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Crystallographic and first‐principles density functional theory study on the structure, noncovalent interactions, and chemical reactivity of 1,5‐benzodiazepin‐2‐ones derivatives
Author(s) -
Hajji Melek,
Mtiraoui Hasan,
Amiri Nesrine,
Msaddek Moncef,
Guerfel Taha
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26000
Subject(s) - non covalent interactions , density functional theory , chemistry , intramolecular force , stacking , intermolecular force , aromaticity , computational chemistry , steric effects , van der waals force , reactivity (psychology) , atoms in molecules , molecule , delocalized electron , chemical physics , hydrogen bond , time dependent density functional theory , supramolecular chemistry , natural bond orbital , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
The present work arose out of a desire to fundamentally understand the molecular geometry, weak interactions, electron density delocalization, and chemical reactivity features of 1,5‐benzodiazepines‐containing family. Herein, a complete X‐ray crystallographic study, supported by trustworthy sets of computational approaches, has been reported for two organic crystals. Quantifying intramolecular and intermolecular interactions by Hirshfeld‐Becke surfaces analysis conjointly with noncovalent interaction‐reduced density gradient topological study revealed that supramolecular assemblies are stabilized by N‐H … O (inter) and O‐H … N (intra) hydrogen bonds, Cg … Cg (π … π) and C‐H(O) … π intercontacts, as well as Van der Waals interactions and steric effects. The long‐range‐corrected functional wB97XD, which uses Grimme's D2 dispersion model, seems to be just right for our systems. The quantum theory of atoms in molecules analysis confirms that both significant O1‐H1…N1 and N2‐H2A…O2 H‐bonds are weak and electrostatic in nature. Furthermore, global reactivity indices computed via the conceptual density functional theory framework allows these molecules to be classified as moderate electrophiles and marginal nucleophiles. The active sites favorable for nucleophilic/electrophilic attacks were also predicted based on local Parr functions. Finally, a comparative evaluation on the aromaticity character and π‐π stacking ability has been done for different (pseudo) rings.