Three new cyano complexes, [Cu(hmp)(2)] [Cu(hmpH)(2)Ni(mu-CN)(2)(CN)(2)](2)center dot 4H(2)O (1), [Zn-3(hmp)(2)(hmpH)(4) Ni-2(mu-CN)(6)(CN)(2)]center dot 2H(2)O (2) and [Cd-2(H2O)(2)(hmpH)(2)Ni(mu-CN)(4)Ni(mu-CN)(2)(CN)(2)] (3) (2-pyridinemethanol abbreviated to hmpH), have been synthesized and characterized by elemental analysis, vibrational spectroscopy (FT-IR and Raman), thermal and single-crystal X-ray diffraction analyses. In 1, Cu(II) ions are connected by the tetracyanonickelate(II) anions to form one-dimensional (1D) zig-zag chains. In 2, tetracyanonickelate(II) ions are coordinated to the neighboring three Zn(II) ions to form a one-dimensional double chain structure. In 3, Cd(II) ions are connected by tetrakis-monodentate tetracyanonickelate(II) ions to form a one-dimensional ladder-like chain. Adjacent ladder-like chains are linked by the bis-monodentate tetracyanonickelate(II) ions to generate a 2D network. The 3D supramolecular network of the complexes constructed by intermolecular interactions such as Ni center dot center dot center dot pi, C-H center dot center dot center dot Ni, pi...pi and hydrogen bonding interactions.