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Two new dicyanamide (dicyanamide=[N(CN)2]−, dca) bridged complexes, [Cu(μ1,5-dca)2(phen)]n (1) and [Cd(μ1,5-dca)2(py)2]n (2) have been synthesized and their structures have been determined by X-ray crystallography diffraction. Complex 1 crystallizes in the monoclinic space group P2(1)/c with a=10.1502(3), b=10.9815(4), c=14.5839(4) A˚ and Z=4. The adjacent copper atoms are connected by single end-to-end dca bridges to form a chain structure along the b axis. The chains are linked via Cu⋯N weak interactions to give rise to a 2D layer structure, which furthermore into a 3D structure by the π–π interaction between aromatic rings of adjacent layers. Complex 2 crystallizes in the monoclinic space group C2/m with a=6.6849(10), b=17.476(2), c=13.231(2) A˚ and Z=4. The cadmium(II) center is six-coordinated with a distorted octahedral geometry, bounded to four N atoms of four dca ligands and two N atoms of two-chelated py ligands. Neighbor Cd(II) atoms are linked by the double end-to-end dca bridges to generate a chain structure, which result in a 2D layer structure through the π–π interactions between the adjacent chains with distances 3.641 A˚. EPR and magnetic results of 1 suggest that the complex exhibits a weak ferromagnetic interaction through Cu&z.sbnd;N&z.tbnd6;C&z.sbnd;N&z.sbnd;C&z.tbnd6;N&z.sbnd;Cu pathways. [Copyright &y& Elsevier]