Two new derivatives of cadmium(II) dicyanamide (dicyanamide=[N(CN) 2 ] - , dca), [Cd(N(CN) 2 ) 2 (phen)] n (1) and [Cd(N(CN) 2 ) 2 (2,2'-bipy)] n (2), have been synthesized and structurally characterized. The cadmium(II) centers in 1 are connected through single or double end-to-end dca bridging ligand to form a 2-D layer structure, which furthermore condense into a 3-D structure through the π-π interaction between aromatic rings of adjacent layers. In 2, the cadmium(II) coordination sphere is a distorted octahedron, bound to four dca ligands and one chelate 2,2'-bipy ligand, and the adjacent cadmium(II) centers are bridged by the double end-to-end μ 1 , 5 -N=C N C=N to form an extended structure with a zigzag 1-D chain, and a 2-D layer structure results from the π-π interactions of the adjacent chains.