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The crystal structures of the mixed-valence tellurium oxysalts tlapallite, (Ca,Pb)3CaCu6[Te4+3Te6+O12]2(Te4+O3)2(SO4)2·3H2O, and carlfriesite, CaTe4+2Te6+O8

Published online by Cambridge University Press:  12 February 2019

Owen P. Missen
Affiliation:
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia School of Earth, Atmosphere and Environment, 9 Rainforest Walk, Monash University, Clayton 3800, Victoria, Australia
Anthony R. Kampf
Affiliation:
Mineral Sciences Department, Natural History Museum of Los Angeles County, 900 Exposition Boulevard, Los Angeles, CA 90007, USA
Stuart J. Mills
Affiliation:
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
Robert M. Housley
Affiliation:
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA
John Spratt
Affiliation:
Department of Core Research Laboratories, Natural History Museum, Cromwell Road, London SW7 5BD, UK
Mark D. Welch
Affiliation:
Department of Earth Sciences, Natural History Museum, Cromwell Road, London SW7 5BD, UK
Mark F. Coolbaugh
Affiliation:
Renaissance Gold Inc., 4750 Longley Lane, Suite 106, Reno, NV 89502, USA
Joe Marty
Affiliation:
5199 East Silver Oak Road, Salt Lake City, UT 84108, USA
Marek Chorazewicz
Affiliation:
124 Pineplank Lane, Simi Valley, CA 93065, USA
Cristiano Ferraris
Affiliation:
Laboratoire de Physique des Milieux Condensés (LPMC), CNRS-UMR 7590, Muséum National d'Histoire Naturelle (MNHN), 61 rue Buffon, 75005 Paris, France
Corresponding
E-mail address:

Abstract

The crystal structure of tlapallite has been determined using single-crystal X-ray diffraction and supported by electron probe micro-analysis, powder diffraction and Raman spectroscopy. Tlapallite is trigonal, space group P321, with a = 9.1219(17) Å, c = 11.9320(9) Å and V = 859.8(3) Å3, and was refined to R1 = 0.0296 for 786 reflections with I > 2σ(I). This study resulted from the discovery of well-crystallised tlapallite at the Wildcat prospect, Utah, USA. The chemical formula of tlapallite has been revised to (Ca,Pb)3CaCu6[Te4+3Te6+O12]2(Te4+O3)2(SO4)2·3H2O, or more simply (Ca,Pb)3CaCu6Te4+8Te6+2O30(SO4)2·3H2O, from H6(Ca,Pb)2(Cu,Zn)3(TeO3)4(TeO6)(SO4). The tlapallite structure consists of layers containing distorted Cu2+O6 octahedra, Te6+O6 octahedra and Te4+O4 disphenoids (which together form the new mixed-valence phyllotellurate anion [Te4+3Te6+O12]12−), Te4+O3 trigonal pyramids and CaO8 polyhedra. SO4 tetrahedra, Ca(H2O)3O6 polyhedra and H2O groups fill the space between the layers. Tlapallite is only the second naturally occurring compound containing tellurium in both the 4+ and 6+ oxidation states with a known crystal structure, the other being carlfriesite, CaTe4+2Te6+O8. Carlfriesite is the predominant secondary tellurium mineral at the Wildcat prospect. We also present an updated structure for carlfriesite, which has been refined to R1 = 0.0230 for 874 reflections with I > 2σ(I). This updated structural refinement improves upon the one reported previously by refining all atoms anisotropically and presenting models of bond valence and Te4+ secondary bonding.

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Article
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

Associate Editor: Oleg I Siidra

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The crystal structures of the mixed-valence tellurium oxysalts tlapallite, (Ca,Pb)3CaCu6[Te4+3Te6+O12]2(Te4+O3)2(SO4)2·3H2O, and carlfriesite, CaTe4+2Te6+O8
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The crystal structures of the mixed-valence tellurium oxysalts tlapallite, (Ca,Pb)3CaCu6[Te4+3Te6+O12]2(Te4+O3)2(SO4)2·3H2O, and carlfriesite, CaTe4+2Te6+O8
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The crystal structures of the mixed-valence tellurium oxysalts tlapallite, (Ca,Pb)3CaCu6[Te4+3Te6+O12]2(Te4+O3)2(SO4)2·3H2O, and carlfriesite, CaTe4+2Te6+O8
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