Contribution of Directional. Dihydrogen Interactions in the Supramolecular Assembly of Single Crystals: Quantum Chemical and Structural Investigation of C17H17N3O2 Azine

Author(s)

de Almeida, Leonardo R. ^[1] ; Carvalho, Jr., Paulo S. ^[1] ; Napolitano, Hamilton B. ^[1] ; Oliveira, Solemar S. ^[1] ; Camargo, Ademir J. ^[1] ; Figueredo, Andreza S. ^[1] ; de Aquino, Gilberto L. B. ^[1] ; Carvalho-Silva, Valter H. ^[1]

Affiliation

^[1] Univ Fed Goias, Grp Quim Teor & Estrut Anapolis, Campus Ciencias Exatas & Tecnol, Caixa Postal 459, BR-75001970 Anapolis, Go - Brazil

• Document type: Journal article
• Source: Crystal Growth & Design; v. 17, n. 10, p. 5145-5153, OCT 2017.
• Web of Science Citations: 6

Abstract

Crystalline systems can be organized from several types of intermolecular interactions, among which classical and weak H-bonds are the most common, playing a very important role in the supramolecular assembly. However, in recent years a number of works have considered the influence of the homonuclear dihydrogen interaction, which had been neglected for a long time, to describe the supramolecular assembly of single crystals. In the C17H17N3O2 azine of the present study, a nonclassical dihydrogen interactions (C-H center dot center dot center dot H-C contact) have appeared in the crystal structure with a fundamental contribution toward the stability of crystalline packing. Nonetheless, an X-ray structural analysis is not conclusive to assess the real importance of the C-H center dot center dot center dot H-C contact. In order to characterize the nature and implications of C-H center dot center dot center dot H-C contacts concomitant with the classical interactions, the crystallized compound was evaluated by Hirshfeld surface, Quantum Theory of Atoms in Molecules, natural bond orbital, and Car-Parrinello molecular dynamics. The results establish that these interactions really exist, and their extension is responsible for the cooperative effect on the stability of crystalline packing. We expect that a more thorough understanding and description of homonuclear dihydrogen interactions in the supramolecular assembly of C17H17N3O2 can assist in the crystal engineering of small molecules, offering progress on physical-chemistry parameters of biological and material processes. (AU)

• FAPESP's process: 12/05616-7 - Solid-state characterization of anticonvulsant and antidepressant phamaceutical compounds: Design of new crystal forms.
• Grantee: Paulo de Sousa Carvalho Júnior
• Support Opportunities: Scholarships in Brazil - Doctorate