Hydrothermal synthesis and structural characterization of organically templated zincophosphites: [Zn(C4N3H13)][Zn4(HPO3)6]⋅(C4N3H15) and [Zn5(H2O)4(HPO3)6]⋅(C7NH10)2(H2O)

Two organically templated zincophosphites, [Zn(C4N3H13)][Zn4(HPO3)6]⋅(C4N3H15) and [Zn5(H2O)4(HPO3)6]⋅(C7NH10)2(H2O) were synthesized using diethylenetriamine and benzylamine as templates and characterized by single-crystal X-ray diffraction. [Zn(C4N3H13)][Zn4(HPO3)6]⋅(C4N3H15) crystallizes in orthorhombic Cmca   with cell parameters a=18.9617(7) Åa=18.9617(7) Å, b=10.0192(3) Åb=10.0192(3) Å, c=16.1415(4) Åc=16.1415(4) Å. [Zn5(H2O)4(HPO3)6]⋅(C7NH10)2(H2O) crystallizes in triclinic P-1P-1 with cell parameters a=10.0039(9) Åa=10.0039(9) Å, b=10.2172(9) Åb=10.2172(9) Å, c=11.6488(9) Åc=11.6488(9) Å, and α=69.646(5)°α=69.646(5)°, β=88.003(5)°β=88.003(5)°, γ=62.994(5)°γ=62.994(5)°. [Zn(C4N3H13)][Zn4(HPO3)6]⋅(C4N3H15) consist of alternatively linked ZnO4, ZnO2N3 and [HPO32−] units. In this structure, the structure-directing amines as ligands to zinc are present in two distinct forms, the free state and bonded state, and the two species occurring in channels. [Zn5(H2O)4(HPO3)6]⋅(C7NH10)2(H2O) is made up of ZnO4, ZnO6 and [HPO32−] moieties forming distinct channels, the protonated aromatic amine molecules are located in the intersection of the channels. In the compounds, the connections ZnO2N3 and ZnO6 of Zn atoms are the first reported in the synthesis of zincophosphite materials. Two zincophosphites, having two-dimensional structures with 4, 6, 8-membered rings channels, were also characterized by IR spectroscopy, thermogravimetric and differential thermal analyses.

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