Electron density distribution studies on ZnS 4N 2 chromophore in solution and solid phases: XPS and cyclic voltammetric studies on 1,10-phenanthroline and 2,2′-bipyridine adducts of bis(piperidinecarbodithioato-S,S′)zinc(II). Single crystal X-ray structure of (2,2′-bipyridine)bis-(piperidinecarbodithioato-S,S′)zinc(II)

Abstract

(1,10-phenanthroline)bis(piperidinecarbodithioato-S,S′)zinc(II), [Zn(pipdtc) 2(1,10-phen)] ( 1) and (2,2′-bipyridine)bis(piperidinecarbodithioatao-S,S′)zinc(II), [Zn(pipdtc) 2(bipy)] ( 2) adducts were prepared and the crystal structure of 2 is reported. The Zn–S distances in 2 are longer than those in Zn(dtc) 2 complexes. The presence of an additional neutral ligand causes an increase of the Zn–S bond lengths. S2p binding energies show a significant reduction in value compared to the parent dithiocarbmate [Zn(pipdtc) 2]( 3), indicating the weakening of the Zn–S bond on adduct formation. The observed reduction in binding energy is due to the increased electron density on the metal in the adducts. The cyclic voltammetric study on the complexes also show an increase of electron density on zinc in the adducts compared to Zn(pipdtc) 2. The S–Zn–S angle in the adduct shows a reduction due to increased coordination around zinc. The thioureide C–N distance of 1.343(13) Å in compound 2 is in line with the νC–N observed at 1469 cm −1.