The title compound, {(C10H10N2)[Ce2(C7H3NO4)4(H2O)4]·5H2O}n, is composed of a one-dimensional anionic complex, a doubly protonated 4,4′-bipyridine molecule as a counter-ion and five uncoordinated water molecules. The anion bears two nine-coordinate CeIII ions, each with a distorted tricapped trigonal–prismatic geometry. In the crystal, intermolecular C—H⋯O, N—H⋯O and O—H⋯O hydrogen bonds, as well as π–π interactions with centroid–centroid distances of 3.514 (3) Å connect the various components into a supramolecular structure.
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