Sulfonamide derived Schiff base Mn (II), Co (II), and Ni (II) complexes: Crystal structures, density functional theory and Hirshfeld surface analysis

Abstract

The three transition metal complexes of the ligand named as 2,4‐dibromo‐6‐{[2‐(1,1‐dioxo‐1H‐benzoisothiazole‐3‐yl‐amino)‐ethylimino]‐methyl}‐phenol 3 were synthesized with divalent manganese, cobalt and nickel metal ions and characterized by employing different analytical methods including UV–visible, FT‐IR and elemental analyses. The crystal structures of Mn (II) complex 4, Co (II) complex 5, and Ni (II) complex 6 are determined by single beam X‐rays crystallography, which confirm the distorted octahedral coordination of the complexes 4–6. The non‐covalent interactions of the complexes 4–6 are investigated by the Hirshfeld surface analysis. The tendency of the pair of chemical species to form crystal packing interactions are computed, which provide the favorable contacts in the crystal packing for the complexes 4–6. For the sake of computing strength of the crystal packing, void analysis is performed for the complexes 4–6. The non‐electrolytic nature of synthesized metal complexes was confirmed by molar conductance. The spectral analyses suggested that sulfonamide functionalized Schiff base behaves as bidentate ligand and coordinates with the metal center through phenolic oxygen and iminic nitrogen atoms. The density functional theory (DFT) studies were performed for the Mn (II), Co (II), and Ni (II) metal complexes at the B3LYP/LANL2DZ level of theory. The structural characteristics, vibrational analysis (IR), NMR analysis, UV–Vis, natural bonding orbital (NBO), frontier molecular orbital (FMO), charges (Mulliken and NPA), global reactivity descriptors, molecular electrostatic potential (MEP), and dipole moments were investigated using this method. The large values of stabilization energy, that is, 12.02, 15.25, and 23.81 kcal/mol were found for the complexes Mn (II) 4, Co (II) 5, and Ni (II) 6, respectively by NBO analysis. The global reactivity findings suggested the positive values of electron affinity for all complexes, which indicate the involvement of charge transfer reaction. Among these complexes, complex 6 is the most stable and complex 4 is the least. Further, FMO analysis indicated large HOMO‐LUMO gap (3.85–3.97 eV) with higher LUMO values for all metal complexes.

Synthesis of dimeric 1,2-benzothiazine 1,1-dioxide scaffolds: molecular structures, Hirshfeld surface analysis, DFT and enzyme inhibition studies

“…The sulphonamide asymmetric and symmetric vibrations were found at 1365–1327 cm −1 and 1160–1122 cm −1 . 22,23 Furthermore, FTIR of the synthesized compounds were also computed from output files of the DFT studies. It was found a strong relation between experimental and theoretical studies (Fig.…”

Zn(ii) and Cd(ii) pincer complexes bearing meta alkylated pyridinium amidates; synthesis & preliminary anticancer studies

“…42 The normalized distances from the closest atoms inside ( d i ) and outside ( d e ) the surface to the Hirshfeld surface were combined to create the d norm , which displayed all of the crystal structure's interactions. 43–45 Red regions showed interactions that were shorter than the total van der Waals radii of the participating atoms, whereas blue and white regions represented contacts that were longer and closer to the van der Waals limit, respectively. The HS plots over d norm of the complexes ( C3 and C4 ) are shown in Fig.…”

Trivalent Metal Complexes of Rich-Hyrdoxy Schiff base Ligand: Synthesis, Characterization, DFT Calculations and Antimicrobial Activity

“…The Gaussian09 software was used to perform density functional theory (DFT) calculations [40]. To optimize the different complexes, we applied the most accurate and reasonable functional B3LYP and LANL2DZ/6-311G(d,p) basis set via DFT [41][42][43]. The LANL2DZ basis set was limited to core potential metals Cr(III), Fe(III), and Ru(III), and the 6-311G(d,p) basis set involved one set of d and p functions to describe the molecular and electronic properties of organic molecules (C, H, N, O, and Cl) [44]- [48].…”