Five novel metal pamidronates (3-ammonium-1-hydroxypropylidene-1,1-bisphosphonate, APD) formulated as Ni-2(C3NH10P2O7) (4)center dot 4H(2)O ( 1), M(C3NH9P2O7)center dot H2O ( M = Co ( 2), Mn ( 3), Zn ( 4)) and Cu-3(C3NH8P2O7)(2)center dot 2H(2)O ( 5) have been hydrothermally synthesized under similar conditions. Compound 1 is a molecular binuclear nickel cluster. Compounds 2 and 3 exhibit similar one-dimensional ladderlike structures. Compound 4 possesses a novel two-dimensional gridlike framework. Compound 5 shows an unusual three-dimensional architecture, in which two-dimensional layers with a parquet motif are pillared by {CuO4} planar squares. Different dinuclear secondary building units (SBUs) are observed in compounds 1 -5, depending on the different coordination modes of APD. They also exhibit different photoluminescence properties.