Abstract[V2(μ‐S2)2(S2CNEt2)4] 2CH3Cl was synthesized by the reaction of NaS2CNEt2, Li2S and VOCl3at room temperature. Crystal data:M= 1061.3, space groupPbca, with the orthorhombic parameters:a=20.123(3),b= 20.485(4)1c=10.911(3)A,V=4497.7Å3,Z=4,Dc=1.57 g/cm3, MoKoradiation (λ=0.71069 Å), μ = 13.2 cm−1,F(000)—2168. FinalR= 0.041 andRw=0.047 for 2288 observed reflections withI>3σ(I). The coordination sphere of each V atom in title compound is a distorted tetragonal prism composed of two bidentate dithiocarbamate and two S21−ligands. The V—V distance is 2.890 Å while the V—S distances fall in the rang