How does the combination of the nitro group and fluorine atoms affect the (co)crystallization behaviour of arylenediamines?

How does the combination of the nitro group and fluorine atoms affect the (co)crystallization behaviour of arylenediamines? Full article

Journal

CrystEngComm
ISSN: 1466-8033

Output data

Year: 2023, Number: 25, Pages: 3284 Pages count : 1 DOI: 10.1039/d3ce00327b

Tags

SOLID-STATEINTERMOLECULAR INTERACTIONSCRYSTALDESIGNTHERMOCHROMISMPREDICTIONENERGETICSSTACKINGANILINESCOMPLEX

Authors

Vaganova Tamara A. ¹ , Gatilov Yurij V. ¹ , Kryuchkova Natalia A. ² , Pishchur Denis P. ² , Zhukovets Anastasia A. ¹ , Malykhin Evgenij V. ¹

Affiliations

1	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences
2	Nikolaev Institute of Inorganic Chemistry of the Siberian Branch of the RAS

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-HMIDLINE HORIZONTAL ELLIPSISOcr 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-HMIDLINE HORIZONTAL ELLIPSISOnitro H-bond and pMIDLINE HORIZONTAL ELLIPSIS pi electron contacts. Analysis of the structure of diaminonitrobenzene homocrystals showed that in di- and trifluorinated diaminonitrobenzenes, F atoms contribute to the formation of pMIDLINE HORIZONTAL ELLIPSIS pi electron interactions, while in mono- and non-fluorinated co-formers, the ability of NH2 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-HMIDLINE HORIZONTAL ELLIPSISX (X = O-cr, O-nitro, N-amino) and pMIDLINE HORIZONTAL ELLIPSIS pi electron interactions, as well as the MEP and NCI analyses.

Vaganova T.A. , Gatilov Y.V. , Kryuchkova N.A. , Pishchur D.P. , Zhukovets A.A. , Malykhin E.V.
How does the combination of the nitro group and fluorine atoms affect the (co)crystallization behaviour of arylenediamines?
CrystEngComm. 2023. N25. P.3284. DOI: 10.1039/d3ce00327b WOS РИНЦ

Submitted:	Apr 6, 2023
Accepted:	Apr 27, 2023

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