Six copper(II) and manganese(II) coordination polymers with 5-methoxyisophthalate (CH3O-ip) and three related flexible N-donor ancillary ligands, {[Cu-3(CH3O-ip)(2)(bie)(OH)(2)]}(n) (1), {[Cu-2(CH3O-ip)(2)(bib)(2)]center dot H2O}(n) (2), {[Cu(CH3O-ip)(bbb)(H2O)]center dot H2O}(n) (3), {[Mn-3(CH3O-ip)(4)(H2O)(2)]center dot(H-2-bie)center dot 4H(2)O}(n) (4), {[Mn(CH3O-ip)(bib)]}(n) (5) and {[Mn(CH3O-ip)(bbb)]}(n) (6) [bie = 1,2-bis(imidazol-1'-yl)ethane; bib = 1,4-bis(imidazol-1-ylmethyl)benzene; bbb = 1,1'-(1,4-butanediyl)bis(benzimidazole)], have been synthesized under hydrothermal conditions. Complexes 1-6 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 exhibits a three-dimensional (3D) framework with a (3,4)-connected (5 center dot 8 center dot 9)(5 center dot 11(2))(5 center dot 8(3)center dot 11(2)) topology. Complex 2 shows a two-dimensional (2D) layered structure with a (3,5)-connected (4(2)center dot 6)(4(2)center dot 6(7)center dot 8) topology and further stacks via hydrogen-bonding interactions to give a 3D supramolecular architecture. Complex 3 possesses a 1D chain and further stacks into a 2D supramolecular architecture via hydrogen-bonding interactions. Complex 4 is a 2D layered structure with a (4,4) topology and further stacks via hydrogen-bonding interactions to generate a 3D supramolecular architecture. Similar to 2, complex 5 displays a 2D layered structure with a (3,5)-connected (4(2)center dot 6)(4(2)center dot 6(7)center dot 8) topology. Complex 6 features a 3D structure with a (3,5)-connected (4 center dot 6 center dot 8)(4 center dot 6(4)center dot 8(5)) topology. Thermogravimetric properties and magnetic properties of 1-6 were also investigated.