Supramolecular diiodo-chlorometalates(iii) of group 15 elements with halogen-substituted pyridiniums: an interplay of cation⋯anion and I2⋯halometalate halogen bonds

Abstract

Four new hybrid polychloro-iodometallates with halogen-substituted cations (3-BrPyH)₂{[MCl₅](I₂)} (M = Sb(III) (1) and M = Bi(III) (2)) and (3-ClPyH)₂{[MCl₅](I₂)} (M = Sb(III) (3) and M = Bi(III) (4)) were synthesized. The halogen bond formation ability of the Br atom in 1 and 2 is prominent, which is confirmed by a comparison of the noncovalent contact energies in 1–4. The relationship of thermal stability and optical properties with structural parameters is discussed in detail.