Preparation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1(-))] complexes, [Sb-v(dmit)(3)](-). Crystal structure of the 1,4-dimethylpyridinium salt

Ionic complexes, [Q] [Sb(dmit)(3)] [Q = 1,4-MR(2)-pyridinium or NEt(4)], have been isolated from the reaction of [Q], [Zn(dmit)(2)] and SbI5, prepared in situ from SbI3 and I-2 (H-2-dmit = 4,5-dimercapto-1,3-dithiole-2-thione). A crystal structure determination of [1,4-Me(2)-pyridinium] [Sb(dmit)] revealed that the anions contain octahedral Sb atoms, with Sb-S bond lengths between 2.504(1) and 2.553(1) Angstrom. The chelate bite angles are in the range 80.30(4)-83.50(5)degrees. Sulfur-sulfur contacts, at distances less than the van der Waals radii, link the anions into a 3-D (three-dimensional) framework: each of the three dmit ligands in an anion have weak S- - -S interactions with neighbouring anions. Copyright (C) 1996 Elsevier Science Ltd