On the Coordination Role of Pyridyl-Nitrogen in the Structural Chemistry of Pyridyl-Substituted Dithiocarbamate Ligands

A search of the Cambridge Structural Database was conducted for pyridyl-substituted dithiocarbamate ligands. This entailed molecules containing both an NCS2− residue and pyridyl group(s), in order to study their complexation behavior in their transition metal and main group element crystals, i.e., d- and p-block elements. In all, 73 different structures were identified with 30 distinct dithiocarbamate ligands. As a general observation, the structures of the transition metal dithiocarbamates resembled those of their non-pyridyl derivatives, there being no role for the pyridyl-nitrogen atom in coordination. While the same is true for many main group element dithiocarbamates, a far greater role for coordination of the pyridyl-nitrogen atoms was evident, in particular, for the heavier elements. The participation of pyridyl-nitrogen in coordination often leads to the formation of dimeric aggregates but also one-dimensional chains and two-dimensional arrays. Capricious behaviour in closely related species that adopted very different architectures is noted. Sometimes different molecules comprising the asymmetric-unit of a crystal behave differently. The foregoing suggests this to be an area in early development and is a fertile avenue for systematic research for probing further crystallization outcomes and for the rational generation of supramolecular architectures.

The remarkable propensity for the formation of C–H⋯π(chelate ring) interactions in the crystals of the first-row transition metal dithiocarbamates and the supramolecular architectures they sustain

C–H⋯π(chelate ring) interactions play an important role in assembling first-row transition metal dithiocarbamates in their crystals.

Self-assembled transition metal dithiocarbamates of pyridine-3-carboxamide: synthesis, spectral characterization, thermal and biological studies

Synthesis of self assembled transition metal dithiocarbamates of pyridine-3-carboxamide by conventional as well as in situ methodology was reported. Characterization was done with a variety of spectroscopic techniques. Anticancer and antioxidant activity of ligand and its complexes is also tested.

Identification of Metal Dithiocarbamates as a Novel Class of Antileishmanial Agents

ABSTRACTDithiocarbamates have emerged as potent carbonic anhydrase (CA) inhibitors in recent years. Given that CAs are important players in cellular metabolism, the objective of this work was to exploit the CA-inhibitory property of dithiocarbamates as a chemotherapeutic weapon against theLeishmaniaparasite. We report here strong antileishmanial activity of three hitherto unexplored metal dithiocarbamates, maneb, zineb, and propineb. They inhibited CA activity inLeishmania majorpromastigotes at submicromolar concentrations and resulted in a dose-dependent inhibition of parasite growth. Treatment with maneb, zineb, and propineb caused morphological deformities of the parasite andLeishmaniacell death with 50% lethal dose (LD50) values of 0.56 μM, 0.61 μM, and 0.27 μM, respectively. These compounds were even more effective against parasites growing in acidic medium, in which their LD50values were severalfold lower. Intracellular acidosis leading to apoptotic and necrotic death ofL. majorpromastigotes was found to be the basis of their leishmanicidal activity. Maneb, zineb, and propineb also efficiently reduced the intracellular parasite burden, suggesting that amastigote forms of the parasite are also susceptible to these metal dithiocarbamates. Interestingly, mammalian cells were unaffected by these compounds even at concentrations which are severalfold higher than their antileishmanial LD50s). Our data thus establish maneb, zineb, and propineb as a new class of antileishmanial compounds having broad therapeutic indices.

Intermolecular anagostic interactions in group 10 metal dithiocarbamates

The effects of substituents on the dithiocarbamate backbone on novel C–H⋯M and C–H⋯CG(CS2M) (M = Ni, Pd, Pt) interactions have been investigated.