Synthesis and crystal structures of two 1H-benzo[d]imidazole derivatives: DFT and anticorrosion studies, and Hirshfeld surface analysis

Nadir Ghichi; Amel Djedouani; Douniazed Hannachid; Mohamed Elhadi Said; Ali Benboudiaf; Hocine Merazig; Louiza Ouksel; Abdelkader Hellal; Helen Stoeckli-Evans

doi:10.1107/S2053229623005545

Synthesis and crystal structures of two 1H-benzo[d]imidazole derivatives: DFT and anticorrosion studies, and Hirshfeld surface analysis

Acta Crystallogr C Struct Chem. 2023 Jul 1;79(Pt 7):292-304. doi: 10.1107/S2053229623005545. Epub 2023 Jun 29.

Authors

Nadir Ghichi¹, Amel Djedouani², Douniazed Hannachid³, Mohamed Elhadi Said¹, Ali Benboudiaf¹, Hocine Merazig¹, Louiza Ouksel⁴, Abdelkader Hellal⁵, Helen Stoeckli-Evans⁶

Affiliations

¹ Unit of Research CHEMS, Chemistry Department, University of Mentouri Brothers, Constantine 1, Algeria.
² Laboratory of Analytical Physicochemistry and Crystallochemistry of Organometallic and Biomolecular Materials, University of Constantine 1, 25000, Algeria.
³ Laboratory of Electrochemistry, Molecular Engineering and Redox Catalysis (LEIMCR), Department of Basic Education in Technology, Faculty of Technology, University Ferhat Abbas, Setif-1, Algeria.
⁴ Laboratory of Electrochemistry and Materials (LEM), Department of Process Engineering, Faculty of Technology, Ferhat Abbas University, Setif-1, 19000, Algeria.
⁵ Laboratory of Electrochemistry of Molecular Materials and Complexes (LEMMC), Ferhat Abbas University, Setif-1, 19000, Algeria.
⁶ Institute of Physics, University of Neuchâtel, rue Emile-Argand 11, 2000 Neuchâtel, Switzerland.

PMID: 37403838
DOI: 10.1107/S2053229623005545

Abstract

The title benzimidazole compounds, namely, 2-(4-methoxynaphthalen-1-yl)-1H-benzo[d]imidazole, C₁₈H₁₄N₂O (I) and 2-(4-methoxynaphthalen-1-yl)-1-[(4-methoxynaphthalen-1-yl)methyl]-1H-benzo[d]imidazole ethanol monosolvate, C₃₀H₂₄N₂O₂·C₂H₆O (II), were synthesized by the condensation reaction of benzene-1,2-diamine with 4-methoxynaphthalene-1-carbaldehyde in the ratios 1:1 and 1:2, respectively. In I, the mean plane of the naphthalene ring system is inclined to that of the benzimidazole ring by 39.22 (8)°, while in II, the corresponding dihedral angle is 64.76 (6)°. This difference is probably influenced by the position of the second naphthalene ring system in II; it is inclined to the benzimidazole ring mean plane by 77.68 (6)°. The two naphthalene ring systems in II are inclined to one another by 75.58 (6)°. In the crystal of I, molecules are linked by N-H...N hydrogen bonds to form chains propagating along the a-axis direction. Inversion-related molecules are also linked by a C-H...π interaction linking the chains to form layers lying parallel to the ac plane. In the crystal of II, the disordered ethanol molecule is linked to the molecule of II by an O-H...N hydrogen bond. There are a number of C-H...π interactions present, both intra- and intermolecular. Molecules related by an inversion centre are linked by C-H...π interactions, forming a dimer. The dimers are linked by further C-H...π interactions, forming ribbons propagating along the b-axis direction. The interatomic contacts in the crystal structures of both compounds were explored using Hirshfeld surface analysis. The molecular structures of I and II were determined by density functional theory (DFT) calculations at the M062X/6-311+g(d) level of theory and compared with the experimentally determined molecular structures in the solid state. Local and global reactivity descriptors were computed to predict the reactivity of the title compounds. Both compounds were shown to exhibit significant anticorrosion properties with respect to iron and copper.

Keywords: 4-methoxynaphthalene; DFT calculations; Hirshfeld surfaces; anticorrosion; benzo[d]imidazole; crystal structure; hydrogen bonding.