Synthesis, spectroscopic studies, thermal analyses, biological activity of tridentate-coordinated transition-metal complexes [M(L)X-2] and crystal structure of [ZnBr2(2,6-bis(tert-butylthiomethyl)pyridine)]

摘要

A new terdentate acyclic pincer ligand, 2,6-bis(tert-butylthiomethyl)pyridine (tbtmp), was synthesized and reacted with several complexes of iron, zinc, nickel, cobalt, and copper. The ligand and its coordination compounds were characterized using elemental analysis, infrared, H-1- and C-13-NMR-spectroscopy, thermal analyses, plus-for the Zn complex single-crystal X-ray diffractometry. The structure of [Zn(L)Br-2] was solved in the tetragonal crystal system, chiral space groups P4(1)2(1)2 and P4(3)2(1)2 (No. 92 and No. 96, a = 947.2(1) pm, c = 2265.2(5) pm), revealing five-fold coordination of the metal atoms. According to spectroscopy, all complexes share the same coordination environment around the metal atoms, consisting of two halide anions and a sulfur-methylene-pyridine-methylene-sulfur entity; tbtmp acts as a tridentate ligand with the pyridine N atom and both tert-butylthio S atoms coordinating to the metal ions (NS2). The analysis results indicate that the metal ions are coordinated as distorted pseudo-bipyramids, LMX2, with the chelate ligand meridionally arranged. One of the complexes contains ethanol as an additional ligand, resulting in a pseudo-octahedral coordination sphere [Ni(L)Cl2EtOH]. The latter was obtained in the form of green crystals, which turn into a red powder with loss of the ethanol molecule. Fe (III), Co(II), Ni(II) and Cu(II) metal complexes [M(L)Cl-2] were screened for their antibacterial activity against B. subtilis G(+) and Escherichia coli G(-) bacteria, and fungus (Candida albicans and Aspergillus flavus). (C) 2014 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.