A new compound of zinc(II) with the ligand 4,4'-dimethoxy-2,2'-bipyridine(4,4'-dmo-2,2'-bpy), [Zn(4,4'-dmo-2,2'-bpy)(2)(CH3COO)](2)[Zn(SCN)(4)]center dot H2O, has been obtained as white single crystals by the branched tube method and characterized by elemental analysis, IR and (1)HNMRspectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied. The crystal structure consits of two discrete [Zn(4,4'-dmo-2,2'-bpy)(2)(CH3COO)](+) cations and a [Zn(SCN)(4)](2)(-) anion. Zinc(II) cations in the [Zn(4,4'-dmo-2,2'-bpy)(2)(CH3COO)](+) units have a distorted octahedral surrounding by ZnN4O2 coordinated through four N atoms of 4,4'-dmo-2,2'-bpy and two O atoms of acetate. Zinc(II) in [Zn(SCN)(4)](2-) has a distorted tetrahedral coordination environment with an ZnN4 ligated by four N atoms of the terminal thiocyanates. In the solid state, [Zn(4,4'-dmo-2,2'-bpy)(CH3COO)](+) cations are interconnected by tetrahedral [Zn(NCS)(4)](2-) units by cooperative C-H center dot center dot center dot O, C-H center dot center dot center dot S, C-H center dot center dot center dot N and pi-pi stacking interactions resulting in a 2D network structure. Establishment of such networks seems to be aiding the crystallization.