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

Autori
Uran, Erik ; Fotović, Luka ; Bedeković, Nikola ; Stilinović, Vladimir ; Cinčić, Dominik

Izvornik
Crystals (2073-4352) 11 (2021), 5; 529-541

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
halogen bonding ; aromatic diamines ; perfluorinated iodobenzenes ; amine group

Sažetak
In order to study the proclivity of primary amine groups to act as halogen bond acceptors, three aromatic diamines (p-phenylenediamine (pphda), benzidine (bnzd) and o-tolidine (otol)) were cocrystallised with three perfluorinated iodobenzenes (1, 4- tetrafluorodiiodobenzene (14tfib), 1, 3- tetrafluorodiiodobenzene (13tfib) and 1, 3, 5- trifluorotriiodobenzene (135tfib)) as halogen bond donors. Five cocrystals were obtained: (pphda)(14tfib), (bnzd)(13tfib)2, (bnzd) (135tfib)4, (otol)(14tfib) and (otol) (135tfib)2. In spite of the variability of both stoichiometries and structures of the cocrystals, in all the prepared cocrystals the amine groups form exclusively I···N halogen bonds, while the amine hydrogen atoms participate mostly in N–H⋯F contacts. The preference of the amine nitrogen atom toward the halogen bond, as opposed to the hydrogen bond (with amine as a donor), is rationalised by means of computed hydrogen and halogen bond energies, indicating that the halogen bond energy between a simple primary amine (methylamine) and a perfluorinated iodobenzene (pentafluoroiodobenze ne) is ca. 15 kJ mol−1 higher than the energy of the (H)NH∙∙∙NH2 hydrogen bond between two amine molecules.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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