Synthesis, characterization, and biological properties of mono-, di- and poly-nuclear bismuth(III) halide complexes containing thiophene-2-carbaldehyde thiosemicarbazones

Abstract

In order to investigate the coordination chemistry and pharmacological applications of bismuth compounds, a series of new bismuth(III) halide thiosemicarbazone complexes were synthesized. The reactions of thiophene-2-carbaldehyde-N-substituted thiosemicarbazones with bismuth(III) halides resulted in the formation of the {[[BiCl2(eta 1-S-Httsc)4]+.Cl-][BiCl2(mu 2-Cl)(eta 1-S-Httsc)2]2} (1), {[BiCl3(eta 1-S-Htmtsc)3].CH3OH} (2), {[BiCl3(eta 1-S-Htetsc)3].CH3OH} (3), {[BiBr2(mu 2-Br)(eta 1-S-Httsc)2]2.CH3OH} (4), {[BiBr2(mu 2-Br)(eta 1-S-Htmtsc)2]n} (5), and {[BiI2(mu 2-I)(eta 1-S-Httsc)2]2} (6) complexes (Httsc: thiophene-2-carbaldehyde thiosemicarbazone, Htmtsc: thio-phene-2-carbaldehyde-N-methyl thiosemicarbazone, Htetsc: thiophene-2-carbaldehyde-N-ethyl thio-semicarbazone). The complexes were characterized by a number of different spectroscopic techniques and the crystal structures of all bismuth(III) complexes (1-6) were determined by using single crystal X-ray diffraction study. In addition, the thermal stability of the complexes was compared using Thermogravimetric-differential thermal analysis. Crystal structures of the two free ligands, thiophene-2-carbaldehyde-N-methyl-thio-semicarbazone and thiophene-2-carbaldehyde-N-ethyl-thiosemicarbazone, were also determined by using single crystal X-ray diffraction analysis. The Hirshfeld surface of the bismuth(III) complexes and free ligands were additionally analyzed to verify the intermolecular interactions. Biological studies showed that all six bismuth(III) thiosemicarbazone complexes (1-6) exhibited biological activities against selected bacteria and the human breast adenocarcinoma (MCF-7) cell line.