COMPLEXES OF GROUP-15 METALS WITH STERICALLY HINDERED THIOLATE LIGANDS - CRYSTAL AND MOLECULAR-STRUCTURES OF [SB(2-SC5H4N)3], [SB(2-SC5H3N-3-SIME3)3], AND [BI(2-SC5H3N-3-SIME3)3]

The complexes [Sb(2-C5H4N)3] (1), [Sb(2-SC5H3N-3-SiMe3)3] (2), and [Bi(2-SC5H3N-3-SiMe3)3] (3) were prepared from the reaction of the appropriate metal salt and the ligand in methanol. The structure of 1 consists of a distorted octahedral arrangement of S and N donors, which adopt a facial ligand arrangement. The stereochemically active lone pair of the Sb(III) center occupies a position capping the N3 face of the octahedron. In contrast, the donor groups in 2 are so disposed that the lone pair occupies an octahedral vertex trans to a sulfur donor, with one nitrogen donor now defining the face capping position. The structure of the bismuth derivative (3) is analogous to that of 2. Crystal data: C15H12N3S3Sb (1); trigonal R3cBAR, a = 12.562 (2) angstrom, c = 37.960 (4) angstrom, V = 5187.6 (10) angstrom 3, Z = 12, R = 0.026; C24H36N3Si3S3Sb (2), monoclinic P2(1)/c, a = 17.876 (3) angstrom, b = 10.772 (2) angstrom, c = 18.617 (4) angstrom, beta = 116.08 (1)-degrees, V = 3219.8 (11) angstrom 3, Z = 4, R = 0.028; C24H36N3Si3S3Bi (3), monoclinic C2/c, a = 24.682 (4) angstrom, b = 12.927 (2) angstrom, c = 24.782 (4) angstrom, beta = 123.04 (1)-degrees, V = 6629.1 (12) angstrom 3, Z = 8, R = 0.049.