Studies on solid state reactions of coordination compounds. XLVII. Solid state syntheses and crystal structures of cluster compounds {Cu₃MoS₃I} (PPh₃)₃S and {Cu₃WS₃Br} (PPh₃)₃S

Abstract

Abstract Reactions of [NH 4 ] 2 [MS 4 ](M = Mo,W), CuX(X = Br, I) and PPh 3 in the solid state produced four mixed‐metal sulfur containing clusters {Cu 3 MS 3 X}(PPh 3 ) 3 S(M = Mo, W; X = Br, I), two of which (1: M = Mo, X = I; 2: M = W, X = Br) were structurally determined. Crystals of 1 and 2 are triclinic, space group P 1 (1: a = 11.895(3), b = 13.107(1), c = 20.473(2)Å, α = 74.95(6), β = 84.87(8), γ = 64.27(7)°, Z =2, V =2776.1 Å 3 , R w = 0.064 for 6443 observed reflections. 2: a = 11.876 (1), b = 13.065 (2), c = 20.325(2)Å, α = 74.95(1), β= 85.39(1), γ = 64.09(1)°, Z = 2, V = 2737.3Å 3 , R w = 0.055 for ·5303 observed reflections). The results of the structure determination showed that the central units of the two cubane‐like cluster compounds are composed of four metal atoms and four non‐metal atoms situated at alternate corners. The differences of cubane‐like cluster compounds obtained from solid state reactions and from solution reactions are discussed.