Structure of Metal Aluminophosphates: Al9-x Mx P12 O48 (TREN)4 · yNH4 · zH2O [TREN = N (CH2 CH2 NH3) Hm, M = Mn, Co]1

Two large-pore metal-doped aluminophosphates, Mn4 Al5 (PO4)12 [N (C2 H4 NH3)3]3 [N(C2 H4 NH3)2 · (C2H4NH2)] (NH4)2 · 14H2O(Mn4-NJU) and Co4Al5 (PO4)12 [N(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.