Synthesis and structure of the first neutral octahedral cis-dioxorhenium(V) complex

The reaction of 1 mole equivalent of sulfuryl chloride with N-methylbenzothiazole-2-selone, mbts, produces the yellow 1:1 addition compound, mbts·Cl2 (1), which exhibits a T-shaped geometry with intermolecular Cl–Cl interactions. These give rise to a novel ‘zipper’ packing arrangement of linear chains of ClSeClClSeCl atoms in the crystalline state. Both T-shaped ClSeCl and linear SeCl⋯Cl moieties can be observed because of this; the latter interaction being essentially ionic rather than charge transfer. FT-Raman studies imply the presence of a green metastable isomer (2) of 1. Compound 1 represents the first structurally characterised 1:1 dichloride adduct of the form R2CSeCl2.