Synthesis and structures of new cyanide and thiocyanate complexes base on Nb6Cli12 cluster core:: Cs4[Nb6Cli12(CNa6]•H2O, Cs4[Nb6Cli12(NCS)a6] and the double salt (Me4N4)4[Nb6Cli12(CN)a6]•2Me4MCl•H2O

The synthesis and structures, determined by X-ray single crystal diffraction, of Cs-4[Nb6Cl12i(CN)(6)(a)].H2O (1), CS4[Nb6Cl12i(NCS)(6)(a)] (2), Me4N)(4)[Nb6Cl12i(CN)(6)(a)].2Me(4)NCl.H2O (3), are reported in this work. Crystal data: Cs-4[Nb6Cl12i(CN)(6)(a)].H2O (1): monoclinic, C2/m a = 11.9804(l) Angstrom, b = 15.3343(1) Angstrom, c = 9.0816(1) Angstrom, beta = 100.34(1)degrees, Z = 2; Cs-4[Nb6Cl12i(NCS)(6)(a)] (2): monoclinic, P2(1)/n, a = 8.7462(3) Angstrom, b = 11.9561(5) Angstrom, c = 20.6206(10) Angstrom, beta = 90.730(2)degrees, Z = 2; (Me4N)(4)[Nb6Cl12i(CN)(6)(a)].2Me(4)NCl.H2O (3): triclinic, P-1, a = 12.7159(1) Angstrom, b = 12.8099(1) Angstrom, c = 12.9326(1) Angstrom, alpha = 64.93(1)degrees, beta = 78.79(1)degrees, gamma = 60.31(1)degrees, Z = 1. They have been prepared via ligand exchange, starting from the CsLuNb6Cl18 precursor synthesized by solid state chemistry techniques. Their structures are based on La units with CN or NCS groups as apical ligands. Structural findings are discussed and compared to related compounds discrete Nb6Cl(12)(i)L(6)(a) previously reported in the literature. (C) 2003 Editions scientifiques et medicales Elsevier SAS. All rights reserved.