Hybrid Network Formation via Halogen Bonding of the Neutral Bromo-Substituted Organic Molecules with Anionic Metal–Bromide Complexes

Abstract

X-ray measurements revealed that cocrystallization of various bromocarbons and tetraalkylammonium bromometallate salts lead to the formation of hybrid 3D-networks, which show short intermolecular C–Br···Br–M contacts resulting from halogen bonding between electrophilic organic species and anionic metal–bromide complexes. In particular, halogen bondings of carbon tetrabromide with [MBr4]2– complexes (M = Co, Zn, Cd) produce diamandoid networks in which nodes are occupied interchangeably by tetrahedral organic and inorganic counterparts. (NBu4)2[ZnBr4]·C3Br2F6 structure comprises diamandoid-like network in which nodes are occupied by the tetrahedral [ZnBr4]2– species connected via pairs of bromine substituents in C3Br2F6. Halogen bonding of planar [Pt2Br6]2– complexes with CBr4 and linear [CuBr2]− complexes with CHBr3 produces 3D-networks consisting of interconnected ladders. The structural characterization of this series of hybrid networks demonstrates that halogen bonding is strong enough to bring togethe...