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Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes

Martinez, Valentina; Bedeković, Nikola; Stilinović, Vladimir; Cinčić, Dominik (2021) Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes. Crystals, 11 (6). pp. 699-713. ISSN 2073-4352

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In order to study the effect of halogen bond on tautomerism in β-diketones in the solid-state, we have prepared a series of cocrystals derived from an asymmetric β-diketone, benzoyl-4-pyridoylmethane (b4pm), as halogen bond acceptor and perfluorinated iodobenzenes: iodopentaflourobenzene (ipfb), 1, 2-, 1, 3- and 1, 4-diiodotetraflorobenzene (12tfib, 13tfib and 14tfib) and 1, 3, 5-triiodo-2, 4, 6-trifluorobenzene (135titfb). All five cocrystals are assembled by I···N halogen bonds involving pyridyl nitrogen and iodoperfluorobenzene iodine resulting in 1:1 (four compounds) or 1:2 (one compound) cocrystal stoichiometry. Tautomer of b4pm in which hydrogen atom is adjacent to the pyridyl fragment was found to be more stable in vacuo than tautomer with a benzoyl hydroxyl group. This tautomer is also found to be dominant in the majority of crystal structures, somewhat more abundantly in crystal structures of cocrystals in which additional I···O halogen bond with the benzoyl oxygen has been established. Attempts have also been made to prepare an equivalent series of cocrystals using a closely related asymmetric β-diketone, benzoyl-3-pyridoylmethane (b3pm) ; however, all attempts were unsuccessful, which is attributed to more effective crystal packing of b3pm isomer compared to b4pm, which reduced the probability of cocrystal formation.

Item Type: Article
Uncontrolled Keywords: pyridyl-diketone ; halogen bonding ; intramolecular hydrogen bonding ; tautomerization
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Kristalno inženjerstvo višekomponentinih metaloorganksih materijala povezanih halogenskom vezom: ususret supramolekulskom ugađanju strukture i svojstavaCinčić, DominikIP-2014-09-7367HRZZ
Nove građevne jedinke u supramolekulskom dizajnu složenih višekomponentnih molekulskih kristala temeljenih na halogenskim vezamaCinčić, DominikIP-2019-04-1868HRZZ
Depositing User: Valentina Martinez
Date Deposited: 03 Aug 2021 10:41
DOI: 10.3390/cryst11060699

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