Intermolecular interactions in the crystalline structure of some polyhalogenated Di– And triamino Pyridines: Spectroscopical perspectives

Intermolecular interactions in the crystalline structure of some polyhalogenated Di– And triamino Pyridines: Spectroscopical perspectives Full article

Journal

Spectrochimica Acta, Part A
ISSN: 1386-1425 , E-ISSN: 1873-3557

Output data

Year: 2022, Volume: 281, Article number : 121632, Pages count : DOI: 10.1016/j.saa.2022.121632

Authors

Benassi Enrico ¹ , Vaganova Tamara ² , Malykhin Evgenij ² , Gatilov Yurij ² , Nurtay Lazzat ³ , Fan Haiyan ³

Affiliations

1	Novosibirsk State University
2	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences
3	Nazarbayev University

Highlights • 6 polyhalogenated di-/triaminopyridines synthesised and structurally characterised. • Synthons studied by means of vibrational spectroscopies and calculations. • Distinctive features of supramolecular interactions in spectra of solid samples. • Quantitative correlations among dimerisation energies, ring structure and spectra. Abstract Supramolecular synthon is identified as a unit and provides important structural and energetic information in the study of organic crystals. However, the direct estimation of the supramolecular interaction remains challenging. In the present work six polyhalogenated di– or triamino pyridines were synthesised, their crystalline structure was characterised, and corresponding supramolecular synthons were studied using a combination of quantum mechanical calculations and FT–IR and Raman spectroscopy. Some distinctive features were identified especially for three vibrational normal modes (RNMs) related to the pyridine ring (viz. RNM1, RNM3 and RNM7) in the vibrational spectra (FT–IR and Raman) of the solid samples, which are due to the supramolecular interactions, hydrogen bond (hb) in particular, according to the quantum mechanical calculations. The comparison between the IR and Raman spectra of experimental and simulated results indicates that the adjacent intermolecular hydrogen bonds between two same molecules extensively exist in the solid samples. Moreover, some quantitative correlation was established among the dimerisation energies for hb dimers (hb1 dimers for compounds 1 and 2), the ring structure defined by the distribution of the substituents and quantitative characteristics of the vibrational spectra, for instance, the splitting magnitudes for RNM3(2) in IR spectra and the peak gap between RNM1 and RNM2 in Raman spectra.

Benassi E. , Vaganova T. , Malykhin E. , Gatilov Y. , Nurtay L. , Fan H.
Intermolecular interactions in the crystalline structure of some polyhalogenated Di– And triamino Pyridines: Spectroscopical perspectives
Spectrochimica Acta, Part A. 2022. V.281. 121632 . DOI: 10.1016/j.saa.2022.121632 WOS Scopus РИНЦ

Submitted:	May 4, 2022
Accepted:	Jul 12, 2022
Published online:	Jul 16, 2022

Web of science	WOS:000831819900004
Scopus	2-s2.0-85134699915
Elibrary	56824990
OpenAlex	W4285680009