Synthesis and Structure of a Molecular Zinc Phosphate [(C 12 H 8 N 2 Zn) 2 (HPO 4 )(H 2 PO 4 ) 2 ]

A hydrothermal reaction of a mixture of ZnCO 3 , phosphoric acid, 1, 10‐phenanthroline in H 2 O gave rise to large plates of a new zinc phosphate, [(C 12 H 8 N 2 Zn) 2 (HPO 4 )(H 2 PO 4 ) 2 ], I . The structure consists of ZnO 3 N 2 distorted trigonal‐bipyramidal and PO 4 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 = Fdd 2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)Å 3 , Z = 8.