Synthesis and structures of new cyanide and thiocyanate complexes based on Nb_6C1_(12)~i cluster core: Cs_4[Nb_6C1_(12)~i (CN)_6~a] .H_2O, Cs_4[Nb_6Cl_(12)~i (NCS)_6~a] and the double salt (Me_4N)_4[Nb_6C1_(12)~i (CN)_6~a] 2Me_4NCl H_2O

摘要

The synthesis and structures, determined by X-ray single crystal diffraction, of CS_4[Nb_6Cl_(12)~i(CN)_6~a].H_2O (1), Cs_4[Nb_6Cl_(12)~i(NCS)_6~a] (2), (Me_4N)_4[Nb_6Cl_(12)~i(CN)_6~a].2Me_4NC1.H_2O (3), are reported in this work. Crystal data: Cs_4[Nb_6C1_(12)~i(CN)_6~a].H_2O (1): monoclinic, C2/m, a = 11.9804(1) A, b = 15.3343(1) A, c = 9.0816(1) A, beta = 100.34(1)~centre dot, Z = 2; Cs_4[Nb_6Cl_(12)~i(NCS)_6~a] (2): monoclinic, P2_1, a = 8.7462(3) A, b = 11.9561(5) A, c = 20.6206(10) A, beta = 90.730(2)~centre dot, Z = 2; (Me_4N)_4[Nb_6Cl_(12)~i(CN)_6~a].2Me_4NCI.H_2O (3): triclinic, P-l, a = 12.7159(1) A, b = 12.8099(1) A, c = 12.9326(1) A, alpha = 64.93(1)~centre dot, beta = 78.79(l)~centre dot, gamma = 60.31(l)~centre dot, Z = 1. They have been prepared via ligand exchange, starting from the CsLuNb_6Cl_(18) precursor synthesized by solid state chemistry techniques Their structures are based on discrete Nb_6C1_(12)~iL_6~a units with CN or NCS groups as apical ligands. Structural findings are discussed and compared to related compounds previously reported in the literature.