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The crystal-structure determination and redefinition of eztlite, Pb22+ Fe33+(Te4+O3)3(SO4)O2Cl

Published online by Cambridge University Press:  15 May 2018

Owen P. Missen ,
Stuart J. Mills ,
John Spratt ,
Mark D. Welch ,
William D. Birch ,
Michael S. Rumsey  and
Jan Vylita
Owen P. Missen*
Affiliation:
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia School of Chemistry, University of Melbourne, Parkville 3010, Victoria, Australia
Stuart J. Mills
Affiliation:
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
John Spratt
Affiliation:
Department of Core Research Laboratories, Natural History Museum, Cromwell Road, London SW7 5BD, England, UK
Mark D. Welch
Affiliation:
Department of Earth Sciences, Natural History Museum, Cromwell Road, London SW7 5BD, England, UK
William D. Birch
Affiliation:
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
Michael S. Rumsey
Affiliation:
Department of Earth Sciences, Natural History Museum, Cromwell Road, London SW7 5BD, England, UK
Jan Vylita
Affiliation:
Na Ostrohu 47, Praha 6, 16000, Czech Republic
*
*E-mail: omissen@museum.vic.gov.au
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Abstract

The crystal structure of eztlite has been determined using single-crystal synchrotron X-ray diffraction and supported using electron microprobe analysis and powder diffraction. Eztlite, a secondary tellurium mineral from the Moctezuma mine, Mexico, is monoclinic, space group Cm, with a = 11.466(2) Å, b = 19.775(4) Å, c = 10.497(2) Å, β = 102.62(3)° and V = 2322.6(9) Å3. The chemical formula of eztlite has been revised to ${\rm Pb}_{\rm 2}^{2 +} {\rm Fe}_3^{3 +} $(Te4+O3)3(SO4)O2Cl from that stated previously as ${\rm Fe}_6^{3 +} {\rm Pb}_{\rm 2}^{2 +} $(Te4+O3)3(Te6+O6)(OH)10·nH2O. This change has been accepted by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association, Proposal 18-A. Eztlite was reported originally to be a mixed-valence Te oxysalt; however the crystal structure, bond-valence analysis and charge balance considerations clearly show that all Te is tetravalent. Eztlite contains a unique combination of elements and is only the second Te oxysalt to contain both sulfate and chloride. The crystal structure of eztlite contains mitridatite-like layers, with a repeating triangular nonameric [${\rm Fe}_9^{3 +} $O36]45– arrangement formed by nine edge-sharing Fe3+O6 octahedra, decorated by four trigonal pyramidal Te4+O3 groups, compared to PO4 or AsO4 tetrahedra in mitridatite-type minerals. In eztlite, all four tellurite groups associated with one nonamer are orientated with the lone pair of the Te atoms pointing in the same direction, whereas in mitridatite the central tetrahedron is orientated in the opposite direction to the others. In mitridatite-type structures, interlayer connections are formed exclusively via Ca2+ and water molecules, whereas the eztlite interlayer contains Pb2+, sulfate tetrahedra and Cl–. Interlayer connectivity in eztlite is achieved primarily by connections via the long bonds of Pbφ8 and Pbφ9 groups to sulfate tetrahedra and to Cl–. Secondary connectivity is via Te–O and Te–Cl bonds.

Keywords

eztlitecrystal structuretelluritesynchrotron radiationtellurium oxysaltmitridatite
Type
Article
Information
Mineralogical Magazine , Volume 82 , Issue 6 , December 2018 , pp. 1355 - 1367
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

Associate Editor: Ferdinando Bosi

‡

Present address: School of Earth, Atmosphere and Environment, Monash University, Clayton 3800, Victoria, Australia.

