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Synthesis,structure and NMR characterization of a new monomeric aluminophosphate [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4 containing four different types of monophosphates
Authors:Peng Chen  Jiyang Li  Jun Xu  Fangzheng Duan  Feng Deng  Ruren Xu
Affiliation:1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China;2. Molecular Physics, Wuhan Institute of Physics and Mathematics, The Chinese Academy of Sciences, Wuhan 430071, PR China
Abstract:A new zero-dimensional (0D) aluminophosphate monomer [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4 (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en)3Cl3 as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO4)2(H1.5PO4)2(H2PO4)2]6? monomer. Notably, there exists intramolecular symmetrical O?H?O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by 31P NMR and 1H NMR spectra. The crystal data are as follows: AlPO-CJ38, [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4, M = 1476.33, monoclinic, C2/c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å3, Z = 4, R1 = 0.0509 (I > 2σ(I)) and wR2 = 0.1074 (all data). CCDC number 689491.
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