Three unusual compounds based on polyoxometalate building blocks, [(H2O)(5)Na-2(C6NO2H4)(C6NO2H5)(3)Ag-2][Ag-2-IMo6O24(H2O)(4)]center dot 6.25H(2)O (1), [(H2O)(4)Na-2(C6NO2H5)(6)Ag-3][IMo6O24]center dot 6H(2)O (2), and (C6NO2H6)(2)[(C6NO2H5)(2)Ag][Cr-(OH)NO6Mo6O18]center dot 4H(2)O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)(5)Na-2(C6NO2H4)(C6NO2H5)(3)Ag-2](3+) and anionic [Ag2IMo(6)O(24)(H2O)(4)](3-) chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24](5-) building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)(6)Ag-3](3+), fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)(6)Mo6O18](3-) building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) angstrom, b = 13.641(3) angstrom, c = 16.356(3) angstrom, alpha = 89.68(3)degrees, beta = 88.31(3)degrees, gamma = 75.87(3)degrees, Z = 2; 2, triclinic, P1, angstrom = 11.978(2) angstrom, b = 12.008(2) angstrom, c = 13.607(3) angstrom, alpha = 116.14(3)degrees, = 108.85(3)degrees, gamma = 93.86(3)0, Z = 1; 3, triclinic, P1, a = 10.458(2) angstrom, b = 10.644(2) angstrom, c = 12.295(3) angstrom, alpha = 97.40(3)degrees, beta = 112.38(3)degrees, gamma = 113.59(3)degrees, Z = 1.