Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

Abstract

The complexes [Ph3PMe]2+[BiI5]2− (I) and [Ph3PMe]2+ [BiI5 · C 5H5N]2− · C 5H5N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-CPh 1.779(2), P-CMe 1.793(1) A. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-Ieq 3.0031(4), Bi-Ieq 3.0485(5) A). The crystal of complex II consists of the anions [BiI5 · C 5H5N]2−, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-CPh 1.785(3)–1.792(3), P-CMe 1.793(3), 1.786(3) A). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) A).