Synthesis and X-ray crystal structure of trichlorotris[1-phenyl-3-(2-pyridyl)-2-thiourea-S]bismuth(III) and di-µ-chloro-tetrachlorotetrakis(NN′-diethylimidazolidine-2-thione-S)dibismuth(III)

Abstract

Two complexes of bismuth, [BiCl₃(pptu)₃](1) and [{BiCl₃(deimdt)₂}₂](2)[pptu = 1-phenyl-3-(2-pyridyl)-2-thiourea, deimdt =NN′-diethylimidazolidine-2-thione], have been synthesized and characterized by elemental analysis, i.r. spectra, and X-ray single-crystal structure determination. Compound (1) is triclinic, a= 10.028(2), b= 11.380(4), c= 9.668(3)Å, α= 112.56(1), β= 103.61(2), γ= 95.22(2)°, Z= 1, space group P; R= 0.057 for 2 876 ‘observed’ data. The bismuth atom, at the origin of the cell, is octahedrally surrounded by two chlorines, two sulphurs from two ligand molecules and one sulphur from a further ligand molecule which is disordered with one chlorine with populations of 50%. Crystals of (2) are monoclinic, a= 13.050(5), b= 15.400(7), c= 13.171(7)Å, β= 117.99(1)°, Z= 2, space group P2₁/n; R= 0.051 for 2 306 ‘observed’ data. Co-ordination around bismuth is rather distorted octahedral involving two sulphurs from two ligands and four chlorines; two of them, more loosely bonded, bridge two adjacent co-ordinated polyhedra forming a dimeric complex molecule.