Crystal structure of a new compound, CuZnCl(OH)3, isostructural with botallackite

Hexing Yang; Isabel F. Barton; Marcelo B. Andrade; Robert T. Downs

doi:10.2138/am-2016-5560

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Crystal structure of a new compound, CuZnCl(OH)₃, isostructural with botallackite

Hexing Yang , Isabel F. Barton , Marcelo B. Andrade und Robert T. Downs

Veröffentlicht/Copyright: 5. April 2016

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Aus der Zeitschrift American Mineralogist Band 101 Heft 4

Abstract

A new compound, ideally CuZnCl(OH)₃, was found on a metallic mining artifact of copper composition at the Rowley mine, Maricopa County, Arizona, U.S.A., and studied with electron microprobe analysis, single-crystal X-ray diffraction, and Raman spectroscopy. It is isostructural with botallackite [Cu₂Cl(OH)₃] with space group P2₁/m and unit-cell parameters a = 5.6883(5), b = 6.3908(6), c = 5.5248(5) Å, β = 90.832(2)°, V= 200.82(3) Å³. The crystal structure of CuZnCl(OH)₃, refined to R₁ = 0.018, is characterized by brucite-type octahedral sheets made of two distinct and considerably distorted octahedra, Ml and M2, which are coordinated by (5OH + 1C1) and (4OH + 2C1), respectively. The octahedral sheets are parallel to (100) and connected by O-H∙∙∙Cl hydrogen bonding. The major structural difference between CuZnCl(OH)₃ and botallackite is the complete replacement of Cu²⁺ in the highly angle-distorted Ml site by non-Jahn-Teller distorting Zn²⁺. The CuZnCl(OH)₃ compound represents the highest Zn content ever documented for the atacamite group of minerals, in conflict with all previous reports that botallackite (like atacamite) is the most resistant, of all copper hydroxylchloride Cu₂Cl(OH)₃ polymorphs, to the substitution of Zn²⁺ for Cu²⁺, even in the presence of large excess of Zn²⁺. Its discovery, along with the recently described new mineral iyoite, CuMnCl(OH)₃, implies that more botallackite-type compounds or minerals with the chemical formula CuMCl(OH)₃(M= Ni²⁺, Co²⁺, Fe²⁺, Mn²⁺, Cd²⁺, and Mg²⁺) may be synthesized or found in nature.

Key words: CuZnCl(OH)3; copper-zinc hydroxychloride; botallackite; atacamite group; crystal structure; Raman spectroscopy

Acknowledgments

We thank Robert Jenkins, Keith Wentz, and Joe Ruiz for providing the CuZnCl(OH)₃ specimens. The funding supports from the Science Foundation Arizona and Sao Paulo Research Foundation (Grant: 2013/03487-8) are gratefully acknowledged.

References

Alejandre, F.J., and Marquez, G. (2006) Copper-zinc hydroxychlorides: origin and occurrence as paint pigments in Arcos de la Frontera’s Chapel of Mercy (Spain). European Journal of Mineralogy, 18, 403–409.10.1127/0935-1221/2006/0018-0403Suche in Google Scholar

Arcuri, T., and Brimhall, G. (2003) The chloride source for atacamite mineralization at the Radomiro Tomic porphyry copper deposit, northern Chile. Economic Geology, 98, 1667–1681.10.2113/gsecongeo.98.8.1667Suche in Google Scholar

Braithwaite, R.S.W., Mereiter, K., Paar, W.H., and Clark, A.M. (2004) Herbertsmi-thite, Cu₃Zn(OH)₆Cl₂, a new species, and the definition of paratacamite. Mineralogical Magazine, 68, 527–539.10.1180/0026461046830204Suche in Google Scholar

Cameron, E.M., Leybourne, M.I., and Palacios, C. (2007) Atacamite in the oxide zone of copper deposits in northern Chile: involvement of deep formation waters? Mineralium Deposita, 42, 205–218.10.1007/s00126-006-0108-0Suche in Google Scholar

