Preparation and structural characterization of nickel(II), cobalt(II), zinc(II) and tin(IV) complexes of the isatin Schiff bases of S-methyl and S-benzyldithiocarbazates

Ali, M. Akbar, Mirza, A. H., Abu Bakar, Hjh Junaidah Hj and Bernhardt, Paul V. (2011) Preparation and structural characterization of nickel(II), cobalt(II), zinc(II) and tin(IV) complexes of the isatin Schiff bases of S-methyl and S-benzyldithiocarbazates. Polyhedron, 30 4: 556-564. doi:10.1016/j.poly.2010.11.016


Author Ali, M. Akbar
Mirza, A. H.
Abu Bakar, Hjh Junaidah Hj
Bernhardt, Paul V.
Title Preparation and structural characterization of nickel(II), cobalt(II), zinc(II) and tin(IV) complexes of the isatin Schiff bases of S-methyl and S-benzyldithiocarbazates
Journal name Polyhedron   Check publisher's open access policy
ISSN 0277-5387
1873-3719
Publication date 2011-03-11
Year available 2010
Sub-type Article (original research)
DOI 10.1016/j.poly.2010.11.016
Open Access Status Not Open Access
Volume 30
Issue 4
Start page 556
End page 564
Total pages 9
Place of publication Oxford, United Kingdom
Publisher Pergamon
Language eng
Formatted abstract
The molecular structures of the isatin Schiff bases of S-methyldithiocarbazate (Hisasme) and S-benzyldithiocarbazate (Hisasbz) have been determined by X-ray diffraction and their complexes of general formula [ML2n(solvate) [M = Co2+, Ni2+, Zn2+; L = anionic forms of Hisasme or Hisasbz; solvate = DMF, DMSO; n = 1, 2] and [Sn(L)Ph2Cl]·nMeOH (n = 0, 1) have been synthesized and characterized by a variety of physicochemical techniques and X-ray diffraction. The bis-ligand complexes, [Ni(isasbz)2]·2DMSO and [Co(isasme)2]·DMF have a six-coordinate, distorted octahedral geometry with the two uninegatively charged tridentate ONS ligands coordinated to the metal ions meridionally via the amide O-atoms, the azomethine nitrogen atoms and the thiolate sulfur atoms. By contrast, the crystal structure of [Zn(isasbz)2]·2DMF shows a four-coordinate distorted tetrahedral geometry with the two Schiff bases coordinated as NS bidentate ligands via the azomethine nitrogen atoms and the thiolate sulfur atoms. Steric constraints of the rigid tridentate ligands lead to unusual ‘pseudo-coordination’ of the O-donors which occupy sites close to the metal but too distant to be considered as true coordinate bonds.

The crystal structures of the tin(IV) complexes [SnLPh2Cl]·nMeOH (L = isasme and isasbz; n = 0, 1) also show that the Schiff bases act as monoanionic bidentate NS chelating agents coordinating the tin(IV) ion via the azomethine nitrogen atoms and the thiolate sulfur atoms, the tin atom in each complex is five-coordinate with a highly distorted geometry intermediate of square pyramidal and trigonal bipyramidal. Again Sn⋯O contacts are weak and do not qualify as coordinate bonds.
Keyword Isatin Schiff base of S-methyldithiocarbazate
and S-benzyldithiocarbazate
Nickel(II), cobalt(II), zinc(II), copper(II) and tin(IV) complexes
Crystal structure
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Available online 21 November 2010

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Mon, 27 Feb 2012, 21:23:32 EST by Lucy O'Brien on behalf of School of Chemistry & Molecular Biosciences