Hydrothermal Synthesis, Crystal Structures and Characterization of Two Hydrogen Phosphates Templated by 4-Amino-2,2,6,6-tetramethylpiperidine

Abstract

Chemical preparations, crystal structures, thermal analyses, and IR spectroscopic studies are given for two new hydrogen phosphates templated by 4-amino-2,2,6,6-tetramethylpiperidine: (C9H22N2)2·(H2PO4)·(HPO4)·(F)·H2O (I) and (C9H22N2)·(H2PO4)2(II). The structures are determined by single crystal X-ray diffraction. Both compounds crystallize in the P21/c (N°14) monoclinic space group with the unit cell parameters: a = 14.856 (1) Å, b = 14.092 (2) Å, c = 14.7166 (9) Å, β = 118.434 (7)°, V = 2709.2 (4) Å 3, and Z = 4 for (I) and a = 9.803 (2) Å, c = 0.466 (2) Å, c = 15.640 (8) Å, β = 94.990 (4), V = 1598.68 (7) Å3, and Z = 4 for (II). The structure of I, refined to R = 0.042 and Rw = 0.067 for 6009 reflections (I ≥ 2σ (I)), exhibits infinite inorganic chains ∞((H2PO4)·(HPO4)·(F)·H2O)4− linked together through weak hydrogen bonds to form layers onto which the diprotonated [C9H22N2]2 + amine molecules are anchored. The structure of II, refined to R = 0.060 and Rw = 0.086 for 1435 reflections (I ≥ 2σ (I)), consists of ∞(H2PO4)− (100) layers between which [C9H22N2]2+ cations are inserted. A network of hydrogen bonds connects the different components. IR spectra of I and II show the characteristic bands of amine groups and phosphate anions.