Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. V Bismuth(III) Halide/N,N′-Bidentate Ligand (1 : 2) Systems

Abstract

Syntheses and room-temperature single-crystal X-ray determinations are recorded for a number of adducts of BiX₃/N,N′-bidentate 1 : 2 stoichiometry (N,N′-bidentate = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen)). BiX₃/bpy (1 : 2), X = Br, I, are isomorphous, monoclinic, P2₁/c, a ≈ 7·5, b ≈ 31, c ≈ 10·3 Å, β ≈ 113°, Z = 4; conventional R on |F| were 0·058, 0·055 for N_o 1744, 2068 independent ‘observed’ (I > 3σ(I)) reflections. BiCl₃/phen (1 : 2) is monoclinic, P2₁/C, a 9·675(3), b 31·845(7), c 7·756(2) Å, β 109·94(2), Z = 4, R 0·071 for N_o 2537, while BiBr₃/phen (1 : 2), also monoclinic, P2₁/c, has a 17·590(5), b 8·812(2), c 17·537(7) Å, β 117·58(3)°, Z = 4; R 0·083 for N_o 890. BiX₃/phen (1 : 2).S, X/S = Br/MeCN, I/CH₂Cl₂, are isomorphous, orthorhombic, Pna2₁, a ≈ 20·7, b ≈ 14·2, c ≈ 8·9 Å, Z = 4, R 0·060, 0·046 for N_o 1553, 2423 respectively. All complexes are mononuclear with seven-coordinate (N₂)₂BiX₃ bismuth environments. Bands in the far-infrared spectra due to the v(BiX) vibrations in [(phen)₂BiCl₃] and [(bpy)₂BiX₃] (X = Br, I) are assigned and discussed in relation to the structures of the complexes.