Fleet, M.E. (1975) The crystal structure of paratacamite, Cu₂(OH)₃Cl. Acta Crystal-lographica, B31, 183–187.10.1107/S0567740875002324Suche in Google Scholar

Frost, R.L., Martens, W., Kloprogge, J.T., and Williams, PA. (2002) Raman spec-troscopy of the basic copper chloride minerals atacamite and paratacamite: implications for the study of copper, brass and bronze objects of archeological significance, Journal of Raman Spectroscopy, 33, 801–806.10.1002/jrs.921Suche in Google Scholar

Garrels, R.M. (1954) Mineral species as functions of pH and oxidation-reduction potentials, with special reference to the zone of oxidation and secondary enrichment of sulphide ore deposits. Geochimica et Cosmochimica Acta, 4, 153–168.10.1016/0016-7037(54)90030-7Suche in Google Scholar

Grice, J.D., Szymanski, J.T., and Jambor, J.L. (1996) The crystal structure of clino-atacamite, a new polymorph of Cu₂(OH)₃Cl. Canadian Mineralogist, 34, 73–78.Suche in Google Scholar

Hawthorne, FC. (1985) Refinement of the crystal structure of botallackite. Mineralogical Magazine, 49, 87–89.10.1180/minmag.1985.049.350.12Suche in Google Scholar

Jambor, J.L., Dutnzac, J.E., Roberts, A.C., Grice, J.D., and Szymanski, J.T (1996) Clinoatacamite, a new polymorph of Cu₂(OH)₃Cl, and its relationship to paratacamite and “anarakite.” Canadian Mineralogist, 34, 61–72.Suche in Google Scholar

Krause, W., Bernhardt, H.J., Braithwaite, R.S.W., Kohtsch, U., and Pritchard, R. (2006) Kapellasite, Cu₃Zn(OH)₆Cl₂, a new mineral from Lavrion, Greece, and its crystal structure. Mineralogical Magazine, 70, 329–340.10.1180/0026461067030336Suche in Google Scholar

Lichtenegger, H.C., Schoberl, T, Bartl, M.H., Waite, H., and Stucky, G.D. (2002) High abrasion resistance with sparse mineralization: Copper biomineral in worm jaws. Science, 298, 389–392.10.1126/science.1075433Suche in Google Scholar PubMed

Liu, X., Hagihala, M., Zheng, X., and Guo, Q. (2011a) Vibrational spectroscopic properties of botallackite-structure basic copper halides. Vibrational Spectroscopy, 56, 177–183.10.1016/j.vibspec.2011.02.002Suche in Google Scholar

Liu, X., Meng, D., Hagihala, M., and Zheng, X. (2011b) Microstructuralhydroxyl environments and Raman spectroscopy in selected basic transition-metal halides. Chinese Physics, B20, 087801.10.1088/1674-1056/20/8/087801Suche in Google Scholar

Mann, A.W., and Deutscher, R.L. (1980) Solution geochemistry of lead and zinc in water containing carbonate, sulphate and chloride ions. Chemical Geology, 29,293–311.10.1016/0009-2541(80)90026-1Suche in Google Scholar

Martens, W., Frost, R.L., and Williams, PA. (2003) Raman and infrared spectroscopic study of the basic copper chloride minerals—implications for the study of the copper and brass corrosion and “bronze disease.” Neues Jahrbuch fur Mineralogie Abhandlungen, 178, 197–215.10.1127/0077-7757/2003/0178-0197Suche in Google Scholar

Mossman, D. J., and Heffernan, K. J. (1978) On the possible primary precipitation of atacamite and other metal chlorides in certain stratabound deposits. Chemical Geology, 21, 151–159.10.1016/0009-2541(78)90011-6Suche in Google Scholar

Nishio-Hamane, D., Momma, K., Ohnishi, M., Shimobayashi, N, Miyawaki, R., Tomita, N, and Minakawa, T (2014) Iyoite, IMA 2013–130. Mineralogical Magazine, 78, 549–558.Suche in Google Scholar

