A novel three dimensional network complex polymer [Cu4（oxen）2（N3）3]n（ClO4）n·2nH2O, where oxen is N,N’ -bis（2-aminoethyl）oxamide dianion, has been synthesized. It crystallizes in triclinic system, space group P（?）, with a=11.486（2）, b=11.706（3）, c=12.291（3） （?）, α=77.42（2）, β=67.59（2）, γ=77.96（2）°, and z=2. The least-square refinements converged at R=0.047, with 3416 observed unique reflections. The complex has a pronounced three-dimensional character and can be viewed as the tetranuclear asymmetric repeating units through inversion and translation operations to extend a three-dimensional network. The structure of Cu4 asymmetric unit consists of two square planar and two square pyramidal Cu central atoms linked by both azide ligands in end-on and end-to-end bonding modes, and oxamidate bridge in trans conformation.
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