Tetrakis[2-(2-pyridyl)pyridinium] tetra-mu3-iodo-hexa-mu2-iodo-dodecaiodohexabismuthate and bis[tris(2,2'-bipyridine)ruthenium(II)] di-mu4-iodo-octa-mu2-iodo-dodecaiodohexabismuthate.

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-mu3-iodo-hexa-mu2-iodo-dodecaiodohexabismuthate, (C10H9N2)4[Bi6I22], crystallizes in the triclinic space group P-1 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-mu4-iodo-octa-mu2-iodo-dodecaiodohexabismuthate, [Ru(C10H8N2)3]2[Bi6I22], which also crystallizes in the triclinic space group P-1. 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.