Tetra­kis[2-(2-pyridyl)pyridinium] tetra-μ₃-iodo-hexa-μ₂-iodo-dodeca­iodo­hexa­bismuthate and bis­[tris­(2,2′-bipyridine)ruthenium(II)] di-μ₄-iodo-octa-μ₂-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 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. 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.