The title compound, [Zn(C(9)H(7)N(3))(2)(H(2)O)(4)](CF(3)O(3)S)(2), contains an octahedral [ZnL(2)(H(2)O)(4)](2+) cationic complex with trans geometry (Zn site symmetry -1), and each 5-(3-pyridyl)pyrimidine (L) ligand is coordinated in a monodentate fashion through the pyridine N atom. In the extended structure, these complexes, with both hydrogen-bond acceptor (pyrimidine) and donor (H(2)O) functions, are linked to each other by intermolecular water-pyrimidine O-H···N hydrogen-bonding interactions, resulting in a double chain along the crystallographic a axis. The trifluoromethanesulfonate anions are integrated into the chains via O-H···O hydrogen bonds between the coordinated water and sulfonate O atoms. These double chains are associated into a novel three-dimensional network through interchain water-pyrimidine O-H···N hydrogen bonds. The asymmetric ligand plays an important role in constructing this unusual supramolecular structure.
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