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-μ3-iodo-hexa-μ2-iodo-dodeca­iodo­hexa­bismuthate, (C10H9N2)4[Bi6I22], crystallizes in the triclinic space group P\overline{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-μ4-iodo-octa-μ2-iodo-dodeca­iodo­hexa­bismuthate, [Ru(C10H8N2)3]2[Bi6I22], which also crystallizes in the triclinic space group P\overline{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.