Isopoly- und Heteropoly-Thioanionen. Kristall- und Molekülstrukturen von (PPh₄)₂[(WS₄)WS(WS₄)],CS₂[(WS₄)WO(WS₄)H₂O]·2H₂O und (AsPh₄)₂[(WS₄)Ni(WS₄)]/Isopoly- and Heteropoly-Thioanions. Crystal and Molecular Structures of (PPh₄)₂[(WS₄)WS(WS₄)], Cs₂[(WS₄)WO(WS₄)H₂O] · 2 H₂O and (AsPh₄)₂[(WS₄)Ni(WS₄)]

Abstract

The crystal and molecular structures of (PPh 4 ) 2 [(WS 4 )WS(WS 4 )] (1a) and CS 2 [(WS 4 )WO(WS 4 )H 2 O] · 2 H 2 O (2a), which contain the first reported isopoly-thioanion of a transition metal have been determined: 1a: (P1̅, a = 913.0(1), b = 1060.1(2), c = 1333.9(2) pm, α = 87.11(1), β = 85.18(1), γ = 83.07(1)°, V = 1277.6 · 10 6 pm 3 , Z = 1); 2a: (P2 1 /n, a = 671.6(2), b = 2018.5(4), c = 714.4(2) pm, β = 101.42(2)°, V = 949,3 · 10 6 pm 3 , Z = 2) and compared with that of the trimetallic heteropoly-thioanion of (AsPh 4 ) 2 [(WS 4 )Ni(WS 4 )] (3a). 3a: (P1̄, a = 1255.2(3), b = 1277.1(3), c = 939.0(2) pm, α = 113.19(2), β = 96.28(2), γ = 108.72(2)°, V = 1261.5 · 10 6 pm 3 , Z = 1). Though there are delocalized orbitals in the isopoly-thioanions they can be regarded as coordination compounds of W IV X 2+ containing two W VI S 4 2- ligands.