Synthesis and Crystal Structure of α-Mo4XS3(μ-dtp)3(dtp)3 (X=0.6S + 0.4O)

The title compound (Mo4XS15P6O12C24H30), α-Mo4XS3(μ-dtp)3(dtp)3 (X=0.6S+0.4O; dtp=-S2P[OEt]2), isolated as a prismatic black crystal, was prepared from ethanolic solution of Mo(CO)6, MoCl5 and P2S5. It crystallizes in triclinic system, space group P with a=14.031(4), b=13.372(2), c=16.270(8)(A), α=92.15(2), β = 72.91(3), γ = 95.20(2)°, V = 2905.4(2)(A)3, Z = 2, Dc = 1.82 g/cm3, Mr=1598.93, F(000)=1564.8, λ=0.71069(A)(MoKα), μ=1.584 mm-1. The final R=0.058, Rw=0.057 for 5016 observed reflections with I≥3.0σ(I). The structure analysis reveals that the title compound has a [Mo4XS3] core, belonging to the cubane-type tetranuclear molybdenum clusters family, with one of its four μ3-caps being statistically occupied by S and O. Three dtp ligands chelated three μ-X capped Mo atoms as terminal ligands, while another three dtp bridged these three Mo atoms and the fourth one, forming an α-type cluster compound.