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

Abstract

• FHPE hydrazone crystals grown by the slow evaporation solution growth. • FHPE crystals showed higher transparent characteristics. • Inter and intramolecular interactions were determined employing the DFT. • FHPE possessed higher hyperpolarizability (3264.29×10 -30 esu). • The higher chemical stability and reactivity of hydrazone were proved. 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 ( 1 H and 13 C 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 ¯ . 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 (3264.29×10 −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.