The crystal structures of [Ni(Hbim)(3)](2)(NEt(4))(2)(H(2)bim). MeOH (1) (Hbim(-) = mono diprotonated 2,2’-biimidazolate and NEt4(+) = cation) has been determined. The structure was consists of Ni(II) centers hexacoordinated by three Hbim(-) ligands in octahedral arrangement. Complex 1 possesses an intermolecular H-bonding structure of interpenetrating polycatenane to give double-interlocking honeycomb sheet structures.