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New insights into the crystal chemistry of zemannite: Trigonal rather than hexagonal symmetry due to ordering within the host-guest structure

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Abstract

The microporous crystal structure of zemannite, Mg(H2O)6[Zn2+Fe3+(TeO3)3]2·nH2O, n ≤ 3, was re-investigated based on single-crystal X-ray diffraction data measured at 298 ± 0.5 K, 200 ± 1 K and 100 ± 3 K. So far, zemannite was described in space group P63 exhibiting a pronounced pseudosymmetry (P63/m). All refinements confirm the [Zn2+Fe3+(TeO3)3]1− framework topology with the extra-framework constituents (Mg atoms and H2O molecules) being located within the channels along [001]. Measurements on a sample from the type locality revealed the unexpected occurrence of 00l reflections with l = 2n + 1, which clearly violate the 63 screw-axis symmetry. The minor but significant intensities of the low-order 00l reflections are assigned to the small differences in the scattering power between the Fe and Zn atoms; thus, the Zn and Fe cations are partly ordered between crystallographically distinct sites within the framework. In addition, the low symmetry allows a full order of the extra-framework atoms for the first time. A series of comparative refinement models were performed in the space groups P63/m, P63, P\(\overline{6}\), and P3. A fully ordered arrangement of the extra-framework guest atoms confirms the earlier postulated theoretical structure model with a hexahydrated Mg2+ ion besides additional interstitial H2O molecules. The final refinements in space group P3 yield R1 ≤ 0.025 for the entire data sets measured at the distinct temperatures (2θmax = 101.4°, MoKα radiation). The polarity of the arrangement in the channels is restricted to individual domains of equal twin fractions related by a mirror plane parallel to (0001).

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Acknowledgements

The article is dedicated to Prof. Dr. Josef Zemann (1923-2022) on the occasion of the 100th anniversary of his birthday. The authors acknowledge information about ongoing investigations of zemannite-type compounds by Matthias Weil and Felix Eder (Technical University of Vienna). We thank two anonymous reviewers and Guest Editor Thomas Armbruster for their constructive comments, which significantly improved the manuscript. University of Vienna is thanked for financial support within the scope of the grants BE532003, IP532010 and IP532022 dedicated to instrumentation.

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  1. Institut für Mineralogie und Kristallographie, Universität Wien, Josef-Holaubek-Platz 2, 1090, Wien, Austria

    Herta S. Effenberger, Martin Ende & Ronald Miletich

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  1. Herta S. Effenberger
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Correspondence to Herta S. Effenberger.

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Effenberger, H.S., Ende, M. & Miletich, R. New insights into the crystal chemistry of zemannite: Trigonal rather than hexagonal symmetry due to ordering within the host-guest structure. Miner Petrol 117, 117–131 (2023). https://doi.org/10.1007/s00710-023-00820-7

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