Simple design for metal-based halogen-bonded cocrystals utilizing the M–Cl?I motif?

CrystEngComm Pub Date: 2018-06-06 DOI: 10.1039/C8CE00754C

Abstract

We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing metal complexes whose pendant chloride group enables halogen bonding. A series of 12 cocrystals involving octahedral CoCl2L2 complexes (L = 2,2′-bipyridine or 1,10 phenantroline) as halogen bond acceptors were prepared by both liquid-assisted grinding and conventional solution-based methods. The efficacy of this strategy is evident by the assembly of a large family of cocrystals involving six perfluorinated halogen bond donors: 1,4-diiodotetrafluorobenzene, 1,3-diiodotetrafluorobenzene, 1,2-diiodotetrafluorobenzene, 1,3,5-triiodotrifluorobenzene, iodopentafluorobenzene and octafluoro-1,4-diiodobutane. Single crystal X-ray diffraction experiments have shown that cocrystals display different crystal packing governed by Cl?I halogen bonds between halogen bond donor iodine atoms and metal complex chlorine atoms (varying from 3.061 to 3.471 ?) based on zero-, one-, two- and three- dimensional halogen-bonded architectures.

Graphical abstract: Simple design for metal-based halogen-bonded cocrystals utilizing the M–Cl?I motif
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