Reaction of bis(diethanoldithiocarbamato)copper(II), [Cu(deadtc)2] and bis(di-n-propyldithiocarbamato)zinc(II), [Zn(dnpdtc)2] complexes with 2,2’-bipyridine (2,2’-bipy) (1:1 ratio) in ethanol was investigated. Simple mixing of the reactants in 1:1 ratio resulted in five-coordinated [Cu(2,2’--bipy)2S]•CH3CH2OSO3H (1) and [Zn(2,2’-bipy)2S]•CH3CH2OSO3H·2H2O (2). Refluxing the reactants and cooling the contents result in the formation of [Zn(2,2’-bipy)(H2O)2]SO4 (3) and [Cu(2,2’-bipy)(H2O)2]SO4 (4). Complexes 1 and 2 are monomeric with trigonal bipyramidal geometry. A distorted octahedral environment was observed in complexes 3 and 4. The crystal structure of 4 has already been reported in the literature. Crystal structures of 1, 2 and 3 are reported in this paper. The M–S distances in 1 and 2 are 2.318(1) Å and 2.323 Å, respectively. The N–M–S angles are larger than the N–M–N angles due to the steric requirements.