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Abstract
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} n , (I), and poly[(benzene-1,2-di-amine)(μ5-phospho-nato)zinc], [Zn(HPO3)(C6H8N2)] n , (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.
Highlights
Compound (I) features unusual disorder of the zincophosphite component of the structure, in a 0.7962 (13):0.2038 (13) ratio for the major and minor components, respectively
The stated motivations for studying these phases include their potential applications in catalysis, separation and as ‘functional materials’ (Wang et al, 2003). Important features of their crystal structures include the nature of the polyhedral building units [ZnO4, ZnO3(H2O), ZnO3N, HPO3] and their connectivity, which defines the Zn:P ratio; for example, ZnO4 and HPO3 units sharing all their vertices as Zn—O—P bonds will lead to an anionic [Zn3(HPO3)4]n2nÀ framework (a 3:4 Zn:P ratio), the charge of which must be balanced by the organic templating cation (e.g. Katinaite & Harrison, 2017)
This has an important effect on the zinc-to-phosphorus ratio; for example, a combination of ZnO3N and HPO3 units leads to a neutral [Zn(HPO3)]n (1:1 Zn:P ratio) network (e.g. Lin et al, 2004b)
Summary
Templated zinc phosphites (ZnPOs) are a wellestablished family of organic/inorganic open frameworks (e.g. Harrison et al, 2001; Dong et al, 2015; Huang et al, 2017). The stated motivations for studying these phases include their potential applications in catalysis, separation and as ‘functional materials’ (Wang et al, 2003) Important features of their crystal structures include the nature of the polyhedral building units [ZnO4, ZnO3(H2O), ZnO3N, HPO3] and their connectivity, which defines the Zn:P ratio; for example, ZnO4 and HPO3 units sharing all their vertices as Zn—O—P bonds will lead to an anionic [Zn3(HPO3)4]n2nÀ framework (a 3:4 Zn:P ratio), the charge of which must be balanced by the organic templating cation Fan et al, 2005), in which case the (unprotonated) organic species could be said to be acting as a ligand, its steric bulk means that it does exert a ‘templating effect’ on the extended structure This has an important effect on the zinc-to-phosphorus ratio; for example, a combination of ZnO3N and HPO3 (all vertices bonding) units leads to a neutral [Zn(HPO3)]n (1:1 Zn:P ratio) network As part of our ongoing studies in this area we describe the syntheses and structures of (C5H7N2O)[Zn(HPO3)2]Á2H2O, (I), and [Zn(HPO3)(C6H8N2)], (II), where C5H7N2O+ is the 2-amino-3-hydroxypyridinium cation and C6H8N2 is neutral 1,2-diaminobenzene ( known as o-phenylenediamine)
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