Synthesis, X-Ray Structure, Hirshfeld Surface Analysis, DFT Calculations, and Molecular Docking Studies of Nickel(II) Complex with Thiosemicarbazone Derivative.

Uwaisulqarni M Osman,Sharmili Silvarajoo,Suhana Arshad,Ainizatul Husna Anizaim,Fazira Ilyana Abdul Razak,Muhamad Fairus Noor Hassim,Massimiliano F Peana

doi:10.1155/2021/5536902

Abstract

This article presents both experimental and computational study of a new Ni(II) complex, namely, bis{2-(2-trifluoromethylbenzylidene)hydrazine-1-carbothioamido-κ2N2, S}nickel(II) (abbreviate as NiL2). The complex was synthesized and well characterized using various spectroscopic methods. The single X-ray crystallographic study revealed a distorted square planar geometry around Ni(II) metal ion centre in which the angles deviated from ideal 90° with a maximum value of 6.57° occupied by nitrogen and sulphur donor atoms. The theoretical bond lengths and angles for the NiL2 complex were obtained by using the B3LYP level of density function theory (DFT) with LANL2DZ/6-311G (d, p) basis sets. These results showed very good agreement with the experimental X-ray values. The electrophilicity index (ω = 50.233 eV) shows that the NiL2 complex is a very strong electrophile. In addition, strong F⋯H/H⋯F interactions with 28.5% of the total Hirshfeld surface analyses in NiL2 were obtained indicating that the complex could bind with protein effectively. Furthermore, the new NiL2 complex was docked with plasma retinol-binding protein 4 (RBP4) (PDB id: 5NU7), which implied that the NiL2 complex bound to Tyrosine 133 and Aspartate 102 amino acids via N-H intermolecular hydrogen bonds.

Highlights

E versatility of thiosemicarbazone derivatives and its metal complexes allows for the design and development of bioactive compounds, including anticancer [6], antioxidant [7], and antibacterial [8]. (E)-2-(1-(3-Bromophenyl)ethylidene)hydrazine-1-carbothioamide molecule shows high potential in behaving as antimalarial agents [9]
Bioinorganic Chemistry and Applicationsbenzene, and thiosemicarbazone moieties have been synthesized, characterized, and computationally optimized using B3LYP level of density function theory (DFT) with LANL2DZ/6-311G (d, p) basis sets. e experimental X-ray crystallographic structure of the Ni(II) complex has been correlated with the corresponding structure optimized at DFT/ B3LYP/LANL2DZ/6-311G (d, p) level
Selected experimental and theoretical geometric parameters optimized of NiL2 complex structure are shown in Table 2. e molecular structure of the NiL2 complex obtained empirically was compared with theoretical calculation via DFT (Figure 1)

Summary

Introduction

Recent interest in the chemistry of thiosemicarbazone ligands arises mainly from the potential from both azomethine nitrogen and thiolate sulphur donor atoms with variance coordination modes of either monodentate [1], bidentate [2], or tridentate [3].is variance can be performed by introducing different substituents in order to form a selection of mononuclear [4] and polynuclear [5] complexes.e versatility of thiosemicarbazone derivatives and its metal complexes allows for the design and development of bioactive compounds, including anticancer [6], antioxidant [7], and antibacterial [8]. (E)-2-(1-(3-Bromophenyl)ethylidene)hydrazine-1-carbothioamide molecule shows high potential in behaving as antimalarial agents [9]. (E)-2-(1-(3-Bromophenyl)ethylidene)hydrazine-1-carbothioamide molecule shows high potential in behaving as antimalarial agents [9]. Due to these reasons, their structural details are considered useful for structure activity relationships (SAR) design for future applications. In continuation of our research to develop coordination chemistry of thiosemicarbazones and their transition metal complexes [10, 11], a new Ni(II) complex, namely, bis{2-(2-trifluoromethylbenzylidene)hydrazine1-carbothioamido-κ2N2, S} nickel(II), NiL2 containing. Bioinorganic Chemistry and Applications (trifluoromethyl)benzene, and thiosemicarbazone moieties have been synthesized, characterized, and computationally optimized using B3LYP level of density function theory (DFT) with LANL2DZ/6-311G (d, p) basis sets. E experimental X-ray crystallographic structure of the Ni(II) complex has been correlated with the corresponding structure optimized at DFT/ B3LYP/LANL2DZ/6-311G (d, p) level. Hirshfeld surface analysis was used to interpret intermolecular interactions in the NiL2 complex by visual representations whereas molecular docking was studied to know the receptor-amino acid interactions, to predict the important functional groups or atoms in the complex

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Conclusion