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

Abstract

Crystal structures of six new phosphoramides with the main parts [C(O)NH]P(O)[N]2 and [NH]2P(O)[N] were determined by single crystal X‐ray diffraction and characterized by spectroscopic methods (FT‐IR and 1H, 13C, 31P 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.

Structural and Molecular Packing study of Three New Amidophosphoric Acid Esters and Assessment of Their Inhibiting Activity Against SARS‐CoV‐2 by Molecular Docking

“…The FPs are derived from HS as a 2D grid formed by ( d i , d e ) pairs to facilitate the study of intermolecular interactions. Moreover, the enrichment ratio ( E ) calculations resulted from the collected data from Hirshfeld surface analysis is employed for a detailed evaluation of the intermolecular contacts [25,46] …”

“…Moreover, the enrichment ratio ( E ) calculations resulted from the collected data from Hirshfeld surface analysis is employed for a detailed evaluation of the intermolecular contacts. [ 25 , 46 ]…”

Coordination versus hydrogen bonds in the structures of different tris(pyridin-2-yl)phosphoric triamide derivatives

“…The P atom is in all structures in a distorted tetrahedral environment made up by a terminal oxygen and three nitrogen atoms of amide substitutes with standard bond angles of O–P–N and N–P–N for the phosphoramides 36 (Tables S1 and S2 † ). The P O and P–N bond lengths and C–N–P angles (Tables S1 and S2 † ) are similar to those in previous reported compounds.…”