Four new hybrid chloroantimonates(iii) and chlorobismuthates(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 a reaction between Sb2O3/Bi2O3, I2 and the corresponding bis(pyridines) in HCl. Despite sharing the same formulae of supramolecular anionic parts, they showed significant structural diversity, revealing three different structural types. Features of the halogen bond in 1-4 were examined via theoretical methods.