Synthesis and Characterization of a New Two-Dimensional Aluminophosphate Layer and Structural Diversity in Anionic Aluminophosphates with Al₂P₃O₁₂^3- Stoichiometry

A new two-dimensional aluminophosphate layer [Al₂P₃O₁₀(OH)₂][C₆NH ₈] (compound 1) has been prepared from an alcoholic system using 4-methylpyridine (C₆NH₇) as a template. The as-synthesized product is characterized by powder X-ray diffraction, dynamic thermogravimetric, and ³¹P-, ²⁷Al-, and ¹³C magic-angle spinning (MAS) NMR analyses. The structure has been solved by single-crystal X-ray diffraction analysis. Compound 1 crystallized in the monoclinic space group P2₁/c (no. 14), with a = 8.686 (3) Å, b = 21.240 (3) Å, c = 8.799 (2) Å, β = 113.23 (3)°, and Z = 4. The inorganic layers are constructed from alternating aluminum units (AlO₄ and AlO₅) and phosphorus units [PO₄, PO₃(OH), PO₂(=O)(OH)] and are featured by rows of edge-sharing bridged six-membered rings (6MRs) and zigzag four rings (4MRs). The layers are held with each other through strong H-bondings between the terminal oxygens attached to the 2-connected phosphate groups in adjacent layers. The organic ammonium cations (C₆NH₈⁺) are located in the large cavities between the interlayer regions. The structural features and relationships in the anionic aluminophosphates with Al₂P₃O₁₂^3- stoichiometry, including compound 1 and previously reported compounds, are discussed. Furthermore, new two-dimensional (2-D) networks have been proposed on the basis of the discovered building rules for aluminophosphates with Al₂P₃O₁₂^3- stoichiometry.