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)Å, 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)Å, 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.