Two pentacoordinated dinuclear compounds of the type [M 2 (dca)(L) 2 ](ClO 4 ) 3 ·H 2 O [M=Cu (1), Cd (2); L=N,N′-bis(3-aminopropyl)-1,2-ethanediamine; dca=dicyanamide] have been prepared and characterized on the basis of microanalytical, spectroscopic and other physicochemical properties. Structures of 1 and 2 are solved by single crystal X-ray diffraction measurements. Structural study reveals that in both compounds each pentacoordinated metal(II) center adopts a distorted square pyramidal geometry with an MN 5 chromophore coordinated by four N atoms of the polyamine (L) in the basal plane and nitrile N atom of single μ 1,5 bridged dca in the apical position. The dinuclear units in 1 and 2 are engaged in weak intermolecular O–H⋯O, N–H⋯O, N–H⋯N and C–H⋯O hydrogen bondings resulting in 3D network structures in which the crystalline water molecules and counter ions are embedded. Variable-temperature magnetic susceptibility measurement of 1 indicates weak antiferromagnetic interactions among the metal centers.