Formation of One-, Two-, and Threedimensional Open-framework Zinc Phosphates in the Presence of a Tetramine


Five new open-framework zinc phosphates, encompassing the entire hierarchy of open-framework structures, have been synthesized hydrothermally in the presence of triethylenetetramine. The structures include one-dimensional ladders, two-dimensional layers, and three-dimensional structures as well as a zinc phosphate where the amine acts as a ligand. [C6N4H22]0.5[Zn(HPO4)2] (I):  monoclinic, space group P21/c (no. 14), a = 5.2677(1) Å, b = 13.3025(1) Å, c = 14.7833(1) Å, β = 96.049°, Z = 4. [C6N4H22]0.5[Zn2(HPO4)3] (II):  triclinic, space group P1̄ (no. 2), a = 7.515(1) Å, b = 8.2553(1) Å, c = 12.911(1) Å, α = 98.654(1)°, β = 101.274(1)°, γ = 115.791(1)°, Z = 2. [C6N4H22]0.5[Zn2P2O8] (III):  triclinic, space group P1̄ (no. 2), a = 8.064(1) Å, b = 8.457(1) Å, c = 9.023(1) Å, α = 111.9(1)°, β = 108.0(1)°, γ = 103.6(1)°, Z = 2. [C6N4H22]0.5[Zn3(PO4)2(HPO4)] (IV):  triclinic, space group P1̄ (no. 2), a = 5.218(1) Å, b = 8.780(1) Å, c = 16.081(1) Å, α = 89.3(1)°, β = 83.5(1)°, γ = 74.3(1)°, Z = 2. [C6N4H20]0.5[Zn4P4O16] (V):  monoclinic, space group P21/c (no. 14), a = 9.219(1) Å, b = 15.239(1) Å, c = 10.227(1) Å, β = 105.2(1), Z = 4. The structure of I is composed of ZnO4 and HPO4 tetrahedra, which are edge-shared to form four-membered rings, which, in turn, form a one-dimensional chain (ladder). In II, these ladders are fused into a layer. The structures of III and IV comprise networks of ZnO4 and PO4 tetrahedra forming three-dimensional architectures. In V, the amine molecule coordinates to the Zn and acts as a pillar supporting the zinc phosphate layers, which possess infinite Zn−O−Zn linkages. The 16-membered one-dimensional channel in IV and the ZnO3N pillar, along with infinite Zn−O−Zn linkages in V, are novel features. The structure of the open-framework zinc phosphates is found to depend sensitively on the relative concentrations of the amine and phosphoric acid, with high concentrations of the latter favoring structures with lower dimensions.



Document Type

Article - Journal

Document Version


File Type





© 2000 American Chemical Society (ACS), All rights reserved.