Abstract: Four new nitrito-bridged coordination polymers of formulation Zn(NO2)2(H2O)2n(1) andM(bipy)(NO2)2nM=Zn(2);Co(3),Mn(4) were synthesized under solvothermal condition using DMF as reducing solvent.All the complexes were characterized by elemental analysis,FT-IR spectroscopy,UV-vis spectroscopy,TG analysis and single crystal X-ray diffraction methods. For complex 1,two crystallographically independent Zn(Ⅱ) ions were bridged by μ1,3-NO^-_2,resulting in a 3D framework,which can be rationalized as 6-connected uninodal mab net by topological point.Complexes 2—4 are isostructural,and can be simplified as uninodal 6-connected jsm net.The NO^-_2 ligand in 2—4 presents significantly twisted conformation,which responsible for the formation of double helical chains in the crystal structure.In addition,this work also describes the preliminary study of catalytic properties of heterogeneous oxidation of cyclohexene by 2 and 3.