SYNTHESIS AND CRYSTAL-STRUCTURE OF [LI(THF)4]2[BI4I14(THF)2], [LI(THF)4]4[BI5I19], AND (PH4P)4[BI6I22]

Solutions of BiI3 in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19], [Na(thf)6]4[Bi6I22] and (Ph4P)4[Bi6I22] are described. The anions of these compounds consist of edge-sharing BiI6 and BiI5(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)4]2[Bi4I14(thf)2]: Space group P1BAR (No. 2), a = 1159.9(6), b = 1364.6(7), c = 1426.5(7) pm, alpha = 114.05(3), beta = 90.01(3), gamma = 100.62(3)-degrees. [Li(thf)4]4[Bi5I19]: Space group P2(1)/n (No. 14), a = 1653.0(9), b = 4350(4), c = 1836.3(13) pm, beta = 114.70(4)-degrees. [Na(thf)6]4[Bi6I22]: Space group P2(1)/n (No. 14), a = 1636.4(3), b = 2926.7(7), c = 1845.8(4) pm, beta = 111.42(2)-degrees. (Ph4P)4[Bi6I22]: Space group P1BAR (No. 2), a = 1368.6(7), b = 1508.1(9), c = 1684.9(8) pm, alpha = 98.28(4), beta = 95.13(4), gamma = 109.48(4)-degrees.