nb6Cl12(NCS)6](H2O)4 (1); a = 887.6(3) pm, b = 1184.0(4) pm, c = 1195.4(4) pm, α = 114.95(2)°, β = 98.84(2)°, γ = 101.31(2)° for Rb4[Nb6Cl12(NCS)6](H2O)4 (2) and a = 886.0(4) pm, b = 1181.1(6) pm, c = 1183.9(6) pm, α = 114.49(2)°, β = 99.48(3)°, γ = 101.53(1)° for (NH4)4[Nb6Cl12(NCS)6](H2O)4 (3). Each centrosymmetric [Nb6Cl12(NCS)6]4- ion of the isotypic compounds contains six terminal thiocyanate groups being bound to the corners of the octahedral niobium cluster through the nitrogen atoms (dNb—N = 221.5(6)-224.3(6) pm, bond angles Nb—N—C 168.6(5)-176.4(6)°). The [Nb6Cl12(NCS)6]4- ions are linked via A—S and A—Cl interactions with the A cations. Half of the cations occur to be disordered along two crystallographic sites.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 2083-2088 
    ISSN: 0044-2313
    Keywords: Tl3[Nb6SBr17] ; Cs3[Nb6SBr17] ; K3[Nb6SBr17] ; synthesis ; crystal structure ; electronic structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Trigonal-prismatic Nb6-Units in Compounds of the Type A3[Nb6SBr17] (A = Tl, K, Cs)The new compounds A3[Nb6SBr17] (A = Tl, K, Cs) were synthesized and their lattice parameters were calculated from indexed X-ray powder patterns. An intensity measurement based on a single-crystal of Tl3[Nb6SBr17] was performed with an automatic four-circle diffractometer (a = 1704.9(1) pm, b = 1862.8(3) pm, c = 932.51(7) pm; β = 90.747(7)°, Vm = 445.9(3) cm3/mol; C2/c, Z = 4). The structure refinement confirmed consistency with the Rb3[Nb6SBr17] structure, found previously. The comparison of both structures yielded no significant differences concerning the distances within the sulfur-centered Nb6S cluster core.Extended Hückel calculations revealed a maximum of the niobium-niobium overlap populations for (the actual present number of) 14 electrons occupying metal-metal bonding states.
    Notes: Die neuen Verbindungen A3[Nb6SBr17] mit A = Tl, K, Cs wurden dargestellt und ihre Gitterkonstanten aus Röntgen-Pulverdiagrammen ermittelt. An einem Einkristall von Tl3[Nb6SBr17] wurde eine Intensitätsmessung mit einem automatischen Vierkreisdiffraktometer vorgenommen (a = 1704,9(1)pm, b = 1862,8(3)pm, c = 932,51(7)pm; β = 90,747(7)°, Vm = 445,9(3) cm3/mol; C2/c, Z = 4). Die Strukturverfeinerung bestätigte die Übereinstimmung mit der vor kurzem verfeinerten Struktur von Rb3[Nb6SBr17]. Ein Vergleich beider Verbindungen zeigt keine signifikanten Unterschiede der interatomaren Abstände für die schwefelzentrierten Nb6S-Cluster.Extended-Hückel-Berechnungen ergaben ein relatives Maximum der Niob-Niob-Überlappungspopulationen für (die tatsächlich vorliegende Anzahl von) 14 Elektronen in den Metall-Metall-bindenden Zuständen des Clusters.
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