ISSN:
1572-8854
Keywords:
Zinc complexes
;
dithiocarbamate
;
bipyridyl
;
1,10-phenanthroline
;
x-ray structure
;
thermal analysis
;
IR spectra
Source:
Springer Online Journal Archives 1860-2000
Topics:
Geosciences
,
Physics
Notes:
Abstract Synthesis, spectral, and single crystal X-ray structural studies on (2,2′-bipyridyl)bis (dimethyldithiocarbamato)zinc(II) (1) and (l,10-phenanthroline)bis(dimethyldithiocarbamato)zinc(II) (2) complexes are reported in this paper. The complex (1) crystallizes in the orthorhombic lattice, space group Pcca, a = 18.456(3), b = 6.529(2), and c = 17.092(2) Å. The complex (2) crystallizes in the monoclinic space group C2/c, a = 13.372(2), b = 13.850(2), c = 24.680(3) Å, and β = 102.71(4)°. IR spectra of the complexes (1) and (2) show the thioureide υ(C-N) bands at 1489 and 1510 cm−1, respectively, which are lower than the value observed for the parent bisdithiocarbamate. Reduction in the thioureide stretching frequency is due to the increase in coordination around the zinc ion and the resultant increase in electron density. Thermal studies indicate that the 1,10-phenanthroline adduct is marginally more stable than the other complex. X-ray crystal structures of the two adducts show them to be octahedrally coordinated and monomeric in nature. The Zn-S distances are longer than those observed in the parent bisdithiocarbamate. The thioureide C-N bond distances in (1) and in (2) indicate the partial double bond character. The most important structural changes as a result of the adduct formation are observed in the Zn-S bond distances and S-Zn-S bond angles, in terms of very significant increases in Zn-S bond distances and reductions in S-Zn-S angles, compared to the parent bisdithiocarbamate. The observed changes are indicative of a strong steric force in operation in the adducts rather than electronic effects.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1023/A:1022838200412
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