[Mo2S10]2-, a complex with terminal sulfido, bridging sulfido, persulfido, and tetrasulfido groups

Article abstract of DOI:10.1021/ic50219a045

The complex [Mo₂S₁₀]^2- has been isolated as one product of the reaction between [NH₄]₂[Mo₂S₁₂] and PhSNa (1:16) in MeOH/Me₂SO (10:1). [AsPh₄]₂[Mo₂S₁₀]·0.5MeCN crystallizes in the triclinic space group P1 (Z = 2), with a = 10.489 (2) A?, b = 11.756 (2) A?, c = 21.856 (4) A?, α = 77.11 (2)°, β = 85.46 (2)°, and γ = 77.92 (2)°. The structure has been determined from 6774 X-ray counter intensities by Patterson and Fourier techniques and refined by full-matrix least-squares methods to R = 0.054 (0.064 weighted). The anion has a terminal sulfido group bonded to each of the molybdenum atoms (Mo-S = 2.110 (2) A?) which are bridged by two μ-sulfido groups (Mo-S = 2.289 (2)-2.351 (2) A?); one of the molybdenum atoms is also coordinated to a persulfido group (Mo-S = 2.395 (3), S-S = 2.071 (3) A?) whereas the other is bonded to a tetrasulfido group (Mo-S = 2.406 (3) A?). The two central atoms of the tetrasulfido group are disordered and this disorder has been refined in terms of an 80-20% distribution of two components; in each case the length of the S-S bond involving the noncoordinated sulfur atoms (1.970 (6) A? for the major component) is significantly shorter than those involving a coordinated sulfur atom (2.018 (5) and 2.116 (5) A? for the major component).