Synthesis, crystal growth, spectroscopic characterization, Hirshfeld surface analysis and DFT investigations of novel nonlinear optically active 4-benzoylpyridine-derived hydrazone

Hydrazones are the vital compounds which possess remarkable properties and are widely used in organic synthesis, analytical chemistry and medicine. In this research, single crystals of a novel hydrazone, 4-(2-(furan-2-carbonyl)hydrazono(phenyl)methyl)-pyridin-1-ium ethylsulphate hydrate (FHPE), were grown via the slow evaporation from solution growth technique. The FHPE crystal was characterized using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (H-1 and C-13 NMR) spectroscopy, single crystal X-ray diffraction, powder X-ray diffraction (PXRD), UV-Vis absorption and scanning electron microscopy (SEM) techniques. Single crystal X-ray diffraction analysis revealed that FHPE hydrazone belonged to the triclinic system with centrosymmetric space group P (1) over bar. PXRD and SEM studies substantiated the good crystallinity of the as-grown specimen. Result of the UV-Vis absorption study proved higher transparent characteristics of FHPE crystals. The dipole moment, polarizability, HOMO-LUMO energies, oscillator strength and Mulliken charge populations were determined by density functional theory (DFT) method with B3LYP/6-31G(d,p). The optimized molecular structure of FHPE was in concurrence with the ORTEP results. The FHPE hydrazone possessed great hyperpolarizability (3264.29 x 10(-30) esu) compared to that of the reference material, urea, as determined by theoretical calculations. Hirshfeld surface analysis results demonstrated proton transfer induced charge transfer and inter or intramolecular interactions, contributing superior nonlinearity of crystals. Investigations of electronic properties confirmed the greater chemical stability and reactivity of hydrazone. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

The novel hydrazone crystal FHPE was successfully synthesized and characterized using various techniques. Results showed that FHPE has high transparency, superior hyperpolarizability, and greater chemical stability.