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In the title compound, [Na4Zn(C6H5O7)2]n, the ZnII ion lies on an inversion center and is coordinated by six O atoms from two citrate ligands, forming a distorted octahedral geometry. There are two crystallographically independent Na+ cations in the asymmetric unit. One Na+ cation exhibits a distorted square-pyramidal geometry defined by five O atoms from four citrate ligands. The other Na+ cation is surrounded by six O atoms from five citrate ligands in a distorted octahedral geometry. The Na+ cations are bridged by citrate carboxylate groups, forming a layer parallel to (100). The layers are further assembled into a three-dimensional network with the [Zn(citrate)2]4− building units as `pillars'; O—H...O hydrogen bonds also stabilize the structure.

The Zn(II) atom in the title compound, [Zn(SO4)(C12H8N2)(H2O)3], is coordinated by one O atom from a sulfate dianion, two N atoms from a 1,10-phenanthroline molecule and three water O atoms in an octahedral geometry. An intramolecular O—H...O hydrogen bond occurs. Intermolecular O—H...O hydrogen bonds generate a layer structure parallel to (001). There are weak C—H...O interactions within the layers.