Novel zigzag-chain, cyclic-octanuclear Ca- and hexanuclear Na-phosphate complexes were synthesized using bulky amide aryl dihydrogen phosphate ligands. The metal complexes with bulky amides have a unique unsymmetric ligand position. The zigzag-chain structure transformed into a cyclic-octa nuclear one in cooperating with the coordination of DMF molecule and reorganization of the intermolecular/intramolecular hydrogen bond networks.