Experimental and computational studies on creatininium 4-nitrobenzoate - An organic proton transfer complex.

A new organic proton transfer complex of creatininium 4-nitrobenzoate (C4NB) has been synthesized and its single crystals were grown successfully by slow evaporation technique. The grown single crystal was subjected to various characterization techniques like single crystal X-ray diffraction (SCXRD), FTIR, FT-Raman and Kurtz-Perry powder second harmonic generation (SHG). The SCXRD analysis revealed that C4NB was crystallized into orthorhombic crystal system, with noncentrosymmetric (NCS), P 2 1 2 1 2 1 space group. The creatininium cation and 4-nitrobenzoate anion were connected through a pair of N __ H⋯O hydrogen bonds (N(3) __ H(6) ⋯ O(3) (x+1, y, z) and N(2) __ H(5) &ctdot O(2) (x-1/2, -y-1/2, -z+2)) and fashioned a R 2 2 ( 8 ) ring motif. The crystal structure was stabilized by strong N __ H⋯O and weak C __ H⋯O intermolecular interactions and it was quantitatively analysed by Hirshfeld surface and fingerprint (FP) analysis. FTIR and FT-Raman studies confirmed the vibrational modes of functional groups present in C4NB compound indubitably. SHG efficiency of grown crystal was 4.6 times greater than that of standard potassium dihydrogen phosphate (KDP) material. Moreover, density functional theory (DFT) studies such as Mulliken charge distribution, frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) map, natural bond orbital analysis (NBO) and first order hyperpolarizability (β 0 ) were calculated to explore the structure-property relationship. [ABSTRACT FROM AUTHOR]