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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 Ron |F| were 0·058, 0·055 for No1744, 2068 independent ‘observed’ (I> 3σ(I)) reflections. BiCl3/phen (1 : 2) is monoclinic, P21/C, a9·675(3), b31·845(7), c7·756(2) Å, β 109·94(2), Z= 4, R0·071 for No2537, while BiBr3/phen (1 : 2), also monoclinic, P21/c, has a17·590(5), b8·812(2), c17·537(7) Å, β 117·58(3)°, Z= 4; R0·083 for No890. 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, R0·060, 0·046 for No1553, 2423 respectively. All complexes are mononuclear with seven-coordinate (N2)2BiX3bismuth 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.