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Synthesis, characterization and thermal studies of Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate: the single crystal structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2).

Onwudiwe DC, Ajibade PA - Int J Mol Sci (2011)

Bottom Line: Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR).One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring.Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Fort Hare, Private Bag X1314, ALICE 5700, South Africa; E-Mail: donwudiwe@ufh.ac.za.

ABSTRACT
Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.

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(a) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing S4···S4 intermolecular interactions; (b) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing C—H···π intermolecular interactions.
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f7-ijms-12-01964: (a) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing S4···S4 intermolecular interactions; (b) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing C—H···π intermolecular interactions.

Mentions: The packing of the complex in the unit cell (Figure 6) is characterized by S….S (Figure 7a) and C-H…л intermolecular interactions (Figure 7b). S….S intermolecular interactions (S4….S4 =3.560(x)Å), (symmetry operator = 2 – x, 1 – y, 1− z) link dinuclear molecules along the crystallographic b axis. The C—H…л intermolecular interactions H6….π = 2.9565 (2)° and <C6–H6….π = 155 (2)°; (symmetry operator = x + 1, −y + ½, z + ½) join S4….S4 also along the crystallographic b axis. The structural diversity observed in the Hg(S2CNR2)2 compounds can be ascribed to intra- or intermolecular association giving rise to distortions from linearity and result in varied coordination geometries [37,42]. The additional interactions observed in the title compound are dictated by the need to maximize intermolecular associations made possible by the absence of steric restrictions precluding association in the lattice. Hence, Hg-S interactions are present which give rise to dimeric structures.


Synthesis, characterization and thermal studies of Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate: the single crystal structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2).

Onwudiwe DC, Ajibade PA - Int J Mol Sci (2011)

(a) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing S4···S4 intermolecular interactions; (b) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing C—H···π intermolecular interactions.
© Copyright Policy - open-access
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC3111644&req=5

f7-ijms-12-01964: (a) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing S4···S4 intermolecular interactions; (b) Packing diagram of [(C6H5)(CH3)NCS2]4Hg2 showing C—H···π intermolecular interactions.
Mentions: The packing of the complex in the unit cell (Figure 6) is characterized by S….S (Figure 7a) and C-H…л intermolecular interactions (Figure 7b). S….S intermolecular interactions (S4….S4 =3.560(x)Å), (symmetry operator = 2 – x, 1 – y, 1− z) link dinuclear molecules along the crystallographic b axis. The C—H…л intermolecular interactions H6….π = 2.9565 (2)° and <C6–H6….π = 155 (2)°; (symmetry operator = x + 1, −y + ½, z + ½) join S4….S4 also along the crystallographic b axis. The structural diversity observed in the Hg(S2CNR2)2 compounds can be ascribed to intra- or intermolecular association giving rise to distortions from linearity and result in varied coordination geometries [37,42]. The additional interactions observed in the title compound are dictated by the need to maximize intermolecular associations made possible by the absence of steric restrictions precluding association in the lattice. Hence, Hg-S interactions are present which give rise to dimeric structures.

Bottom Line: Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR).One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring.Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Fort Hare, Private Bag X1314, ALICE 5700, South Africa; E-Mail: donwudiwe@ufh.ac.za.

ABSTRACT
Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.

Show MeSH
Related in: MedlinePlus