Synthesis, Structural Characterization, Hirshfeld Surface Analysis, and Antibacterial Study of Pd(II) and Ni(II) Schiff Base Complexes Derived from Aliphatic Diamine

Abstract

A Schiff base bearing two methyl substituents, namely, 6,6'-((1<i>E</i>,1'<i>E</i>)-((2,2-dimethylpropane-1,3-diyl) bis(azanylylidene)) bis(methanylylidene)) bis(2-methylphenol) [H₂AD1Me] was synthesized and characterized through physicochemical and spectroscopic analyses. Then, the Schiff base was complexed with Pd(II) and Ni(II) to form [Pd(AD1Me)] and [Ni(AD1Me)], respectively. Both metal complexes were successfully obtained and characterized through several analyses, <i>viz</i>., melting point, elemental analysis, molar conductivity, magnetic susceptibility, FTIR, ¹H NMR, UV-vis, and single crystal X-ray diffraction. A quantitative analysis of the intermolecular interactions in the crystal structures has been performed using Hirshfeld surface analysis. Both metal complexes were crystallized in a monoclinic crystal system with the space group of <i>P</i>2₁/<i>c</i>. Additionally, the deprotonated phenolic oxygen atom (O1/O2) and azomethine nitrogen atom (N1/N2) of the ligand chelate the Pd(II) and Ni(II) ions, forming a slightly distorted square-planar complex containing three six-membered rings encircling the metal core with dsp² hybridization. The shift of ν(C=N) to a higher frequency in FTIR by 26-28 cm^-1 indicated that the complexation to Pd(II) and Ni(II) through the azomethine N was established. It was further supported through the shifting of the azomethine proton signal to higher or lower chemical shifts with Δδ = 0.43-1.15 ppm in ¹H NMR. In addition, the shifting of the n-π*(C=N) band in UV-vis spectra with Δλ = 24-40 nm indicated the involvement of azomethine nitrogen in the complexation. All the compounds showed no significant antibacterial activity against three bacterial strains, namely, <i>Staphylococcus aureus</i> subsp. <i>aureus</i> Rosenbach (ATCC 6538), <i>Streptococcus mutans</i> Clarke (ATCC 700,610), and <i>Proteus vulgaris</i> (ATCC 6380), as the percent growth inhibition calculated was less than 90%.