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Metal-loaded pollucite-like aluminophosphates: dissymmetrisation of crystal structures and physical properties

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Abstract

Two aluminophosphate analogues of the mineral pollucite with the general formula Cs2(M,Al)3P3O12 (where M = Cu or Mn) have been synthesized by high-temperature flux and structurally characterized using the single-crystal X-ray diffraction. Both samples crystallize in cubic I4132 space group, Z = 8, with a = 13.5911(5) and a = 13.8544(7) for Cu- and Mn-loaded phases, respectively. Their framework structures are based on the ANA-type topology and exhibit the partial ordering of the metal (M/Al) and phosphorus (P) cations over the tetrahedral sites. The regular changes in cell dimensions and volumes in the row Cs2(Cu,Al)3P3O12→Cs2(Mn,Al)3P3O12 obviously correspond to increasing radii of the transition metal. The crystal chemical analysis of both pollucite-like phases show correlations between the difference in the radii size of tetrahedral cations and the degree of distortion of flexible ANA-type framework due to decreasing of the intertetrahedral angles (T–O–T). Magnetic susceptibility measurements indicate that both compounds are paramagnets in the temperature range of 2–300 K.

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Notes

  1. ANA comes from analcime according Atlas of zeolite framework types (Baerlocher et al. 2001).

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Acknowledgements

We thank V. O. Yapaskurt for the microprobe analysis of the crystals and N. V. Zubkova for help in X-ray experiments. L.S. acknowledges financial support by Russian Foundation for Basic Research Grants No.15-05-06742. This work was supported in part from the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST “MISiS” (K2-2017-084) and by Act 211 of the Russian federation Government, Contracts No. 02.A03.21.0004 and 02.A03.21.0011.

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Authors and Affiliations

  1. M.V. Lomonosov Moscow State University, Moscow, 119991, Russia

    L. V. Shvanskaya, O. V. Yakubovich, A. V. Koshelev & A. N. Vasiliev

  2. National University of Science and technology “MISiS”, Moscow, 110049, Russia

    L. V. Shvanskaya & A. N. Vasiliev

  3. National Research South, Ural State University, Chelyabinsk, 454080, Russia

    A. N. Vasiliev

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  1. L. V. Shvanskaya
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  2. O. V. Yakubovich
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  3. A. V. Koshelev
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  4. A. N. Vasiliev
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Correspondence to L. V. Shvanskaya.

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Shvanskaya, L.V., Yakubovich, O.V., Koshelev, A.V. et al. Metal-loaded pollucite-like aluminophosphates: dissymmetrisation of crystal structures and physical properties. Phys Chem Minerals 45, 633–640 (2018). https://doi.org/10.1007/s00269-018-0948-z

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