X-ray, vibrational spectra and quantum chemical studies on a new semiorganic crystal: 4-Chloroanilinium perchlorate

Abstract

A new semi-organic material 4-chloroanilinium perchlorate was synthesized and grown as a single crystal by slow evaporation solution growth technique. A good X-ray quality single crystal was selected from the grown crops and used for the single crystal diffraction studies. The asymmetric part of the unit cell contains a 4-chloroanilinium cation and a perchlorate anion. The protonation on the N site of the chloroaniline is confirmed from the CN bond distance and the deprotonation on perchloric acid is confirmed from ClO bond geometry. The molecular aggregations are stabilized through intricate three dimensional hydrogen bonding network formed by the classical NH⋯O hydrogen bonds. It form two infinite chains running along the b-axis of the unit cell which are cross-linked through another NH⋯O bond leading to alternate ring R44(12) motifs. These ring and chain motifs lead to alternate hydrophilic and hydrophobic layers along c-axis of the unit cell. The presence of different functional groups and the nature of their vibrations were identified in experimental vibrational studies through Infra-Red and Raman measurements in the range of 4000–400cm−1. The optimized molecular structure, vibrational mode, computed spectra, molecular properties and NBO analysis of the 4-chloroanilinium perchlorate were found out by quantum chemical calculations with HF and DFT/B3LYP methods invoking 6-311++G(d,p) basis sets. Computed geometrical parameters and harmonic frequencies of fundamental, combination and overtone transitions were found in satisfactory agreement with the experimental data. The electronic properties such as HOMO and LUMO energies were carried out.