Abstract: Two new isostructural d10 metal complexes, M(AmThAA)2 (M=Zn(II), Cd(II); AmThAA=2-amino, 3-thiazoleacetate), with square pyramidal geometries have been synthesized and characterized by elemental analysis, single-crystal X-ray diffraction and TG analysis. Both complexes crystallize in a monoclinic crystal system, having the C 2/c space group, which by utilizing built-in hydrogen-bonding groups (−NH2 and −COO−) extends the molecular complexes into hydrogen-bonded metallo-supramolecular networks. It has been shown that heteromeric N−HO and O−HO hydrogen bonds based on and supramolecular synthons can be relied upon as effective tools for the assembly and organization of penta-coordinated complexes. Furthermore, both compounds show strong photoluminescence properties at room temperature. [Copyright &y& Elsevier]