We report on the synthesis of two acentric and one centrosymmetric Zn metal–organic complexes with 3-tetrazolemethyl pyridine spacers obtained in situ by hydrothermal routes. X-ray diffraction structural analysis reveals that they have the same equivalent nodes but with dissimilar topologies. The two acentric frameworks [Zn(Tzmp)Cl]n (1) and ([Zn(Tzmp)Br]n (2), HTzmp=3-tetrazolemethyl pyridine) are isomorphism which exhibit an acentric 3D framework with (10, 3)-b net calledths, while the centrosymmetric complex ([Zn(Tzmp)N3]n (3)) features a distinctive 2D sheet with Shubnikov hexagonal plane net. Photo-luminescent studies suggest the ligand-field strength of coordinated negative ions (Cl->Br->N3-) has ordered adjusting effects on the emission redshift. The second harmonic generation (SHG) measurement shows that compounds 1 and 2 are nonlinear optically active, with SHG responses being 2/3 and half of the standard potassium dihydrogen phosphate (KDP), respectively.