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The Amine Group as Halogen Bond Acceptor in Cocrystals of Aromatic Diamines and Perfluorinated Iodobenzenes
Article

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

1
Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102A, 10 000 Zagreb, Croatia
2
Ruđer Bošković Institute, Bijenička cesta 54, 10 000 Zagreb, Croatia
*
Authors to whom correspondence should be addressed.
Academic Editors: Sergiy Rosokha and Atash V. Gurbanov
Crystals 2021, 11(6), 699; https://doi.org/10.3390/cryst11060699
Received: 20 May 2021 / Revised: 14 June 2021 / Accepted: 16 June 2021 / Published: 18 June 2021
(This article belongs to the Special Issue Advanced Research in Halogen Bonding)
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. View Full-Text
Keywords: pyridyl-diketone; halogen bonding; intramolecular hydrogen bonding; tautomerization pyridyl-diketone; halogen bonding; intramolecular hydrogen bonding; tautomerization
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MDPI and ACS Style

Martinez, V.; Bedeković, N.; Stilinović, V.; Cinčić, D. Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes. Crystals 2021, 11, 699. https://doi.org/10.3390/cryst11060699

AMA Style

Martinez V, Bedeković N, Stilinović V, Cinčić D. Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes. Crystals. 2021; 11(6):699. https://doi.org/10.3390/cryst11060699

Chicago/Turabian Style

Martinez, Valentina, Nikola Bedeković, Vladimir Stilinović, and Dominik Cinčić. 2021. "Tautomeric Equilibrium of an Asymmetric β-Diketone in Halogen-Bonded Cocrystals with Perfluorinated Iodobenzenes" Crystals 11, no. 6: 699. https://doi.org/10.3390/cryst11060699

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