Bismuth Compounds [Ph3BuP]~+I-, [Ph3BuP]2[Bi2I8 · 2Me2C=O]~(2-), and [Ph3BuP]2[Bi2I8 · 2Me2S=O]~(2-): Syntheses and Crystal Structures

摘要

The complexes [Ph3BuP]]2 [Bi2I8 · 2Me2C=O]~(2-) (II) and [Ph3BuP]2 [Bi2I8 · 2Me2S=O]~(2-) (III) are synthesized by the reactions of triphenyl(n-butyl)phosphonium iodide (I) with bismuth iodide in acetone and dimethyl sulfoxide. In the cations of complexes I-III, the P atoms have a distorted tetrahedral coordination (CPC angles 106.3(2)°-112.0(3)°). The butyl group in cation I is disordered over two positions. In the binuclear cen-trosymmetric anions of structures II and III, the octahedrally coordinated bismuth atoms are linked in pairs by two bridging (br) iodine atoms (Bi-I_(br) 3.1508(7) and 3.2824(8) A in compound II, 3.1961(3) and 3.3108(3) A in complex III), which are coplanar to four terminal (t) iodine atoms (Bi-I_t 2.9260(7) and 2.9953(6) A in complex II, 2.9206(3) and 2.9786(3) A in complex III). The two remaining positions at the bismuth atom are occupied by the iodine atom (Bi-I_t 2.8531 (7) A in complex II, 2.8984(3) A in complex III) and O atom of the organic molecule (Bi-O 2.747(6) A in complex II, 2.507(3) A in complex III).