The syntheses and crystal structures of two one-dimensional coordination polymers, [Mn(C5HO2F6)(2)(C16H20N2)] (n) (1) and [Mn(C5HO2F6)(2)(C20H20N2)] (n) (2), are described, where C5HO2F6 (-) is the hexafluoro acetylacetonate anion, C16H20N2 is 1,6-bis(4-pyridyl)-hexane, and C20H20N2 is 1,4-bis[2-(3-pyridyl)ethyl]-benzene. In both phases, the metal ion lies on a crystallographic twofold axis and is coordinated by two chelating C5HO2F6 (-) anions and two bridging bipyridyl ligands to generate a cis-MnN2O4 octahedron. The bridging ligands, which are completed by crystallographic inversion symmetry in both compounds, connect the metal nodes into zigzag [20 1 ] chains in 1 and contorted [001] chains in 2. Intrachain C-HaEuro cent aEuro cent aEuro cent O interactions occur in 1 but not in 2, which may be correlated with the relative orientations of the ligands. Crystal data: 1, C26H22F12MnN2O4, M (r) = 709.40, monoclinic, C2/c (No. 15), a = 9.3475(2) , b = 16.6547(3) , c = 18.3649(4) , beta = 91.1135(8)A degrees, V = 2858.50(10) (3), Z = 4, R(F) = 0.030, w R(F (2)) = 0.075. 2, C30H22F12MnN2O4, M (r) = 757.44, monoclinic, C2/c (No. 15), a = 19.9198(2) , b = 10.6459(2) , c = 16.8185(3) , beta = 119.8344(8)A degrees, V = 3093.91(9) 3, Z = 4, R(F) = 0.032, w R(F (2)) = 0.078.