Crystal structure, Hirshfeld surface analysis, inter-action energy and DFT calculations and energy frameworks of methyl 6-chloro-1-methyl-2-oxo-1,2-di-hydro-quinoline-4-carboxyl-ate

Yassir Filali Baba; Sonia Hayani; Samira Dalbouha; Tuncer Hökelek; Fouad Ouazzani Chahdi; Joel T Mague; Youssef Kandri Rodi; Nada Kheira Sebbar; El Mokhtar Essassi

doi:10.1107/S2056989022002912

Crystal structure, Hirshfeld surface analysis, inter-action energy and DFT calculations and energy frameworks of methyl 6-chloro-1-methyl-2-oxo-1,2-di-hydro-quinoline-4-carboxyl-ate

Acta Crystallogr E Crystallogr Commun. 2022 Mar 22;78(Pt 4):425-432. doi: 10.1107/S2056989022002912. eCollection 2022 Apr 1.

Authors

Affiliations

¹ Laboratory of Applied Organic Chemistry, Faculty of Science and Technology, Sidi Mohammed Ben Abdullah University, Route d'Immouzzer, BP 2202, Fez, Morocco.
² Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, CERNE2D, Faculty of Sciences-Rabat, Mohammed V University, Av. Ibn Battouta, BP 1014 Rabat, Morocco.
³ Research team: Materials and Environmental Applications, Laboratory of Applied Chemistry and Environment, Department of Chemistry, Faculty of Sciences-Agadir, Ibn Zohr University, BP 8106 Agadir, Morocco.
⁴ Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey.
⁵ Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.
⁶ Laboratory of Applied Chemistry and Environment, Applied Bioorganic Chemistry Team, Faculty of Science, Ibn Zohr University, Agadir, Morocco.
⁷ Laboratory of Heterocyclic Organic Chemistry, Pharmacochemistry Competence Center, Drug Science Research Center, Faculty of Sciences, Mohammed V University of Rabat, Rabat, Morocco.

Abstract

In the title compound, C₁₂H₁₀ClNO₃, the di-hydro-quinoline moiety is not planar with a dihedral angle between the two ring planes of 1.61 (6)°. An intra-molecular C-H⋯O hydrogen bond helps to establish the rotational orientation of the carboxyl group. In the crystal, sheets of mol-ecules parallel to (10) are generated by C-H⋯O and C-H⋯Cl hydrogen bonds, and are stacked through slipped π-stacking inter-actions between inversion-related di-hydro-quinoline units. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (34.2%), H⋯O/O⋯H (19.9%), H⋯Cl/Cl⋯H (12.8%), H⋯C/C⋯H (10.3%) and C⋯C (9.7%) inter-actions. Computational chemistry indicates that in the crystal, the C-H⋯Cl hydrogen-bond energy is -37.4 kJ mol^-1, while the C-H⋯O hydrogen-bond energies are -45.4 and -29.2 kJ mol^-1. An evaluation of the electrostatic, dispersion and total energy frameworks revealed that the stabilization is dominated via the dispersion energy contribution. Density functional theory (DFT) optimized structures at the B3LYP/6-311 G(d,p) level are compared with the experimentally determined mol-ecular structure in the solid state, and the HOMO-LUMO behaviour was elucidated to determine the energy gap.

Keywords: crystal structure; dihydroquinoline; hydrogen-bonding; π-stacking.

Grants and funding

This work was funded by Tulane University; Hacettepe University Scientific Research Project Unit grant 013 D04 602 004.