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. 2019 Nov 19;75(Pt 12):1897-1901.
doi: 10.1107/S2056989019015330. eCollection 2019 Dec 1.

Structure refinement of (NH4)3Al2(PO4)3 prepared by ionothermal synthesis in phospho-nium based ionic liquids - a redetermination

Christopher P Nicholas  1 , John P S Mowat  2 , Robert W Broach  2
Affiliations

Structure refinement of (NH4)3Al2(PO4)3 prepared by ionothermal synthesis in phospho-nium based ionic liquids - a redetermination

Christopher P Nicholas et al. Acta Crystallogr E Crystallogr Commun. .

Abstract

After crystallization during ionothermal syntheses in phospho-nium-containing ionic liquids, the structure of (NH4)3Al2(PO4)3 [tri-ammonium dialuminum tris-(phosphate)] was refined on the basis of powder X-ray diffraction data from a synchrotron source. (NH4)3Al2(PO4)3 is a member of the structural family with formula A 3Al2(PO4)3, where A is a group 1 element, and of which the NH4, K, and Rb forms were previously known. The NH4 form is isostructural with the K form, and was previously solved from single-crystal X-ray data when the material (SIZ-2) crystallized from a choline-containing eutectic mixture [Cooper et al. (2004 ▸). Nature, 430, 1012-1017]. Our independent refinement incorporates NH4 groups and shows that these NH4 groups are hydrogen bonded to framework O atoms present in rings containing 12 T sites in a channel along the c-axis direction. We describe structural details of (NH4)3Al2(PO4)3 and discuss differences with respect to isostructural forms.

Keywords: Cyphos 169; aluminophosphate; ethyl­tri­butyl­phospho­nium di­ethyl­phosphate; ionothermal synthesis; powder diffraction; redetermination.

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Figures

Figure 1
Figure 1
Polyhedral representation of (NH4)3Al2(PO4)3, showing the overall connectivity and ion channels in the crystal structure. Al is in the center of blue tetra­hedra, P in gray tetra­hedra, and N is represented by blue spheres.
Figure 2
Figure 2
Ball and stick representation of (NH4)3Al2(PO4)3 showing the 12-membered ring with three phosphate groups protruding inward with close contact to ammonium cations.
Figure 3
Figure 3
Atomic position overlay plot of SIZ-2 (blue) and (NH4)3Al2(PO4)3 (red) showing that most atom positions are within 0.03 Å of each other. The most significant difference is in the O11 position.
Figure 4
Figure 4
Ball and stick representation of the key area surrounding O11 where the largest position movement takes place in the two independent refinements of (NH4)3Al2(PO4)3.
Figure 5
Figure 5
XRD pattern (λ = 0.373811 Å) of (NH4)3Al2(PO4)3 synthesized ionothermally in ethyl tri­butyl­phospho­nium di­ethyl­phosphate and Rietveld residuals following structure refinement. Part A shows the fit to the overall pattern, and inset B shows the fit to high-angle regions.
Figure 6
Figure 6
SEM image of polycrystalline (NH4)3Al2(PO4)3 synthesized ionothermally in ethyl tri­butyl­phospho­nium diethyl phosphate and used for structure refinement.
See this image and copyright information in PMC

References

    1. Boughzala, H., Driss, A. & Jouini, T. (1997). Acta Cryst. C53, 3–5.
    1. Byrne, P. J., Warren, J. E., Morris, R. E. & Ashbrook, S. E. (2009). Solid State Sci. 11, 1001–1006.
    1. Cooper, E. R., Andrews, C. D., Wheatley, P. S., Webb, P. B., Wormald, P. & Morris, R. E. (2004). Nature, 430, 1012–1016. - PubMed
    1. Das, S. K., Bhunia, M. K. & Bhaumik, A. (2012). Microporous Mesoporous Mater. 155, 258–264.
    1. Devi, R. N. & Vidyasagar, K. (2000). Inorg. Chem. 39, 2391–2396. - PubMed

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