Structural studies of group 5B–halide–dithio-ligand complexes. Part 1. Crystal structures of bis(NN-diethyldithiocarbamato)-iodo- and -bromo-bismuth(III)

Abstract

The crystal structures of the two compounds [Bi(S₂CNEt₂)₂l], (1), and [Bi(S₂CNEt₂)₂Br], (2), have been determined by single-crystal X-ray diffraction methods at 295(1) K and refined by least-squares procedures to conventional residuals of 0.044 and 0.040 respectively for 1 859 and 3 055 ‘observed’ reflections. Crystals of (1) are monoclinic, space group P2₁/c, with a= 12.054(2), b= 18.444(3), c= 8.815(2)Å, β= 108.09(1)°, and Z= 4. The structure is a linear polymer with bridging iodine atoms cis in the co-ordination sphere of the six-co-ordinate bismuth [Bi–l, 3.257(2), 3.354(1)Å; Bi–S, 2.646(4)–2.860(5)Å]. Crystals of (2) are triclinic, space group P with a= 14.388(7), b= 14.033(5), c= 10.297(2)Å, α= 99.56(2), β= 104.70(3), γ= 108.10(3)°, and Z= 4. The structure comprises a tetranuclear centrosymmetric unit with the bismuth atoms bridged by two- and three-co-ordinate bromine atoms.