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.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220306
Permalink
