Reactions of tetrasulphur tetranitride with titanium and vanadium tetrachlorides; crystal structure of VCl2(S2N3)

Tetrasulphur tetranitride reacts with excess of VCl4 in CH2Cl2to form a mixture of VCl2(S2N3)(2) and S2N2·VCl4(3), whereas with excess of TiCl4 only S4N4·TiCl4(1) is formed. Crystals of (2) are triclinic, space group P, with a= 571.3(2), b= 695.7(3), c= 772.9(3) pm, α= 95.38(3), β= 99.62(3), γ= 97.58(3)°, and Z= 2. The structure was refined to R= 0.053 for 1 601 unique observed diffractometer data. It consists of chlorine-bridged dimers, linked by additional weak V–N interactions to form polymeric chains. The six-membered VNSNSN ring is effectively planar.