Synthetic, structural and vibrational spectroscopic studies in bismuth(III) halide N,N′-aromatic bidentate base systems.: III.: Some novel bismuth(III) halide N,N′-bidentate ligand (1:1) dimethyl sulfoxide solvates

Syntheses and single-crystal room-temperature X-ray structure determinations are recorded for a number of adducts obtained by the crystallization of bismuth(III) halides with 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) from dimethyl sulfoxide (dmso) solution. [(phen)BiX3(O-dmso)(2)].dmso, X = Cl, Br, are triclinic, <P(1)over bar>, a approximate to 14.6, b approximate to 9.7, c approximate to 9.5 Angstrom, alpha approximate to 96, beta approximate to 96, gamma approximate to 98 degrees, Z = 2; conventional R on \F\ were 0.057, 0.037 for N-o 5775, 4847 independent 'observed' (I > 3 sigma(I)) reflections respectively. The metal atom coordination environments are seven-coordinate pentagonal bipyramidal with axial halides and the two O-dmso ligands c is in the equatorial plane. BiI3/phen/dmso (1:1:11/2) is orthorhombic, Pmc2(1), a 12.745(3), b 9.697(3), c 18.335(5) Angstrom, Z = 4, R 0.049 for N-o 2012. The complex is ionic [(phen)BiI2(O-dmso)(3)](+)[(phen)BiI4](-), the halide atoms being axial in a pentagonal bipyramidal array about the metal in the cation, with a quasi-octahedral coordination environment in the anion. With bpy, by contrast, BiI3/bpy/dmso (1:1:1) is obtained, orthorhombic, Pnma, a 17.86(2), b 12.87(1), c 8.47(1) Angstrom, Z = 4, R 0.058 for N-o 1194, a neutral mononuclear complex [(bpy)BiI3(O-dmso)] with a six-coordinate array about the metal, O-dmso trans to an iodine atom. Bands in the far-infrared and Raman spectra due to the vibrations of the O2N2BiX3 cores in [(phen)BiX3(O-dmso)(2)] (X = Cl, Br) are assigned, and discussed in relation to the structures of the complexes.