Abstract
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.
Highlights
A wide spectrum of nitrogen- and sulfur-including ligands like dithiocarbazates, thiosemicarbazones, and dithiocarbamates with their metal ion complexes have experienced supplementary interest in the field of medicine and pharmacology due to their potent applications, such as antibacterial, antiviral, antitumor, antifungal, and antiparasitic activities [1,2,3,4,5,6,7,8]
The hydrazinecarbodithioate Schiff bases derived from S-acetyl, S-alkyl, S-methyl dithiocarbazates, and dithiocarbazate represent the preponderance of advanced reports available on the Cambridge Structural Database
The free thione form of the ligand was subjected to tautomerization to a thiol form [29], (1E,1E)-benzyl hydrogen (1-(4chlorophenyl)ethylidene)carbonhydrazonodithioate, in the solution prior to coordination to the copper metal center
Summary
A wide spectrum of nitrogen- and sulfur-including ligands like dithiocarbazates, thiosemicarbazones, and dithiocarbamates with their metal ion complexes have experienced supplementary interest in the field of medicine and pharmacology due to their potent applications, such as antibacterial, antiviral, antitumor, antifungal, and antiparasitic activities [1,2,3,4,5,6,7,8]. Despite the fact that coordinated hydrazinecarbodithioate Schiff bases to transition metals are scarcely reported and demonstrated on compared to the free ligands, full characterization by XRD analysis is highly demanded in order to obtain a real structural vision. A square planar molecular geometry could be created once the four groups are located at the corners of a square in the same plane of the central metal, with the possibility of possessing cis or trans conformation, e.g., M(N,S), in which N,S is a bidentate ligand. A hybrid molecular geometry, namely, a tetrahedrally distorted square planar shape, can be formed due to the distorted coordinated ligand moieties to the metal center [22,23]. Structural elucidation by XRD analysis offers an excellent level of characterization of the geometry around metal complexes. Optimization and frequency calculations were performed in gaseous state using LanL2DZ basis set for the copper metal, whereas 6-311G(d,p) was designated for all other atoms
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