Association of Non‐covalent Interactions C−H…X (X=O, F, Cl, π) and Cl…π with Hydrogen Bond Interactions N−H…O in Molecular Assembly of New Phosphoramides: A Combined X‐Ray Crystallography and Topology (AIM and Hirshfeld) Analysis. Issue 1 (2nd January 2020)

• Record Type: Journal Article
• Authors: Sebghati, Marjan; Tarahhomi, Atekeh; Kozakiewicz, Anna
• Is Part Of: ChemistrySelect. Volume 5:Issue 1(2020)
• Page Start: 185
• Page End: 195
• Publication Date: 2020-01-02
• Subjects: AIM calculation -- Hirshfeld surface analysis -- Hydrogen bond -- Phosphoric triamide -- X-ray crystallography.; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201903565
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Crystal structures of six new phosphoramides with the main parts [C(O)NH]P(O)[N]2 and [NH]2 P(O)[N] were determined by single crystal X‐ray diffraction and characterized by spectroscopic methods (FT‐IR and 1 H, 13 C, 31 P NMR). X‐ray crystallography data manifest that the hydrogen bond interactions N−H…O (in all structures) accompanied by some contacts such as C−H… X ( X =π, O, F and Cl) and π…π dominate the molecular architectures. Some non‐classical interactions such as Cl…π are also found in feature packing of some studied structures. A detailed investigation of these intermolecular interactions in order to illustrate the importance of non‐classical interactions in construction of molecular assemblies is presented by Hirshfeld surface (HS) analysis reflected the most important van der Waals (vdW) contributions and "Quantum Theory Atom In Molecule" (QTAIM) method especially in term of energetic feature. Hirshfeld surface analysis reveals that the prevalent interactions are of the type O…H for all structures coupled with some other short contacts such as C…C and H…F recognized by red spots on Hirshfeld surfaces and enrichment ratios ( E ) larger than unity ( E > 1). These results are confirmed by AIM method classifying the hydrogen bond interactions N−H…O as moderate non‐covalent closed‐shell interactions and the remaining interactions above‐mentioned as vdW closed‐shell interactions in the studies phosphoric triamides. Such study to categorize the popular hydrogen bond interactions N−H…O in phosphoric triamides and the weak interactions in their molecular packing are used for the first time. Abstract : Our study describe crystal structures and packing features of new phosphoramides completed with a theoretical study which combine the energetic investigation and the electronic characterization of diverse intermolecular interactions contributed in extended supramolecular networks. These investigations are performed by means of Hirshfeld surface method and Bader's theory of ''Atoms In Molecule'' (AIM) classifying the nature of the type of these interactions. Such study on phosphoramides are used for the first time.