Abstract: | The reaction of ZnII nitrate with maleic acid (H2mal) / fumaric acid (H2fum) and 4,4′‐dipyridyl disulfide (4‐pds) resulted under same conditions in two distinct interpenetrated compounds, namely [Zn(4‐dps)2(H2O)2]·2Hmal ( 1 ) and [Zn(4‐dps)(fum)] ( 2 ). In 1 , Hmal anion adopts bridging mode based on hydrogen bonding, affording a 2‐fold parallel interpenetrated 3D→3D α‐Po net hydrogen‐bonded framework, in which 1D double‐stranded chains are formed, and then extended to a 3D supramolecular architecture combining second‐sphere hydrogen‐bonded interactions. For 2 , fum dianion takes on bis‐dentate bridging coordination fashion, furnishing a 2‐fold interpenetrated 2D→2D (4,4) layered coordination network, in which the tetrahedral ZnII atoms are interlinked by 4‐dps and fum. Additionally, the compound 2 shows strong fluorescence in the solid state at room temperature. |