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Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2'-bipyridine and bismuth triiodide as starting materials. Tetrakis[2-(2-pyridyl)pyridinium] tetra-3-iodo-hexa-2-iodo-dodecaiodohexabismuthate, (C10H9N2)4[Bi6I22], crystallizes in the triclinic space group P and is the major reaction product. The asymmetric unit of this compound consists of half a centrosymmetric [Bi6I22]4- anion and two independent 2,2'-bipyridinium cations. The minor product of the reaction is bis[tris(2,2'-bipyridine)ruthenium(II)] di-4-iodo-octa-2-iodo-dodecaiodohexabismuthate, [Ru(C10H8N2)3]2[Bi6I22], which also crystallizes in the triclinic space group P. For this compound, the asymmetric unit consists of one full [Ru(2,2'-bipyridine)3]2+ cation and half a centrosymmetric [Bi6I22]4- anion. Although both compounds contain a centrosymmetric [Bi6I22]4- anion, the polyhedral arrangement of the distorted BiI6 octahedra in the two compounds is quite different, and the anion of the latter compound has not previously been observed in iodobismuthate chemistry.

Formula: (C10H9N2)4[Bi6I22] and [Ru(C10H8N2)3][Bi6I22]

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