Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of 2-chloro-ethyl 2-oxo-1-(prop-2-yn-1-yl)-1,2-di-hydro-quinoline-4-carboxyl-ate

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

doi:10.1107/S2056989019012283

Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of 2-chloro-ethyl 2-oxo-1-(prop-2-yn-1-yl)-1,2-di-hydro-quinoline-4-carboxyl-ate

Acta Crystallogr E Crystallogr Commun. 2019 Sep 6;75(Pt 10):1411-1417. doi: 10.1107/S2056989019012283. eCollection 2019 Oct 1.

Authors

Sonia Hayani¹, Yassir Filali Baba¹, Tuncer Hökelek², Fouad Ouazzani Chahdi¹, Joel T Mague³, Nada Kheira Sebbar⁴, Youssef Kandri Rodi¹

Affiliations

¹ Laboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202, Fez, Morocco.
² Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey.
³ Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.
⁴ Laboratoire de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco.

Abstract

The title compound, C₁₅H₁₂ClNO₃, consists of a 1,2-di-hydro-quinoline-4-carb-oxyl-ate unit with 2-chloro-ethyl and propynyl substituents, where the quinoline moiety is almost planar and the propynyl substituent is nearly perpendicular to its mean plane. In the crystal, the mol-ecules form zigzag stacks along the a-axis direction through slightly offset π-stacking inter-actions between inversion-related quinoline moieties which are tied together by inter-molecular C-H_Prpn-yl⋯O_Carbx and C-H_Chlethy⋯O_Carbx (Prpnyl = propynyl, Carbx = carboxyl-ate and Chlethy = chloro-eth-yl) hydrogen bonds. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (29.9%), H⋯O/O⋯H (21.4%), H⋯C/C⋯ H (19.4%), H⋯Cl/Cl⋯H (16.3%) and C⋯C (8.6%) inter-actions. Hydrogen bonding and van der Waals inter-actions are the dominant inter-actions in the crystal packing. Computational chemistry indicates that in the crystal, the C-H_Prpn-yl⋯O_Carbx and C-H_Chlethy⋯O_Carbx hydrogen bond energies are 67.1 and 61.7 kJ mol^-1, respectively. 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. The HOMO-LUMO behaviour was elucidated to determine the energy gap.

Keywords: Hirshfeld surface; alkyne; crystal structure; hydrogen bond; quinoline; π-stacking.