Design and Supramolecular Structure of Crystal Associates of Polyfluoroarylenediamines and 18-Crown-6 (2:1) | Sciact - CRIS-system of Boreskov Institute of Catalysis

Design and Supramolecular Structure of Crystal Associates of Polyfluoroarylenediamines and 18-Crown-6 (2:1) Full article

Journal

Journal of Molecular Structure
ISSN: 0022-2860

Output data

Year: 2017, Volume: 1133, Pages: 122-134 Pages count : 17 DOI: 10.1016/j.molstruc.2016.11.091

Tags

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

Authors

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

Affiliations

1	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Avenue, 630090, Novosibirsk, Russian Federation
2	Novosibirsk State University, Pirogov Avenue 2, 630090, Novosibirsk, Russian Federation
3	Boreskov Institute of Сatalysis, Siberian Branch of the Russian Academy of Sciences, 5 Lavrentiev Avenue, 630090, Novosibirsk, Russian Federation
4	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Avenue, 630090, Novosibirsk, Russian Federation

Funding (1)

Russian Foundation for Basic Research

15-03-02729

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 hexafluoro-2,7-naphthylenediamine, 4-trifluoromethyltrifluoro- and 2-trifluoromethyl-4,6-difluro-1,3-phenylenediamines, 4-chlorodifluoro-2,6-diaminopyridine. According to X-ray crystallographic data, associates of CF3-containing polyfluorophenylenediamines are 2D assemblies connected via synthon СareNeH...Ocr. Polyfluorinated 2,7-diaminonaphthalene and 2,6-diamino-4-chloropyridine form 1D assemblies, in which the p-stacking of the naphthylenediamine molecules and the hydrogen bond СareNeH...Npy, 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 |DDHsubl| 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.

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 ANCAN OpenAlex

Submitted:	Sep 12, 2016
Accepted:	Nov 28, 2016
Published online:	Nov 30, 2016
Published print:	Apr 1, 2017

Web of science:	WOS:000393931900014
Scopus:	2-s2.0-84999666606
Elibrary:	28554623
Chemical Abstracts:	2016:2016063
Chemical Abstracts (print):	166:263949
OpenAlex:	W2558192126

DB	Citing
Web of science	10
Scopus	10
Elibrary	10
OpenAlex	10