Abstract: | The title compound, [Cd3(C8H10O4)3(C12H9N3)2(H2O)2]n or [Cd3(chdc)3(4‐PyBIm)2(H2O)2]n, was synthesized hydrothermally from the reaction of Cd(CH3COO)2·2H2O with 2‐(pyridin‐4‐yl)‐1H‐benzimidazole (4‐PyBIm) and cyclohexane‐1,4‐dicarboxylic acid (1,4‐chdcH2). The asymmetric unit consists of one and a half CdII cations, one 4‐PyBIm ligand, one and a half 1,4‐chdc2− ligands and one coordinated water molecule. The central CdII cation, located on an inversion centre, is coordinated by six carboxylate O atoms from six 1,4‐chdc2− ligands to complete an elongated octahedral coordination geometry. The two terminal rotationally symmetric CdII cations each exhibits a distorted pentagonal–bipyramidal geometry, coordinated by one N atom from 4‐PyBIm, five O atoms from three 1,4‐chdc2− ligands and one O atom from an aqua ligand. The 1,4‐chdc2− ligands possess two conformations, i.e.e,e‐trans‐chdc2− and e,a‐cis‐chdc2−. The cis‐1,4‐chdc2− ligands bridge the CdII cations to form a trinuclear {Cd3}‐based chain along the b axis, while the trans‐1,4‐chdc2− ligands further link adjacent one‐dimensional chains to construct an interesting two‐dimensional network. |