Structural studies of group 5B-halide-dithio-ligand complexes. Part 6. Crystal structures of dichloro (NN-diethyldithiocarbamato) tris(pyridine)-bismuth(III)-pyridine (1/1) and its di-iodo-analogue

Recrystallization of [Bi(S₂CNEt₂)X₂], X = Cl, Br, or I, from pyridine solution has been shown to yield adducts Bi(S₂CNEt₂)X₂(py)₄. Single-crystal X-ray structure determinations have shown the three compounds to be isomorphous within a monoclinic unit cell (P2₁/c) with a ca. 13.7, b ca. 14.4, c ca. 16.0 Å, β ca. 93-101°, Z = 4, and to comprise [Bi(S₂CNEt₂)X₂(py)₃] molecules with a further pyridine solvate molecule in the lattice. The bismuth environment is pseudo-seven-co-ordinate, the pyridine ligands being rather loosely bound, and the stereochemistry pseudo-pentagonal bipyramidal, with axial halogen substituents (Bi-Cl,2.6₉; Bi-l, 3.0₆Å).