TY - JOUR

T1 - Intermolecular interactions in the crystalline structure of some polyhalogenated Di– And triamino Pyridines: Spectroscopical perspectives

AU - Benassi, Enrico

AU - Vaganova, Tamara

AU - Malykhin, Evgenij

AU - Gatilov, Yurij

AU - Nurtay, Lazzat

AU - Fan, Haiyan

N1 - Funding Information: HF thanks Nazarbayev University small grant 110119FD4542 and 11022021FD2928. TV and EM acknowledge the support by the Ministry of Science and Higher Education of the Russian Federation (project 1021051403061–8–1.4.1). The Authors are grateful to the Siberian Supercomputer Centre of Institute of Computational Mathematics and Mathematical Geophysics (Russian Academy of Sciences, Novosibirsk, Russian Federation) for kindly providing the computational resources; the technical staff of the Institute is also thanked for the assistance. The core and computational facilities offered by Nazarbayev University are acknowledged. Funding Information: TV and EM acknowledge the support by the Ministry of Science and Higher Education of the Russian Federation (project 1021051403061–8–1.4.1 ). Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/11/15

Y1 - 2022/11/15

N2 - 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.

AB - 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.

KW - Intermolecular Interactions

KW - Pyridine derivatives

KW - Quantum Chemical Calculations

KW - Synthons

KW - Vibrational Spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=85134699915&partnerID=8YFLogxK

U2 - 10.1016/j.saa.2022.121632

DO - 10.1016/j.saa.2022.121632

M3 - Article

C2 - 35868054

AN - SCOPUS:85134699915

VL - 281

JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

SN - 1386-1425

M1 - 121632

ER -