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

Abstract

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) ų, 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.