Studies on solid state reactions of coordination compounds. LI. Solid state syntheses of a family of Ag-Mo(W)-S cubane-like cluster compounds: Crystal structures of {Ag3MoS3I](PPh3)3S and {Ag3WS3Cl}(PPh3)3S·0.5P(S)Ph3·3H2O†

Reactions of [NH4]2[MS4] (M = Mo, W), AgX (X = Cl, Br, I, ON, SCN) and PPh3 in the solid state produced six new mixed-metal sulfur containing cluster compounds, two of which, {Ag3MoS3I}(PPh3)3S(1) and {Ag3WS3Cl}(PPh3)3S·0.5P(S)Ph3·3H2O(2), were determined by single crystal X-ray analysis. The crystal data: 1, triclinic, P&1bar;, a=12.114(2), b=13.420(2), c=20.346(3)A, a=74.53(1), βequals;86.73(1), γequals;63.74(1)*, Z=2, R = 0.043 for 4805 independent data, 2, hexagonal, R3, a=b=16.201(3), c=45.091(10)A, Z=6, R = 0.042 for 2729 independent data. The central unit {Ag3MS3X} (M = Mo, W; X = Cl, I) of the two compounds can be described as a slightly distorted cube, four corners being formed by the MS42− ligand (with a terminal S atom). The remaining corners are occupied by one X (Cl or I) atom and three Ag atoms (with one PPh3 ligand bound to each of the latter). The generation of different types of Ag-Mo(W)-S cluster compounds prepared from solid state reactions under different reaction temperatures is discussed.