Template or ligand? Different structural behaviours of aromatic amines in combination with zincophosphite networks

The solution-mediated syntheses and crystal structures of catena-poly[bis(2-amino-3-hydroxypyridinium) [zinc-di-μ-phosphonato] dihydrate], {(C5H7N2O)[Zn(HPO3)2]·2H2O}n, (I), and poly[(benzene-1,2-diamine)(μ5-phosphonato)zinc], [Zn(HPO3)(C6H8N2)]n, (II) are described. The extended structure of (I) features [010] anionic chains of vertex-sharing ZnO4 tetrahedra 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-hydroxypyridinium cations and water molecules of crystallization interact 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-diaminobenzene species as part of ZnO3N tetrahedra 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 interactions. 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.