Electrochemical Syntheses of Pyrimidine-2-thiolato Complexes of Nickel(II) / Crystal and Molecular Structure of 2,2′-Bipyridine-bis(pyrimidine-2-thiolato)nickel(II) Monohydrate

Abstract

The electrochemical oxidation of nickel in pyrimidine-2-thione (pymt H) solution yields a compound of formula [Ni(pymt)2]. When pyridine (py), 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) are added to the solution phase, the product obtained is a complex [Ni(pymt)2py2] or [Ni(pymt)2L] (L = bipy or phen). The crystal structure of [Ni(pymt)2bipy] · H2O is monoclinic, space group P 21/c, with a = 726.6(2), b = 1586.2(2), c = 1696.7(4) pm, β = 99.04(4)° and Z = 4. The nickel atom has highly distorted octahedral coordination and the pyrimidine-2-thiolato ligand is bidentate, forming two four-membered chelate rings with a small “bite” angle of ca. 68°. The two sulphur atoms are in a trans arrangement. The vibrational and electronic spectra of the compounds are discussed.