Parise, J.B., and Hyde, B.G. (1986) The structure of atacamite and its relationship to spinel. Acta Crystallographica, C42, 1277–1280.10.1107/S0108270186092570Suche in Google Scholar

Pollard, A.M., Thomas, R.G., and Williams, PA. (1989) Synthesis and stabilities of the basic copper (II) chlorides atacamite, paratacamite, and botallackite. Mineralogical Magazine, 53, 557–563.10.1180/minmag.1989.053.373.06Suche in Google Scholar

Robinson, K., Gibbs, G.V., and Ribbe, PH. (1971) Quadratic elongation, a quantitative measure of distortion in coordination polyhedra. Science, 172, 567–570.10.1126/science.172.3983.567Suche in Google Scholar PubMed

Scott, DA. (2000) Areview of copper chlorides and related salts in bronze corrosion and as painting pigments. Studies in Conservation, 45, 39–53.Suche in Google Scholar

Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64 112–122.10.1107/S0108767307043930Suche in Google Scholar PubMed

Takeda, S., Maruta, G., Terasawa, K., Fukuda, N, and Yamaguchi, K. (1999) Local magnetic structure of layered compounds Cu₂(OD)₃X with exchangeable acid anion X studied by solid state high resolution deuterium NMR. Molecular Crystals and Liquid Crystals Science and Technology, 335, 11–21.10.1080/10587259908028847Suche in Google Scholar

Vennum, W.R., and Nishi, J.M. (1992) Chemical weathering of Cu, Fe, and Pb sulfides, southern Ellsworth Mountains, West Antarctica. In G.F Webers, C. Craddock, and J.F Splettstoesser, Eds., Geology and Paleontology of the Ellsworth Mountains, West Antarctica, 170, p. 433-442. Geological Society of America Memoir, Boulder, Colorado.10.1130/MEM170-p433Suche in Google Scholar

Welty, J.W, Spencer, J.E., Allen, G.B., Reynbolds, S.J., and Trapp, RA. (1985) Geology and production of Middle Tertiary mineral districts in Arizona. Arizona Bureau of Geology and Mineral Technology Open-File Report 85-1.Suche in Google Scholar

Wilson, WE., and Miller, D.K. (1974) Minerals of the Rowley mine. Mineralogical Record, 5, 10–30.Suche in Google Scholar

Yoder, C.H., Schaeffer, R.W., McCaffrey, RE, Rowand, A., Liu, X., and Schaeffer J. (2011) The synthesis of copper/zinc solid solutions of hydroxyl carbonates, sulphates, nitrates, chlorides and bromides. Mineralogical Magazine, 75, 2573–2582.10.1180/minmag.2011.075.5.2573Suche in Google Scholar

Zheng, X.G., and Xu, C.N. (2004) Antiferromagnetic transition in botallackite Cu₂Cl(OH)₃. Solid State Communications, 131, 509–511.10.1016/j.ssc.2004.06.018Suche in Google Scholar

Zheng, X.G., Mori, T, Nishiyama, K., Higemoto, W, Yamada, H., Nishikubo, K, and Xu, C.N. (2005) Antiferromagnetic transitions in polymorphous minerals of the natural cuprates atacamite and botallackite Cu₂Cl(OH)₃. Physical Review B, 71, 174404.10.1103/PhysRevB.71.174404Suche in Google Scholar

Zheng, X.G., Yamashita, T, Hagihala, M., Fujihala, M., and Kawae, T. (2009) Magnetic transitions in botallackite-structure Cu₂(OH)₃Br and Cu₂(OH)₃I. Physica B, 404, 680–682.10.1016/j.physb.2008.11.221Suche in Google Scholar

Received: 2015-9-18

Accepted: 2015-11-30

Published Online: 2016-4-5

Published in Print: 2016-4-1

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https://doi.org/10.2138/am-2016-5560

Schlagwörter für diesen Artikel

CuZnCl(OH)3; copper-zinc hydroxychloride; botallackite; atacamite group; crystal structure; Raman spectroscopy