Structure of Metal Aluminophosphates:Al9-xMxP12O48(TREN)4·yNH4·zH2O[TREN=N(CH2CH2NH3)Hm, M=Mn, Co]

Two large-pore metal-doped aluminophosphates, Mn4Al5(PO4)12N(C2H4NH3)3]3N(C2H4NH3)2·(C2H4NH2)](NH4)2·14H2O(Mn4-NJU) and Co4Al5(PO4)12N(C2H4NH3)3]N(C2H4NH3)2(C2H4NH2)]3·(NH4)4·13H2O(Co4-NJU), which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I(-4)3m with a=1.6795(2) nm and V=4.7374(9) nm3 for Mn4-NJU, and a=1.67372(19) nm and V=4.6887(9) nm3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-(2-aminoethyl)diethylenetriamine(TREN, C6H18N4) ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M2 (M=Mn, Co) and Al3 disorderedly occupy the same crystallographic positions.