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）12[N（C2H4NH3）3]3[N（C2H4NH3）2·（C2H4NH2）]（NH4）2·14H2O（Mn4-NJU） and Co4Al5（PO4）12[N（C2H4NH3）3][N（C2H4NH3）2（C2H4NH2）]35（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） nm 3 for Mn4-NJU, and a={1.67372（19）} nm and V=4.6887（9） nm 3 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.