Organic templates in zincophosphate synthesis: Zn5(PO4)2(HPO4)4·H2O·2H2N2C6H12, containing two distinct eight-ring channels and Zn3(PO4)(HPO4)2· HN2C6H12, containing tetrahedral three-rings and Zn–N bonds

摘要: The hydrothermal syntheses, single-crystal X-ray structures and some properties of two new microporous, anionic, zinc phosphate frameworks encapsulating organic cations are described. Zn5(PO4)2(HPO4)4·H2O·2H2N2C6H12(ZnPO/dab-C) crystallizes in the triclinic space group P(No. 2) with a= 9.366(1)A, b= 9.882(1)A, c= 19.183(2)A, α= 85.406(3)°, β= 85.029(3)° γ= 114.485(3)°, V= 1596.51 A3 Z= 2, R(F)= 7.11% for 4095 observed reflections [I > 3σ(I)], Zn3(PO4)(HPO4)2·HN2C6H12(ZnPO/dab-D) is orthorhombic, P212121(No. 19), 11.095(2)A, 16.413(2)A, 8.263(1)A, 1505.61 A3, 4, 5.71% 1321 3σ(I)].Both these materials consist a three-dimensional network tetrahedrally coordinted phosphorus atoms, linked through oxygen atom vertices, to form different open structures. ZnPO/dab-C contains distinct one-dimensional eight-ring channels (one regular, one squashed), occupied by extraframework, protonated, 1,4-diazabicyclo[2.2.2]octane (DABCO, [H2N2C6H12]2+) molecules. ZnPO/dab-D framework type containing ‘bridged’ three-rings tetrahedra. DABCO molecule coordinates this phase via Zn–N links. 31P MAS NMR data presented, may be interpreted using simple bond-strength model.