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[Pb2F2](SeO4): a heavier analogue of grandreefite, the first layered fluoride selenate

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Abstract

Co-precipitation of PbF2 and PbSeO4 in weakly acidic media results in the formation of [Pb2F2](SeO4), the selenate analogue of the naturally occurring mineral grandreefite, [Pb2F2](SO4). The new compound is monoclinic, C2/c, a = 14.0784(2) Å, b = 4.6267(1) Å, c = 8.8628(1) Å, β = 108.98(1)°, V = 545.93(1) Å3. Its structure has been refined from powder data to R B = 1.55%. From thermal studies, it is established that the compound is stable in air up to about 300 °C, after which it gradually converts into a single phase with composition [Pb2O](SeO4), space group C2/m, and lattice parameters a = 14.0332(1) Å, b = 5.7532(1) Å, c = 7.2113(1) Å, β = 115.07(1)°, V = 527.37(1) Å3. It is the selenate analogue of lanarkite, [Pb2O](SO4), and phoenicochroite, [Pb2O](CrO4), and its crystal structure was refined to R B = 1.21%. The formation of a single decomposition product upon heating in air suggests that this happens by a thermal hydrolysis mechanism, i.e., Pb2F2SeO4 + H2O (vapor) → Pb2OSeO4 + 2HF↑. This relatively low-temperature process involves complete rearrangement of the crystal structure—from a 2D architecture featuring slabs [Pb2F2]2+ formed by fluorine-centered tetrahedra into a structure characterized by 1D motifs based on [OPb2]2+ chains of oxocentered tetrahedra. The comparative crystal chemistry of the obtained anion-centered structural architectures is discussed.

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Acknowledgements

This work was supported by St. Petersburg State University through the internal Grant 3.38.238.2015. Technical support by the X-Ray Diffraction Resource Centre of Saint-Petersburg State University is gratefully acknowledged.

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Authors and Affiliations

  1. Inorganic Chemistry Division, Department of Chemistry, Moscow State University, Leninskie Gory 1, Moscow, 119991, Russia

    Dmitri O. Charkin, Igor V. Plokhikh & Sergey M. Kazakov

  2. Department of Crystallography, St. Petersburg State University, University emb. 7/9, St. Petersburg, 199034, Russia

    Anastasiya I. Zadoya, Michael S. Kozin & Oleg I. Siidra

  3. Siberian Federal University, Svobodny prosp., 79/10, Krasnoyarsk, 660041, Russia

    Alexander N. Zaloga

  4. Institut für Geowissenschaften der Universität Kiel, Olshausenstr. 40, 24098, Kiel, Germany

    Wulf Depmeier

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  1. Dmitri O. Charkin
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Correspondence to Oleg I. Siidra.

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Charkin, D.O., Plokhikh, I.V., Zadoya, A.I. et al. [Pb2F2](SeO4): a heavier analogue of grandreefite, the first layered fluoride selenate. Phys Chem Minerals 45, 69–76 (2018). https://doi.org/10.1007/s00269-017-0903-4

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