Solvothermal synthesis of an open-framework zinc chlorophosphate, [C8N4H26][Zn3Cl(HPO4)3(PO4)], with a layer structure

A solvothermal reaction of ZnO, HCl, H₃PO₄, and N,N′(3-bisaminopropyl)-1,2-ethylenediamine (BAPEN) in diethyleneglycol at 160°C yields a new zinc chlorophosphate, C₈N₄H₂₆]Zn₃Cl(HPO₄)₃(PO₄)], I. The structure comprises ZnO₄, ZnO₃Cl, HPO₄ and PO₄ tetrahedral units connected through their vertices giving rise to a layered structure with 10-membered apertures. The position of the Zn and P atoms gives rise to double-four ring like building unit with one Zn missing. The fully protonated amine molecules occupy the inter-lamellar region and interacts with the framework through N-H?O hydrogen bonds. Crystal data: M=792.85, orthorhombic, space group=Pca2₁ (no. 29), a=9.8410(2), b=15.0912(2), c=16.1220(4) Å, V=2394.32(8) Å³, Z=4, ρ_calc=2.199 g cm⁻³, μ(MoKα)=3.443 mm⁻¹, R₁=0.0520, wR₂=0.1256 and S=1.054.