Crystal structure, DFT study, Hirshfeld analysis and optical third order nonlinear properties of new 1-naphthylaminium hydrogen fumarate salt

Abstract

This study reports the crystal structure and its supramolecular framework, quantum chemical calculations and nonlinear optical properties of 1-naphthylaminium hydrogen fumarate salt. The supramolecular self-assembly of fumarate anions and 1-naphthylaminium cation of the salt is primarily stabilized by N-H…O, O-H…O and C-H…O interactions. The construction of strong hydrogen bonds such as N-H…O and O-H…O produces two-dimensional corrugated sheet parallel to (010) plane, which resembles a supramolecular grid type architecture in the crystal structure. Two weak C-H…O interactions interlink the parallel (010) supramolecular sheet generating a three-dimensional molecular network. The molecular stability of the experimentally determined structure is theoretically optimized by DFT quantum chemical calculations using 6-31G(++) basis set. The relative molecular interaction-based charge distribution and the chemical reactivity of the titled salt were identified using electrostatic potential contouring and HOMO-LUMO maps. The crystal structure is subjected to Hirshfeld surface analysis to gain better understanding on the intermolecular interactions exhibited by the molecules. The optical nonlinearities of the titled salt are examined using Z-scan experimentation, the optical nonlinear refractive index and optical nonlinear absorption coefficient is estimated by closed and open aperture Z-scan methods. The observed nonlinear values are quite comparable to the conventional optical nonlinear values.