Crystal structure, Hirshfeld surface analysis, inter-action energy and DFT studies of (2 Z)-2-(2,4-di-chloro-benzyl-idene)-4-nonyl-3,4-di-hydro-2 H-1,4-benzo-thia-zin-3-one

Brahim Hni; Nada Kheira Sebbar; Tuncer Hökelek; Achour Redouane; Joel T Mague; Noureddine Hamou Ahabchane; El Mokhtar Essassi

doi:10.1107/S2056989020001036

Crystal structure, Hirshfeld surface analysis, inter-action energy and DFT studies of (2 Z)-2-(2,4-di-chloro-benzyl-idene)-4-nonyl-3,4-di-hydro-2 H-1,4-benzo-thia-zin-3-one

Acta Crystallogr E Crystallogr Commun. 2020 Jan 31;76(Pt 2):281-287. doi: 10.1107/S2056989020001036. eCollection 2020 Feb 1.

Authors

Brahim Hni¹, Nada Kheira Sebbar^{2

1}, Tuncer Hökelek³, Achour Redouane¹, Joel T Mague⁴, Noureddine Hamou Ahabchane¹, El Mokhtar Essassi¹

Affiliations

¹ Laboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco.
² Laboratoire de Chimie Appliquée et Environnement, Equipe de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco.
³ Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey.
⁴ Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.

Abstract

The title compound, C₂₄H₂₇Cl₂NOS, contains 1,4-benzo-thia-zine and 2,4-di-chloro-phenyl-methyl-idene units in which the di-hydro-thia-zine ring adopts a screw-boat conformation. In the crystal, inter-molecular C-H_Bnz⋯O_Thz (Bnz = benzene and Thz = thia-zine) hydrogen bonds form chains of mol-ecules extending along the a-axis direction, which are connected to their inversion-related counterparts by C-H_Bnz⋯Cl_Dchlphy (Dchlphy = 2,4-di-chloro-phen-yl) hydrogen bonds and C-H_Dchlphy⋯π (ring) inter-actions. These double chains are further linked by C-H_Dchlphy⋯O_Thz hydrogen bonds, forming stepped layers approximately parallel to (012). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (44.7%), C⋯H/H⋯C (23.7%), Cl⋯H/H⋯Cl (18.9%), O⋯H/H⋯O (5.0%) and S⋯H/H⋯S (4.8%) 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, C-H_Dchlphy⋯O_Thz, C-H_Bnz⋯O_Thz and C-H_Bnz⋯Cl_Dchlphy hydrogen-bond energies are 134.3, 71.2 and 34.4 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. The two carbon atoms at the end of the nonyl chain are disordered in a 0.562 (4)/0.438 (4) ratio.

Keywords: 1,4-benzothiazin-3-one; Hirshfeld surface; crystal structure; dihydrothiazine; hydrogen bond; π-stacking.

Grants and funding

This work was funded by National Science Foundation grant 1228232. Tulane University grant . Hacettepe Üniversitesi grant 013 D04 602 004 to T. Hokkelek.