Template or ligand? Different structural behaviours of aromatic amines in combination with zinco-phosphite networks

The solution-mediated syntheses and crystal structures of catena-poly[bis-(2-amino-3-hy-droxy-pyridinium) [zinc-di-μ-phospho-nato] dihydrate], {(C₅H₇N₂O)[Zn(HPO₃)₂]·2H₂O} , (I), and poly[(benzene-1,2-di-amine)(μ₅-phospho-nato)zinc], [Zn(HPO₃)(C₆H₈N₂)] , (II) are described. The extended structure of (I) features [010] anionic chains of vertex-sharing ZnO₄ tetra-hedra and HPO₃ pseudopyramids; these chains are characterized by disorder over major [occupancy 0.7962 (13)] and minor [0.2038 (13)] components, which can be superimposed on each other by a nominal translational shift. The 2-amino-3-hy-droxy-pyridinium cations and water mol-ecules of crystallization inter-act with the ZnPO chains by way of numerous O-H⋯O and N-H⋯O hydrogen bonds. The structure of (II) features a direct Zn-N bond to the neutral 1,2-di-amino-benzene species as part of ZnO₃N tetra-hedra as well as HPO₃ pseudopyramids. The Zn- and P-centred groupings are linked through their O-atom vertices into infinite (010) sheets and the structure is consolidated by N-H⋯O hydrogen bonds and N-H⋯π inter-actions. The crystal of (I) chosen for data collection was found to be an inversion twin in a 0.56 (2):0.44 (2) domain ratio.