In our efforts to investigate the relationships between the metal ions and the structures of their complexes based on N-donor ligand, 1-(4-pyridylmethyl)-1H-benzimidazole (L), and their complexes [Ag(L)(ClO4)](n) (1),{[Cu(L)(2) (ClO4)(2)](H2O)(2)}(n) (2) were synthesized and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction analysis. Structural analyses show that 1 possess one-dimensional (1D) double helix chain structure, which further forms two-dimensional supramolecular framework connected by Ag center dot center dot center dot Ag and Ag center dot center dot center dot O weak interactions. When the metal ion was changed to Cu(II), 2 was obtained, which shows a two-fold interpenetrating three-dimensional diamond network. The results show that the metal ions and weak interactions play important roles in the construction of such coordination architectures. X-ray powder diffractions show that the bulk synthesized materials and the crystals used for diffraction are homogeneous. Meanwhile, the photoluminescent property of the complex 1 is investigated in the solid state at room temperature.