В журнале CrystEngComm (IF 3,756) опубликована статья с участием сотрудников Института: к.х.н. Т.А. Ваганова (снс, ЛГетС), д.х.н. Ю.В. Гатилов (внс, ГРСА) А.А. Жуковец и д.х.н. Е.В. Малыхин (гнс, ЛГетС):
How does the combination of the nitro group and fluorine atoms affect the (co)crystallization behaviour of arylenediamines?
Tamara A. Vaganova, Yurij V. Gatilov, Natalia A. Kryuchkova, Denis P. Pishchur, Anastasia A. Zhukovets and Evgenij V. Malykhin
CrystEngComm, 2023, 25(2), 3284-3298
https://doi.org/10.1039/D3CE00327B
Abstract
A series of phenylenediamines containing the NO2 group and 3 to 0 fluorine atoms and 18-crown-6 ether were used to study the dependence of the stoichiometry and supramolecular structure of co-crystals on the degree of fluorination of the aromatic co-former. 2,4-Diamino-3,5,6-trifluoro- and -3,5-difluoronitrobenzenes form co-crystals of two stoichiometries: 2 : 1 (preferably) and 1 : 1. 2,4-Diamino-5-fluoronitrobenzene and the non-fluorinated analogue yield only 1 : 1 co-crystals. DSC analysis indicates complete regeneration of the stoichiometry and structure of the co-crystals in the melting–crystallization cycle. According to X-ray diffraction data, all the 1 : 1 co-crystals are built from the 1D assemblies in which N–H⋯Ocr H-bond is the only structure-directing interaction. The 2 : 1 co-crystals have a 3D or 2D supramolecular structure due to additional interactions formed by the aromatic co-formers, i.e. N–H⋯Onitro H-bond and p⋯π electron contacts. Analysis of the structure of diaminonitrobenzene homocrystals showed that in di- and trifluorinated diaminonitrobenzenes, F atoms contribute to the formation of p⋯π electron interactions, while in mono- and non-fluorinated co-formers, the ability of NH<2 groups to form the H-bonds both as donors and as acceptors increases. Factors controlling the crystallization behaviour were rationalized using quantum-chemical computations of the packing and co-crystallization enthalpies, the energies of N–H⋯X (X = Ocr, Onitro, Namino) and p⋯π electron interactions, as well as the MEP and NCI analyses.
Альметрики:
Метрики PlumX теперь доступны в Scopus: узнайте, как другие ученые используют ваши исследования