Supramolecular interactions in high molecular weight bisdithiocarbamate adducts of divalent Zn(II), Cd(II), and Hg(II): spectral, VBS, and single crystal X-ray structural studies on MS₄N₂ chromophores

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.

Keywords:

• Dithiocarbamate
• Supramolecular
• Thioureide
• NMR
• Thermogravimetry
• Single crystal X-ray structure