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Exploring the Halogen-Bonded Cocrystallization Potential of a Metal-Organic Unit Derived from Copper(II) Chloride and 4-Aminoacetophenone

In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(II) complex and 1, 4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted grinding) and the conventional solution-based method. Crystal structure determination by single crystal X-ray diffraction revealed that the dominant supramolecular interactions are the I...O halogen bond between 14tfib and CuCl2(aap)2 building blocks, and the N–H...Cl hydrogen bonds between CuCl2(aap)2 molecules. The combination of halogen and hydrogen bonding leads to the formation of a 2D network. Overall, this work showcases an example of the possibility for extending the complexity of metal-organic crystal structures by using halogen bonding in a way that does not affect other hydrogen bonding synthons.

halogen bonding ; hydrogen bonding ; cocrystals ; liquid assisted grinding ; coordination compounds

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