Abstract: | A hydrothermal reaction of a mixture of ZnCO3, phosphoric acid, 1, 10‐phenanthroline in H2O gave rise to large plates of a new zinc phosphate, [(C12H8N2Zn)2(HPO4)(H2PO4)2], I . The structure consists of ZnO3N2 distorted trigonal‐bipyramidal and PO4 tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)Å3, Z = 8. |