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)

Abstract

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 R on | F| were 0·057, 0·037 for N_o 5775, 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 cis in the equatorial plane. BiI₃/phen/dmso (1 : 1 : 1 ) is orthorhombic, Pmc2₁, a 12·745(3), b 9·697(3), c 18·335(5) Å, 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) Å, 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.