Design and supramolecular structure of crystal associates of polyfluoroarylenediamines and 18-crown-6 (2:1)

Design and supramolecular structure of crystal associates of polyfluoroarylenediamines and 18-crown-6 (2:1) Научная публикация

Журнал

Journal of Molecular Structure
ISSN: 0022-2860 , E-ISSN: 1872-8014

Вых. Данные

Год: 2017, Том: 1133, Страницы: 122-134 Страниц : 13 DOI: 10.1016/j.molstruc.2016.11.091

Ключевые слова

Supramolecular associates; Polyfluorinated arylenediamines; 18-crown-6; X-ray diffraction analysis; Crystal melting enthalpy; vdW-DFT calculations

Авторы

Vaganova Tamara A. ¹ , Gatilov Yurij V. ^1,2 , Malykhin Sergej E. ³ , Pishchur Denis P. ⁴ , Larichev Yurii V. ^2,3 , Rodionov Vladimir I. ¹ , Malykhin Evgenij V. ¹

Организации

1	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Novosibirsk Inst Organ Chem, Siberian Branch, 9 Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogov Ave 2, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Boreskov Inst Catalysis, Siberian Branch, 5 Lavrentiev Ave, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, Nikolaev Inst Inorgan Chem, Siberian Branch, 3 Lavrentiev Ave, Novosibirsk 630090, Russia

The possibility of co-crystallization of polyfluoroaromatic meta-diamines with 18-crown-6 in the 2:1 ratio was tested using a large group of substrates with various frameworks (benzene, naphthalene, and pyridine) and substituents (H, Cl, CF3). Co-crystals of 2:1 stoichiometry were obtained from hexafluoro2,7-naphthylenediamine, 4-trifluoromethyltrifluoro- and 2-trifluoromethy1-4,6-difluro-1,3-phenyle nediamines, 4-chlorodifluoro-2,6-diaminopyridine. According to X-ray crystallographic data, associates of CF3-containing polyfluorophenylenediamines are 2D assemblies connected via synthon C-ar-N-H ...O-cr.Polyfluorinated 2,7-diaminonaphthalene and 2,6-diamino-4-chloropyridine form 1D assemblies, in which the pi-stacking of the naphthylenediamine molecules and the hydrogen bond C-ar-N-H ... N-py, respectively, are the additional structure-supporting interactions. The co-crystallization of 18-crown-6 with less electron withdrawing arylenediamines gives only associates of stoichiometry 1:1 irrespective of the components ratio and the solvent nature. To rationalize the different co-crystallization behavior of the arylenediamines, the co-crystal structures were studied using a special version of the DFT, which accounts for the van der Waals interactions. The calculated difference between the specific sublimation enthalpies for the 1:1 and 2:1 associates was suggested to be a measure of the preferable co crystallization ratio: the both types of associates are formed when vertical bar Delta Delta H-subl vertical bar is smaller than 15 J g(-1), a higher value indicates a significant energy preference for one of the structures. The experimental melting enthalpy values (DSC data) for the 1:1 and 2:1 co-crystals based on the same diamine are quite similar. (C) 2016 Elsevier B.V. All rights reserved.

Vaganova T.A. , Gatilov Y.V. , Malykhin S.E. , Pishchur D.P. , Larichev Y.V. , Rodionov V.I. , Malykhin E.V.
Design and supramolecular structure of crystal associates of polyfluoroarylenediamines and 18-crown-6 (2:1)
Journal of Molecular Structure. 2017. V.1133. P.122-134. DOI: 10.1016/j.molstruc.2016.11.091 WOS Scopus РИНЦ

Опубликована в печати:

1 апр. 2017 г.

Web of science	WOS:000393931900014
Scopus	2-s2.0-84999666606
РИНЦ	28554623
OpenAlex	W2558192126