References

Andrade, M.B., Morrison, S.M., Di Domizio, A.J., Feinglos, M.N. and Downs, R.T. (2012) Robertsite, Ca2MnIII3O2(PO4)3·3H2O. Acta Crystallographica, E68, i74–i75.Google Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.Google Scholar
Bruker, (2001) SADABS and XPREP. Bruker AXS Inc., Madison, WI, USA.Google Scholar
Burns, P.C., Pluth, J.J., Smith, J.V., Eng, P., Steele, I. and Housley, R.M. (2000) Quetzalcoatlite: a new octahedral-tetrahedral structure from a 2×2×40 μm3 crystal at the Advanced Photon Source-GSE-CARS facility. American Mineralogist, 85, 604–607.Google Scholar
Christy, A.G. and Mills, S.J. (2013) Effect of lone-pair stereoactivity on polyhedral volume and structural flexibility: application to TeIVO6 octahedra. Acta Crystallographica, B69, 446–456.Google Scholar
Christy, A.G., Mills, S.J. and Kampf, A.R. (2016) A review of the structural architecture of tellurium oxycompounds. Mineralogical Magazine, 80, 415–545.Google Scholar
Degen, T., Sadki, M., Bron, E., König, U. and Nénert, G. (2014) The Highscore suite. Powder Diffraction, 29, S13–S18.Google Scholar
Effenberger, H., Zemann, J. and Mayer, H. (1978) Carlfriesite; crystal structure, revision of chemical formula, and synthesis. American Mineralogist, 63, 847–852.Google Scholar
Feger, C.R., Kolis, J.W., Gorny, K. and Pennington, C. (1999) Rodalquilarite revisited: the hydrothermal synthesis and structural reinvestigation of H3Fe2(TeO3)4Cl. Journal of Solid State Chemistry, 143, 254–259.Google Scholar
Gagné, O.C. and Hawthorne, F.C. (2015) Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen. Acta Crystallographica, B71, 562–578.Google Scholar
Huminicki, D.M.C. and Hawthorne, F.C. (2002) The crystal chemistry of phosphate minerals. Pp. 123–253 in: Phosphates – Geochemical, Geobiological and Materials Importance (Kohn, M.L., Rakovan, J. and Hughes, J. M., editors). Reviews in Mineralogy & Geochemistry, 48. Mineralogical Society of America and the Geochemical Society, Washington, DC.Google Scholar
Kabsch, W. (2010). XDS. Acta Crystallographica, D66, 125–132.Google Scholar
Kampf, A.R. and Mills, S.J. (2011) The role of hydrogen in tellurites: crystal structure refinements of juabite, poughite and rodalquilarite. Journal of Geosciences, 56, 235–247.Google Scholar
Kampf, A.R., Mills, S.J. and Rumsey, M.S. (2017) The discreditation of girdite. Mineralogical Magazine, 81, 1125–1128.Google Scholar
Kraus, W. and Nolze, G. (1996) POWDER CELL – a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns. Journal of Applied Crystallography, 29, 301–303.Google Scholar
Krivovichev, S.V. and Brown, I.D. (2001) Are the compressive effects of encapsulation an artifact of the bond valence parameters? Zeitschrift für Kristallographie, 216, 245–247.Google Scholar
Laugier, J. and Bochu, B. (2004) Chekcell: Graphical powder indexing cell and space group assignment software, http://www.ccp14.ac.uk/tutorial/lmgp/.Google Scholar
Mills, S.J. and Christy, A.G. (2013) Revised values of the bond-valence parameters for TeIV–O, TeVI–O and TeIV–Cl. Acta Crystallographica, B69, 145–149.Google Scholar
Moore, P. and Ito, J. (1974) Isotypy of robertsite, mitridatite, and arseniosiderite. American Mineralogist, 59, 48–59.Google Scholar
Moore, P.B. and Araki, T. (1977) Mitridatite, Ca6(H2O)6[${\rm Fe}_9^{3 +} $O6(PO4)9]·3H2O. A noteworthy octahedral sheet structure. Inorganic Chemistry, 16, 1096–1106.Google Scholar
Pasero, M. et al. (2017) The New IMA List of Minerals, http://nrmima.nrm.se/.Google Scholar
Pertlik, F. and Zemann, J. (1988) The crystal structure of nabokoite, Cu7TeO4(SO4)5·KCl: The first example of a Te(IV)O4 pyramid with exactly tetragonal symmetry. Mineralogy and Petrology, 38, 291–298.Google Scholar
Pouchou, J.L. and Pichoir, F. (1991) Quantitative analysis of homogeneous or stratified microvolumes applying the model “PAP”. Pp. 31–75 in: Electron Probe Quantification, (Heinrich, K.F.J. and Newbury, D.E., editors). Plenum Press, New York.Google Scholar
Roberts, A.C., Gault, R.A., Jensen, M.C., Criddle, A.J. and Moffatt, E.A. (1997) Juabite, Cu5(Te6+O4)2(As5+O4)2·3H2O, a new mineral species from the Centennial Eureka mine, Juab County, Utah. Mineralogical Magazine, 61, 139–144.Google Scholar
Sheldrick, G.M. (2015 a) SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallographica, A71, 3–8.Google Scholar
Sheldrick, G.M. (2015 b) Crystal structure refinement with SHELXL. Acta Crystallographica, C71, 3–8.Google Scholar
Voloshin, A., Men'shikov, Y.P., Polezhaeva, L. and Lentsi, A. (1982) Kolfanite, a new mineral from granite pegmatite, Kola Peninsula. Mineralogicheskiy Zhurnal, 4, 90–95.Google Scholar
Williams, S.A. (1982) Cuzticite and eztlite, two new tellurium minerals from Moctezuma, Mexico. Mineralogical Magazine, 46, 257–259.Google Scholar
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