Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of methyl 4-[3,6-bis-(pyridin-2-yl)pyridazin-4-yl]benzoate

Mouad Filali; Lhoussaine El Ghayati; Tuncer Hökelek; Joel T Mague; Abdessalam Ben-Tama; El Mestafa El Hadrami; Nada Kheira Sebbar

doi:10.1107/S2056989019013732

Crystal structure, Hirshfeld surface analysis and inter-action energy and DFT studies of methyl 4-[3,6-bis-(pyridin-2-yl)pyridazin-4-yl]benzoate

Acta Crystallogr E Crystallogr Commun. 2019 Oct 22;75(Pt 11):1672-1678. doi: 10.1107/S2056989019013732. eCollection 2019 Nov 1.

Authors

Mouad Filali¹, Lhoussaine El Ghayati², Tuncer Hökelek³, Joel T Mague⁴, Abdessalam Ben-Tama¹, El Mestafa El Hadrami¹, Nada Kheira Sebbar^{5

2}

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 Laboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco.
³ Department of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey.
⁴ Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.
⁵ Laboratoire de Chimie Appliquée et Environnement, Equipe de Chimie Bioorganique Appliquée, Faculté des sciences, Université Ibn Zohr, Agadir, Morocco.

Abstract

The title com-pound, C₂₂H₁₆N₄O₂, contains two pyridine rings and one meth-oxy-carbonyl-phenyl group attached to a pyridazine ring which deviates very slightly from planarity. In the crystal, ribbons consisting of inversion-related chains of mol-ecules extending along the a-axis direction are formed by C-H_Mthy⋯O_Carbx (Mthy = methyl and Carbx = carboxyl-ate) hydrogen bonds. The ribbons are connected into layers parallel to the bc plane by C-H_Bnz⋯π(ring) (Bnz = benzene) inter-actions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (39.7%), H⋯C/C⋯H (27.5%), H⋯N/N⋯H (15.5%) and O⋯H/H⋯O (11.1%) 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_Mthy⋯O_Carbx hydrogen-bond energies are 62.0 and 34.3 kJ mol^-1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(d,p) level are com-pared 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; crystal structure; hydrogen bond; pyridazine; pyridine.

Grants and funding

This work was funded by Hacettepe University Scientific Research Project Unit grant 013 D04 602 004 to TH. NSF-MRI grant 1228232.