Spectroscopic Insight into Tetrahedrally Distorted Square Planar Copper(II) Complex: XRD/HSA, Physicochemical, DFT, and Thermal Investigations

The reaction of bidentate N-S-thione-Schiff base, (E)-benzyl 2-(1-(4-chlorophenyl)-ethylidene)hydrazinecarbodithioate, with Cu(NO3)2·3H2O produced a cis-Cu(II) complex. The molecular structure was confirmed and characterized by CHN-EA, FAB-MS, IR, and UV-Vis analyses. The XRD supported cis-isomer of the bis anionic bidentate N (azomethine) and S (thiol) ligand coordination mode in tetrahedrally distorted square planar, rarely reported in the literature. The results of the XRD-bond lengths were in perfect agreement with the density functional theory (DFT) calculation. DFT-calculated angles around the Cu(II) center displayed slightly less distortion around the metal center from those of XRD. Additionally, the thermal stability of the complex was evaluated via thermal gravimetric analysis (TGA). Two-dimensional fingerprint (2D-FP), Hirshfeld surface analysis (HSA), and molecular electrostatic potential (MEP) support the XRD-packing results with the existence of the H⸱⸱⸱Cl and CH⸱⸱⸱π bonds as the main interactions in the crystal lattice of the desired complex.