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The compound,[Zn3(C7NO4H3)3Cl4]·[C6NO2H6]4.4H2O (l),was synthesized and structurally characterized by X-ray crystallography.It crystallizes in the monoclinic,space group C2/c with a =16.9018(14),b =12.6902(10),c =25.1170(2 (A),β =90.54°,V=5387.0 (8) (A)3,Z=4,Zn3C45H41CLN7O24,Mr =1401.76,Dc =1.728 g/cm3,F(000) =2840 andμ(MoKa) =1.615 mm-1.The structure was refined to R =0.0764 and wR =0.2219 for 3468 observed reflections (I > 2σ(I)).Analysis of single crystal X-ray diffraction data shows that the compound of (Ⅰ) contains one pyridine-2,6-dicarboxylate complex tetra-anion,four 4-pyridine carboxylic cations and four dissociate water molecules.And it displays an interesting example of 3D supramolecular network beating highly perfect and intricate hydrogen bonding army,which linked by a combination of O-H...O,O-H...O(carboxylate),O-H...O(carbonyl),+N-H...O-(carboxylate),O-H...Cl and +N-H...Cl-hydrogen bonds.