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Hybrid Network Formation via Halogen Bonding of the Neutral Bromo-Substituted Organic Molecules with Anionic Metal–Bromide Complexes
journal contribution
posted on 2012-08-01, 00:00 authored by Sergiy V Rosokha, Michael K. VinakosX-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 together disparate partners such as neutral
aliphatic molecules and ionic salts and is able to accommodate a variety
of geometries of the interacting species. Comparison of the intermolecular
contact locations with the surface electrostatic potentials and molecular
orbital shapes of the bromometallates suggests the importance of the
covalent component in halogen bonding.