Reaction　of　transition　metal(II)　salts　with　2,2＇-biimidazole　(H2biim)　and　co-ligands　formed　a　series　of　new　complexes,　[M(H(2)biim)(2)(biPY)(2)](NO3)(2)center　dot　2H(2)O　(1-3)　(M　=　Co,　Ni,　Zn),　[Co(H(2)biim)(2)(biPY)](ClO4)(2)center　dot　3H(2)O　(4),　{[Cu(H(2)biim)(2)](3)(mu-C3H3O4)(2)　(C3H2O4)(2)}center　dot　6H(2)O　(5),　Ko(H(2)biim)(2)(H2O)(2)](C3H3O4)(2)　(6)　(bipy　=　4,4＇-bipyridine,　C3H2O4　=　malonate　dianion,　C3H3O4　=　malonate　anion).　These　complexes　were　characterized　by　single-crystal　X-ray　diffraction,　and　elemental　analysis.　All　complexes　except　4　were　also　characterized　by　luminescence　spectra　and　thermogravimetric　analysis.　The　crystal　packing　of　these　six　complexes　shows　that　cationic　M(II)(2,2＇-biimidazole)　fragments　are　self-assembled　to　construct　the　3D　supramolecular　networks　by　hydrogen　bonding　and　7C　It　interactions.　The　3D　supramolecular　networks　are　significantly　affected　by　counter　anion　and　co-ligands.　In　complexes　1-3,　there　are　two　sets　of　(4,4)　nets　which　pass　through　each　other　to　form　inclined　2D　interpenetration.　Complex　4　is　obtained　by　similar　reactions　as　1　Compared　with　1,　the　only　difference　in　4　with　the　reactant　Co(NO3)2.6H20　replaced　by　Co(ClO4)center　dot　6H(2)O,　but　it　has　a　very　different　structure.　In　4,　the　3D　networks　containing　cavities　of　23　x　23　angstrom　is　formed.　In　complex　5,　the　uncoordinated　waters　form　an　infinite　1D　pipe　structure　which　is　embedded　in　the　3D　porous　network.　The　acid-water　ring　and　R-2(2)(9)　synthons　in　complex　6　lead　to　the　formation　of　(4,4)　2D　network.　(C)　2015　Elsevier　Ltd.　All　rights　reserved.