Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of 1-methyl-3-(prop-2-yn-1-yl)-2,3-di-hydro-1 H-1,3-benzo-diazol-2-one

Asmaa Saber; Mohamed Srhir; Tuncer Hökelek; Joel T Mague; Noureddine Hamou Ahabchane; Nada Kheira Sebbar; El Mokhtar Essassi

doi:10.1107/S2056989019015779

Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of 1-methyl-3-(prop-2-yn-1-yl)-2,3-di-hydro-1 H-1,3-benzo-diazol-2-one

Acta Crystallogr E Crystallogr Commun. 2019 Nov 29;75(Pt 12):1940-1946. doi: 10.1107/S2056989019015779. eCollection 2019 Dec 1.

Authors

Asmaa Saber¹, Mohamed Srhir¹, Tuncer Hökelek², Joel T Mague³, Noureddine Hamou Ahabchane¹, Nada Kheira Sebbar^{4

1}, 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 Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey.
³ Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.
⁴ Laboratoire de Chimie Appliquée et Environnement, Equipe de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco.

Abstract

In the title mol-ecule, C₁₁H₁₀N₂O, the di-hydro-benzimidazol-2-one moiety is essentially planar, with the prop-2-yn-1-yl substituent rotated well out of this plane. In the crystal, C-H_Mthy⋯π(ring) inter-actions and C-H_Prop⋯O_Dhyr (Mthy = methyl, Prop = prop-2-yn-1-yl and Dhyr = di-hydro) hydrogen bonds form corrugated layers parallel to (10), which are associated through additional C-H_Bnz⋯O_Dhyr (Bnz = benzene) hydrogen bonds and head-to-tail, slipped, π-stacking [centroid-to-centroid distance = 3.7712 (7) Å] inter-actions between di-hydro-benzimidazol-2-one moieties. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (44.1%), H⋯C/C⋯H (33.5%) and O⋯H/H⋯O (13.4%) inter-actions. Hydrogen-bonding and van der Waals inter-actions are the dominant inter-actions in the crystal packing. Computational chemistry calculations indicate that in the crystal, C-H⋯O hydrogen-bond energies are 46.8 and 32.5 (for C-H_Prop⋯O_Dhyr) and 20.2 (for C-H_Bnz⋯O_Dhyr) kJ mol^-1. 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: C—H⋯π(ring) interaction; Hirshfeld surface; benzimidazol-2-one; crystal structure; 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. Hökelek.