Synthesis, spectral and X-ray structural studies on Hg(II) dithiocarbamate complexes: A new precursor for HgS nanoparticles. (16th August 2015)

• Record Type: Journal Article
• Authors: Dar, Sajad Hussain; Thirumaran, S.; Selvanayagam, S.
• Is Part Of: Polyhedron. Volume 96(2015)
• Page Start: 16
• Page End: 24
• Publication Date: 2015-08-16
• Subjects: Mercury(II) dithiocarbamates -- Single source precursor -- Mercury sulfide nanoparticles -- Hydrogen bond -- Crystal structure; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2015.04.020
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: The crystal structures of1 and2 show that the geometries around each mercury atom in1 and2 are distorted square pyramidal and tetrahedral, respectively.2 was used as a single source precursor for the preparation of HgS nanoparticles. The morphology of the nanoparticles depends on the refluxing time of the reaction. Abstract: Bis(N-furfuryl-N-(2-phenylethyl)dithiocarbamato-S, S′)mercury(II) (1 ), bis((furan-2-yl)methyl(2-(thiophen-2-yl)ethyl)dithiocarbamato-S, S′)mercury(II) (2 ), bis(N-benzyl-N-(2-(thiophen-2-yl)ethyl)dithiocarbamato-S, S′)mercury(II) (3 ) and bis(N-furfuryl-N-propyldithiocarbamato-S, S′)mercury(II) (4 ) have been prepared and characterized by IR and NMR spectroscopy. Compounds1 and2 have also been characterized by the X-ray diffraction technique. In complexes1 and2, the metal centres are five and four coordinated, respectively. The coordination geometry of1 is intermediate between a square pyramidal and trigonal bipyramidal coordination polyhedron, with τ 5 = 0.53. Hg(II) is in a distorted [HgS4 ] tetrahedral environment in compound2 . This difference in geometry between complexes1 and2 is probably due to the effect of the N-bound organic moiety of the dithiocarbamate ligand and the crystal packing. The crystal structures show the presence of C–H⋯S interactions. Complex2 has been dissolved in ethylenediamine and refluxed for 15 min and 1 h to yield ethylenediamine capped mercury sulfide and mercury sulfide without a capping agent (en), respectively. The resulting nanoparticles have been characterized by powder X-ray diffraction (PXRD), SEM, EDAX, IR, UV–Vis and fluorescence spectroscopy. The powder X-ray diffraction data confirm the particles to be very crystalline with the α phase (cinnabar) present in both samples.