Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/N,N′-Aromatic Bidentate Base Systems. II Bipyridinium (2,2' Bipyridine) tetraholobismuthate (III) (Halogen = Chloride or Bromide)

Abstract

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 ≈ 15·3, b ≈ 9·6, c ≈ 16·8 Å, β 109°, Z = 4, conventional R on |F| being 0·056, 0·059 for N_o 1456, 769 independent ‘observed’ (I > 3σ(I)) reflections respectively. [bpyH] [(bpy)BiCl₄].1½MeCN is monoclinic, P2₁/m, a 9·572(2), b 34·521(8) c 8·218(2) Å, β 102·13(2)°, 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.