Abstract
This article describes supramolecular interactions induced in a high molecular weight dithiocarbamate, padtc, by its design. Synthesis, spectral studies involving zinc, cadmium and mercury, padtc, and adducts with tmed, such as [Zn(padtc)2] (1), [Zn(padtc)2(tmed)] · C6H5CH3 · 0.5(H2O) (2), [Cd(padtc)2] (3), [Cd(padtc)2(tmed)] · C6H5CH3 · 0.36(H2O) (4), [Hg(padtc)2] · H2O (5), [Hg(padtc)2(2,2′-bipy)] · H2O (6), [Hg(padtc)2(1,10-phen)] · H2O (7), and [Hg(padtc)2(oxine)] · H2O (8) (where padtc− = N,N′-(iminodiethylene)bisphthalimidedithiocarbamate, 1,10-phen = 1,10-phenanthroline, tmed = tetramethylethylenediamine, 2,2′-bipy = 2,2′-bipyridine, oxine = 8-hydroxyquinoline) along with the single crystal X-ray structural analysis of [Zn(padtc)2(tmed)] · C6H5CH3 · 0.5(H2O) (2) and [Cd(padtc)2(tmed)] · C6H5CH3 · 0.36(H2O) (4) are reported. All the complexes were characterized by IR, NMR (1H and 13C), and thermogravimetric study. The IR spectra of the complexes show the contribution of the thioureide form to the structures. In 13C NMR spectra, the most important thioureide (N13CS2) carbon signals are observed at 210–212 ppm. Single crystal X-ray structural analyses of 2 and 4 show the presence of extensive supramolecular interactions stabilizing the solid-state structure. Both zinc and cadmium are in a distorted octahedral environment with MS4N2 chromophores. VBS of Zn and Cd are 1.76 and 1.98, respectively, supporting the correctness of the determined structure and the valence of the central metal ions.