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

Abstract

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)(μ 5-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 Oatom vertices into infinite (010) sheets and the structure is consolidated by N- H⋯O hydrogen bonds and N-H⋯ 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.