Researchers from the Department of Chemistry Lidija Posavec and Dominik Cinčić have published an article titled The Isothiocyanate Sulfur Atom as an Acceptor Site for Halogen-Bonded Cocrystallization of Werner Ni(II) Coordination Compounds and Perfluorinated Iodobenzenes in the ACS journal Crystal Growth & Design (IF 3,2).
The manuscript presents a systematic study of the halogen bond acceptor potential of the isothiocyanate sulfur atom in the synthesis of cocrystals involving metal-organic building blocks, by using Werner Ni(II) coordination compounds whose pendant isothiocyanate group enables halogen bonding. For this purpose, we prepared a series of 14 cocrystals involving octahedral Ni(L)4(NCS)2 coordination compounds (L = pyridine or 4-methylpyridine) by both crystallization from solution and liquid-assisted grinding. Our results demonstrate the effectiveness of this strategy by the assembly of a large family of cocrystals involving five perfluorinated iodobenzenes. For both coordination compounds, we generally obtained one cocrystal with each donor, in one case we obtained an additional two stoichiomorphs, and in another three additional solvates. Single crystal X-ray diffraction experiments revealed that building units in all cocrystals are connected via S∙∙∙I halogen bonds involving the donor iodine atom and the isothiocyanate sulfur atom which is an acceptor of two, and in some cases, even three halogen bonds. Consequently, both coordination compounds act as multitopic acceptors that can form multiple halogen bonds leading to the formation of one-, two- and three-dimensional halogen-bonded architectures.
This research was performed as part of the project New building blocks for the supramolecular design of complex multi-component molecular crystals based on halogen bonds (HaloBond IP-2019-04-1868), financed by the Croatian Science Foundation
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