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)

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,a≈ 14·6, b≈ 9·7, c≈ 9·5 Å, α ≈ 96, β ≈ 96, γ ≈ 98°, Z= 2; conventional Ron | F| were 0·057, 0·037 for No5775, 4847 independent ‘observed’ (I> 3σ(I)) reflections respectively. The metal atom coordination environments are seven-coordinate pentagonal bipyramidal with axial halides and the two O-dmso ligands cisin the equatorial plane. BiI3/phen/dmso (1 : 1 : 1 ) is orthorhombic, Pmc21, a12·745(3), b9·697(3), c18·335(5) Å, Z= 4, R0·049 for No2012. 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, a17·86(2), b12·87(1), c8·47(1) Å, Z= 4, R0·058 for No1194, a neutral mononuclear complex [(bpy)BiI3(O-dmso)] with a six-coordinate array about the metal, O-dmso transto an iodine atom. Bands in the far-infrared and Raman spectra due to the vibrations of the O2N2BiX3cores in [(phen)BiX3(O-dmso)2] (X = Cl, Br) are assigned, and discussed in relation to the structures of the complexes.