ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Probing the significance, nature, and energetics of weak hydrogen bonding in the crystal structure of a 1-chloro-4-methoxybenzene derivative through structural and computational modeling

Amel Haouas

Department of Chemistry, Faculty of Science, Northern Border University, Arar, Saudi Arabia

E-mail: amel.haouas@nbu.edu.sa

Received: 19 August 2023  Accepted: 12 November 2023

Abstract:

Weak hydrogen bonds (WHBs) have been the focus of intense research in recent years, particularly in structural chemistry and molecular biology. Several studies have shown that WHBs play a significant role in both molecular recognition and supramolecular associations. However, the geometrical, electronic, and energetic properties of WHBs remain incompletely characterized. This work presents a combined structural and theoretical investigation into the crystal arrangement of a 1-chloro-4-methoxybenzene derivative. Our study highlights the significant role of weak hydrogen bonding (C–H···X, where X = O, Cl, π, or C–H) as the primary driving force behind the crystal packing. The geometrical features of these WHBs were analyzed structurally. Computational analysis of several selected dimeric substructures was then performed using dispersion-corrected DFT (wB97X-D/aug-cc-pVTZ), MEP and QTAIM approaches to evaluate their electronic properties and energetics. The results showed that cooperative effects and synergies exist among C–H···O/Cl/π interactions. Moreover, the stabilizing contribution of the weakest but attractive C–H···H–C contacts was also confirmed. Natural bond orbital (NBO) methodology further gave insights into the charge transfer and molecular orbital interactions. The findings from this work may have valuable implications for the understanding, characterization, and practical application of weak hydrogen bonding.

Keywords: Non-covalent interactions; Weak hydrogen bonding; Density functional theory; QTAIM; NBO

Full paper is available at www.springerlink.com.

DOI: 10.1007/s11696-023-03245-w

Chemical Papers 78 (4) 2385–2395 (2024)