SYNTHETIC, STRUCTURAL AND VIBRATIONAL SPECTROSCOPIC STUDIES IN BISMUTH(III) HALIDE N,N'-AROMATIC BIDENTATE BASE SYSTEMS - 5 - BISMUTH(III) HALIDE N,N'-BIDENTATE LIGAND(1 2) SYSTEMS/

Syntheses and room-temperature single-crystal X-ray determinations are recorded for a number of adducts of BiX3/N,N'-bidentate 1:2 stoichiom etry (N,N'-bidentate = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (p hen)). BiX3/bpy (1:2), X = Br, I, are isomorphous, monoclinic, P2(1)/c , a approximate to 7.5, b approximate to 31, c approximate to 10.3 Ang strom, beta approximate to 113 degrees, Z = 4; conventional R on \F\ w ere 0.058, 0.055 for N-o 1744, 2068 independent 'observed' (I > 3 sigm a(I)) reflections. BiCl3/phen (1:2) is monoclinic, P2(1)/c, a 9.675(3) , b 31.845(7), c 7.756(2) Angstrom, beta 109.94(2), Z = 4, R 0.071 for N-o 2537, while BiBr3/phen (1:2), also monoclinic, P2(1)/c, has a 17. 590(5), b 8.812(2), c 17.537(7) Angstrom, beta 117.58(3)degrees, Z = 4 ; R 0.083 for N-o 890. BiX3/phen (1:2).S, X/S = Br/MeCN, I/CH2Cl2, are isomorphous, orthorhombic, Pna2(1), a approximate to 20.7, b approxim ate to 14.2, c approximate to 8.9 Angstrom, Z = 4, R 0.060, 0.046 for N-o 1553, 2423 respectively. All complexes are mononuclear with seven- coordinate (N-2)(2)BiX3 bismuth environments. Bands in the far-infrare d spectra due to the nu(BiX) vibrations in [(phen)(2)BiCl3] and [(bpy) (2)BiX3] (X = Br, I) are assigned and discussed in relation to the str uctures of the complexes.