Synthetic, structural and vibrational spectroscopic studies in bismuth(III) halide N,N′-aromatic bidentate base systems.: II.: Bipyridinium (2,2′-bipyridine)tetrahalobismuthate(III) (halogen = chloride or bromide)

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for the title compounds, [bpyH](+)[(bpy)BiX4](-), X = Cl, Br, the chloride being obtained in a second acetonitrile-sesquisolvated form. [bpyH](+)[(bpy)BiX4](-), X = Cl, Br, are isomorphous, monoclinic C2/c, a approximate to 15.3, b approximate to 9.6, c approximate to 16.8 Angstrom, beta 109 degrees, Z = 4, conventional R on \F\ being 0.056, 0.059 for N-o 1456, 769 independent 'observed' (I > 3 sigma(I)) reflections respectively. [bpyH][(bpy)BiCl4]. 11/2MeCN is monoclinic, P 2(1)/m, a 9.572(2), b 34.521(8) c 8.218(2) Angstrom, beta 102.13(2)degrees, Z = 4, R 0.043 for N-o 2635. All anionic species are mononuclear, the bismuth being quasi-octahedral. Bands in the far-infrared and Raman spectra due to the vibrations of the N2BiCl4 core in [(bpy)BiCl4](-) are assigned, and their relationship to the vibrations of [BiCl6](3-) is discussed.