Synthesis, spectra, crystal structures and anticancer studies of 26‐membered macrocyclic dibutyltin(IV) dithiocarbamate complexes: Single‐source precursors for tin sulfide nanoparticles

Abstract

Four new macrocyclic dinuclear dibutyltin(IV) dithiocarbamate complexes of the type [Bu2Sn(dtc)]2, where dtc = hexane‐1,6‐diylbis(4‐fluorobenzyldithiocarbamate) anion (1), hexane‐1,6‐diylbis(4‐chlorobenzyldithiocarbamate) anion (2), hexane‐1,6‐diylbis(furfuryldithiocarbamate) anion (3) and hexane‐1,6‐diylbis(pyrrole‐2‐ylmethyldithiocarbamate) anion (4), have been prepared. The dithiocarbamate ligands efficiently self‐assemble with Bu2Sn(IV) to form bimetallic 26‐membered macrocycles. All the complexes have been characterized using elemental analysis, infrared and NMR (1H and 13C) spectroscopies and X‐ray crystallography. Single‐crystal X‐ray diffraction analysis of all the complexes confirms the formation of the dinuclear metallomacrocycles in which dithiocarbamate ligands are asymmetrically bound to the tin atoms. The coordination sphere around the tin atom in 1–4 can be described as a skew trapezoidal bipyramid. The dimensions of the cavity of the macrocycles of 1–4 are ca 8.0 × 9.0 Å2. Complexes 1–4 were evaluated for their in vitro anticancer activity against MCF‐7 and HL‐60 cells. Complexes 1 and 2 are more active against MCF‐7 and HL‐60. Thermal decomposition of 1 and 4 yielded tin sulfides. They were characterized using powder X‐ray diffraction (PXRD), high‐resolution transmission electron microscopy and UV diffuse reflectance and energy‐dispersive X‐ray spectroscopies. PXRD studies reveal that the as‐prepared tin sulfides are composed of orthorhombic phase of SnS.

A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

“…As with many of the compounds in this overview, the synthesis was facile such as in the metathetical reaction leading to 51: the diorganotin dichloride was reacted with K 2 [L 21 ]. Additional interest in 59-61 related to their putative anti-cancer potential along with utility as precursors for the deposition of tin sulphide nanomaterials [64], each being classical applications of organotin dithiocarbamates [91]. The screening for anti-cancer potential indicated that the halogen-containing substituents in the dithiocarbamate ligands, as in 59 and 60, increase the cytotoxicity [64].…”

“…Additional interest in 59-61 related to their putative anti-cancer potential along with utility as precursors for the deposition of tin sulphide nanomaterials [64], each being classical applications of organotin dithiocarbamates [91]. The screening for anti-cancer potential indicated that the halogen-containing substituents in the dithiocarbamate ligands, as in 59 and 60, increase the cytotoxicity [64]. With the exception of 65, each of the di-nuclear structures in 51-66 is disposed about a centre of inversion; in 51, two independent molecules comprise the asymmetric unit, each being centrosymmetric.…”

“…Indeed, each hydroxyl-hydrogen atom forms a hydrogen-bond to a thione-sulphur atom to form a linear, supramolecular tape. In addition to cytotoxic 59 and 60, [64], several organotin poly-dithiocarbamate compounds showed promising biological activities. Thus, 64 and 87 were tested, in vitro, The next category of molecular structures also resembles the preceding two classes and conforms to the general formula (R 3 Sn) 2 (S 2 C-spacer-CS 2 ).…”

“…Indeed, each hydroxyl-hydrogen atom forms a hydrogen-bond to a thione-sulphur atom to form a linear, supramolecular tape. In addition to cytotoxic 59 and 60, [64], several organotin poly-dithiocarbamate compounds showed promising biological activities. Thus, 64 and 87 were tested, in vitro, In addition to cytotoxic 59 and 60, [64], several organotin poly-dithiocarbamate compounds showed promising biological activities.…”

“…In addition to cytotoxic 59 and 60, [64], several organotin poly-dithiocarbamate compounds showed promising biological activities. Thus, 64 and 87 were tested, in vitro, In addition to cytotoxic 59 and 60, [64], several organotin poly-dithiocarbamate compounds showed promising biological activities. Thus, 64 and 87 were tested, in vitro, for fungicidal activity and were found to display good anti-fungal activity towards S. sclerotiorum [66].…”