Stabilization of Supramolecular Assembly of N‐Substituted Benzylidene Acetohydrazide Analogs by Non‐Covalent Interactions: A Concise Experimental and Theoretical Approach

Abstract

Herein, the crystalline N‐substituted benzylidene acetohydrazide derivatives: N′‐(4‐bromo‐2‐fluorobenzylidene)‐2‐((6‐chloropyridin‐2‐yl)oxy) acetohydrazide (BFBAH) and 2‐((6‐chloropyridin‐2‐yl)oxy)‐N′‐(4‐methoxybenzylidene) acetohydrazide (MOBAH) were produced and the structures were characterized and confirmed by the NMR spectroscopy and single crystal analysis. SC‐XRD study disclosed that the molecules are connected with each other in the form of dimers through hydrogen bonding in the crystalline network of BFBAH and MOBAH. Additionally, the theoretical calculations were performed using the DFT/B3LYP/6‐311G(d,p) functional. The hyperconjugation and intermolecular hydrogen bonding were explored by using NBO analysis. Hirshfeld surface analysis analyzing intra and intermolecular interactions, uncovered that supramolecular assemblies have been stabilized by N−H⋅⋅⋅O and C−H⋅⋅⋅O intermolecular hydrogen bonds, as well as van der Waals interactions. The quantum theory of atoms in molecules (QT‐AIM) study corroborates that both significant N−H⋅⋅⋅O and C−H⋅⋅⋅O H‐bonds are strong in nature. Besides, global reactivity indices were computed via the energies of HOMO and LUMO orbitals.

Efficient Synthesis of Imine-Carboxylic Acid Functionalized Compounds: Single Crystal, Hirshfeld Surface and Quantum Chemical Exploration

“…Herein, we are focused on exploring these interactions in the studied compounds via Hirshfeld surface analysis through Crystal Explorer v. 21.5 [ 43 ]. A Hirshfeld surface (HS), which is constructed on the basis on normalized distances ( ), enables us to explore the hydrogen bonding interactions [ 31 , 44 , 45 , 46 , 47 ]. Red regions on the surface stand for the smaller interatomic contact, whereas blue parts stand for larger interatomic contacts.…”

Synthesis, Crystal Structure, Hirshfeld Surface Analysis, and Computational Study of a Novel Organic Salt Obtained from Benzylamine and an Acidic Component

“…Other such interactions are ALL–C, ALL–O, and ALL–N with percentage contributions of 15.2, 6.2, and 1.7%, respectively. These interactions are important to discuss as they help better understand the crystal packing. − Similarly, the interaction of an atom present inside the HS with all the atoms located in the vicinity of the HS is computed to further explore crystal packing, as shown in Figure b. This investigation inferred that the H atom present inside the HS has the strongest interaction with the atoms of neighboring molecules present as compared to other atoms.…”

Synthesis, Characterization, Crystal Structures, and Supramolecular Assembly of Copper Complexes Derived from Nitroterephthalic Acid along with Hirshfeld Surface Analysis and Quantum Chemical Studies

“…On the HS, the short and long connections are represented by red and blue patches, respectively. The white dots on the HS indicate the connections where the distance between the interacting atoms is smaller than the total of the atoms’ van der Waals radii. − Figure a,b shows the HS over d norm for Cu-NTA and Cu-DNTA , respectively. The red spot on the HS of Cu-NTA near carboxylate O-atoms, water molecules, and ortho CH of the benzene ring indicates that these atoms are involved in the H-bonding interactions.…”