The reaction of Zn（ClO4）2·6H2O with 3,3＇-bis（2-benzimidazolyl）-2,2＇-dipyridine （L） gave a mononuclear zinc（Ⅱ） complex： [ZnL2]（CIO4）2·2DMF·4H2O, which was structurally characterized by EA, IR, UV, ^1H NMR, fluorescence spectrum and single-crystal X-ray diffraction. The crystal （C54H54Cl2N14O14Zn, Mr = 1259.38） belongs to the monoclinic system, space group C2/c with a = 20.874（2）, b = 14.9953（16）, c = 20.462（3）A,β= 101.553（2）°, V= 6274.8（13） A, Z= 4, Dc= 1.333 g/cm^3, F （000） = 2608,/a（MoKcr） = 0.548 mm 1, R = 0.0682 and wR = 0.1931 for 4984 observed reflections with I 〉 2σ（I）. The Zn（Ⅱ） is four-coordinated in a slightly distorted tetrahedral geometry through four N atoms from four benzimidazole units of two ligands. In the crystal lattice, the [ZnL2]2^＋ cations are linked to each other by extensive intermolecular hydrogen bonds between nitrogen atoms of benzimidazole rings, water and DMF molecules.
