Co-crystals of Polyhalogenated Diaminobenzonitriles with 18-crown-6: Effect of Fluorine on the Stoichiometry and Supramolecular Structure | Sciact - CRIS-system of Boreskov Institute of Catalysis

Co-crystals of Polyhalogenated Diaminobenzonitriles with 18-crown-6: Effect of Fluorine on the Stoichiometry and Supramolecular Structure Full article

Journal

CrystEngComm
ISSN: 1466-8033

Output data

Year: 2021, Volume: 23, Number: 27, Pages: 4767-4781 Pages count : 15 DOI: 10.1039/d1ce00530h

Tags

Amines; Crown ethers; Fluorine; Hydrogen bonds; Melting; Quantum chemistry; Stoichiometry; Supramolecular chemistry

Authors

Vaganova Tamara A. ¹ , Gatilov Yurij V. ¹ , Malykhin Sergey E. ^2,3 , Pishchur Denis P. ⁴ , Sukhov Maxim ^1,2 , Zakharov Boris A. ^2,3 , Boldyreva Elena V. ^2,3 , Malykhin Evgenij 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, 2 Pirogov Avenue, 630090 Novosibirsk, Russian Federation
3	Boreskov Institute of Catalysis SB RAS, 5 Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
4	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Lavrentiev Avenue, 630090 Novosibirsk, Russian Federation

Funding (2)

1	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0002
2	Ministry of Science and Higher Education of the Russian Federation	0238-2021-0002 (АААА-А21-121011490017-5)

A series of polyhalogenated diaminobenzonitriles and 18-crown-6 ether were used to reveal the dependence of the stoichiometry and supramolecular architecture of co-crystals on various factors. 2,6-Diamino-3,5-difluoro-, 2,6-diamino-4-chloro-3,5-difluoro-, 2,6-diamino-4-chloro-3-fluorobenzonitriles, as well as 2,4-diamino-3,5-difluorobenzonitrile give 1:1 co-crystals regardless of the diamine:crown ratio in the crystallization solution (from 2.5:1 to 1:2.5) and the nature of the solvent. According to X-ray diffraction data, supramolecular structures of these co-crystals сan be considered as 1D assemblies with the only structure-forming N–H•••Ocr hydrogen bond. 2,4-Diamino-3,5,6-triflurobenzonitrile forms no 1:1 co-crystal, but yields co-crystals of 4:3 (under most of the studied conditions) and 2:1 (in CCl4 solution) stoichiometry. The N–H•••NC hydrogen bond and p•••π electron interactions, alongside with the N–H•••Ocr H-bond, participate in the formation of 3D supramolecular structures of these co-crystals. Effect of the number of F atoms on the co-crystallization behaviour of difluoro- and trifluoro-2,4-diaminobenzonitriles was rationalized using quantum-chemical computations of the interaction energies of N-H•••NC bonded pairs of these diamines in the experimental crystals and DFT simulated models. The DSC curves of each co-crystal contain a single peak corresponding to a crystal-to-liquid phase transition (melting), which does not change in melting-crystallization cycles, indicating that the stoichiometry and crystal structure are reproducible.

Vaganova T.A. , Gatilov Y.V. , Malykhin S.E. , Pishchur D.P. , Sukhov M. , Zakharov B.A. , Boldyreva E.V. , Malykhin E.V.
Co-crystals of Polyhalogenated Diaminobenzonitriles with 18-crown-6: Effect of Fluorine on the Stoichiometry and Supramolecular Structure
CrystEngComm. 2021. V.23. N27. P.4767-4781. DOI: 10.1039/d1ce00530h WOS Scopus РИНЦ AN OpenAlex

Submitted:	Apr 21, 2021
Published online:	Jun 1, 2021
Accepted:	Jun 4, 2021
Published print:	Jul 21, 2021

Web of science:	WOS:000665078400001
Scopus:	2-s2.0-85109920872
Elibrary:	46894798
Chemical Abstracts:	2021:1253050
OpenAlex:	W3169830584

DB	Citing
Web of science	5
Scopus	5
Elibrary	5
OpenAlex	5