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Site-selective As–P substitution and hydrogen bonding in the crystal structure of philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O

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Abstract

Philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O, from the Middle Pit, Gold Hill Mine, Tooele Co., Utah, USA, was studied by single-crystal X-ray diffraction and scanning electron microscopy. The empirical formula of the studied sample is (Cu4.69Zn1.23)(As0.86P0.18O4)2(OH)5.61·H2O, which agrees well with the previous reports on the mineral. Philipsburgite is monoclinic, P21/c, a = 12.385(6), b = 9.261(4), c = 10.770(5) Å, β = 97.10(1)o, V = 1225.7(9) Å3 (at 100 K), and Z = 4. The crystal structure was refined to R1 = 0.046 for 2563 unique observed reflections with |Fo| ≥ 4σF. The crystal structure of philipsburgite is isotypic to that of kipushite and can be considered as a complex three-dimensional framework consisting of two types of layers stacked parallel to the a-axis. The A-type layer is formed by the edge-sharing Jahn–Teller-distorted Cuφ6 octahedra [φ = O2−, (OH)−, H2O]. Two adjacent octahedral layers are linked via (As2O4) tetrahedra. The B-type layer is built by corner-sharing (ZnO4) and (As1O4) tetrahedra and is formed by the four- and eight-membered tetrahedral rings. The A:B ratio of the A and B layers is equal to 2:1. The hydrogen bonding network in philipsburgite is rather complex and consists of two- and three-center hydrogen bonds. The As1 site accommodates ca. 18% of P and is a preferable position for the P substitution in philipsburgite. The observed selectivity of the As1 site for P may indicate that, for the intermediate compositions with the P:As ratios close to 1:1, there is a fully ordered species with P prevalent at the As1 site and As prevalent at the As2 site. The intermediate composition would, therefore, be Cu5Zn(AsO4)(PO4)(OH)6·H2O and such a mineral can be considered as a separate species, according to the rules of the International Mineralogical Association (IMA). Philipsburgite should be considered as structurally complex with the Shannon information contents of 4.954 bits/atom and 614.320 bits/cell. The obvious reason for the structural complexity of the mineral is its modularity, i.e., the presence of two structurally distinct modules, the octahedral–tetrahedral (A) and tetrahedral (B) layers.

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Acknowledgements

We are grateful to Justyna Ciesielczuk and anonymous referee for useful comments on the manuscript and interesting discussion. This work was supported by the Russian Science Foundation (Grant 14-17-00071). The experiments were carried out using facilities of XRD and Geomodel Resource Centers of St. Petersburg State University. The contribution of Fersman Mineralogical Museum is gratefully acknowledged.

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Authors and Affiliations

  1. Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity, 184200, Russia

    Sergey V. Krivovichev

  2. Department of Crystallography, St. Petersburg State University, 7-9 University Emb, St. Petersburg, 199034, Russia

    Sergey V. Krivovichev, Elena S. Zhitova, Rezeda M. Ismagilova & Andrey A. Zolotarev

  3. Institute of Volcanology and Seismology, Russian Academy of Sciences, Piyp blvd. 9, Petropavlovsk-Kamchatsky, 683006, Russia

    Elena S. Zhitova

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  1. Sergey V. Krivovichev
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  4. Andrey A. Zolotarev
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Correspondence to Sergey V. Krivovichev.

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Krivovichev, S.V., Zhitova, E.S., Ismagilova, R.M. et al. Site-selective As–P substitution and hydrogen bonding in the crystal structure of philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O. Phys Chem Minerals 45, 917–923 (2018). https://doi.org/10.1007/s00269-018-0972-z

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  • DOI: https://doi.org/10.1007/s00269-018-0972-z

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