Halogen Bonding Assembles Anion⋅⋅⋅Anion Architectures in Non‐centrosymmetric Iodate and Bromate Crystals

Abstract

AbstractSingle crystal X‐ray diffraction of iodate and bromate salts shows that the I and Br atoms in IO3− and BrO3− anions form short and linear O−I/Br⋅⋅⋅O contacts with the O atoms of nearby anions. Non‐centrosymmetric systems are formed wherein anions are orderly aligned into supramolecular 1D and 2D networks. Theoretical evidences, namely the outcome of QTAIM and NCIplot studies, prove the attractive nature of these contacts and the ability of iodate and bromate anions to act as robust halogen bond (HaB) donors. The HaB is proposed as a general and effective assisting tool to control the architecture of acentric iodate salts.