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

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 Å) based on zero-, one-, two- and three- dimensional halogen-bonded architectures.

halogen bond ; metal-organic cocrystals ; supramolecular architectures ; liquid-assisted grinding

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