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A new W/S/Cu cluster, [Cu(3)WIS(4)(C(21)H(21)O(3)P)(3)]·C(3)H(7)NO, was formed by the reaction of ammonium tetra-thio-tungstate(VI), cuprous iodide and tris-(4-methoxy-phen-yl)phosphine in N,N-dimethyl-formamide. The title compound exhibits a heavily distorted cubane-like skeleton in which the average Cu-I, Cu-S and W-μ(3)-S distances are 2.934, 2.302 and 2.249 Å, respectively. The W atom exhibits tetrahedral geometry, formed by three μ(3)-S and one terminal S atom; the W-S(terminal) bond length is 2.1426 (13) Å. Each Cu atom is coordinated by one P atom from a tris-(4-methoxy-phen-yl)phosphine (mop), two μ(3)-S and one μ(3)-I atom, forming a distorted tetra-hedral coordination geometry. Some of the mop ligand methyl groups have large librations. Together with the three neutral mop ligands, the title compound is neutral; this contrasts with the all-halogen-coordinated Mo/S/Ag clusters with the same structure, which carry negative charge.

acta crystallographica. section e

μ3-Iodo-tri-μ3-sulfido-sulfidotris[tris(4-methoxyphenyl)phosphine-κP]tricopper(I)tungsten(VI)N,N-dimethylformide solvate