Antimony vs bismuth: structural differences in Cat{[MCl5](I2)} halogen bond-linked supramolecular complexes

Four new hybrid chloroantimonates(III) and chrorobismuthates(III) with halogen bond-linked I2, (H2bpe){[MCl5](I2)} (M = Sb(III) (1); M = Bi(III) (2); bpe – 1,2-bis(4-pyridil)ethane) and (H2bpp){[MCl5](I2)} – (M = Sb(III) (3); M = Bi(III) (4); bpp = 1,3-bis(4-pyridil)propane)) were synthesized via reaction between Sb2O3/Bi2O3, I2 and corresponding bis(pyridines) in HCl. Despite sharing the same formulae of supramolecular anionic parts, they show significant structural diversity, revealing three different structural types. Features of halogen bond in 1-4 were examined by theoretical methods.