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Shilovite, natural copper(II) tetrammine nitrate, a new mineral species

Published online by Cambridge University Press:  02 January 2018

Nikita V. Chukanov ,
Sergey N. Britvin ,
Gerhard Möhn ,
Igor V. Pekov ,
Natalia V. Zubkova ,
Fabrizio Nestola ,
Anatoly V. Kasatkin  and
Maurizio Dini
Nikita V. Chukanov*
Affiliation:
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow region, 142432 Russia
Sergey N. Britvin
Affiliation:
Institute of Geosciences, St Petersburg State University, Universitetskaya Nab. 7/9, St Petersburg, 199034 Russia
Gerhard Möhn
Affiliation:
Dr J. Wittemannstrasse 5, 65527 Niedernhausen, Germany
Igor V. Pekov
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow, 119991 Russia
Natalia V. Zubkova
Affiliation:
Faculty of Geology, Moscow State University, Vorobievy Gory, Moscow, 119991 Russia
Fabrizio Nestola
Affiliation:
Dipartimento di Geoscienze, Università di Padova, Via Gradenigo 6, I-35131, Padova, Italy
Anatoly V. Kasatkin
Affiliation:
V/O “Almazjuvelirexport”, Ostozhenka Street 22, Block 1, 119034 Moscow, Russia
Maurizio Dini
Affiliation:
Pasaje San Augustin 4045, La Serena, Chile
*
*E-mail: [email protected]
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Abstract

The new mineral shilovite, the first natural tetrammine copper complex, was found in a guano deposit located on the Pabellón de Pica Mountain, near Chanabaya, Iquique Province, Tarapacá Region, Chile. It is associated with halite, ammineite, atacamite (a product of ammineite alteration) and thénardite. The gabbro host rock consists of amphibole, plagioclase and minor clinochlore, and contains accessory chalcopyrite. The latter is considered the source of Cu for shilovite. The new mineral occurs as deep violet blue, imperfect, thick tabular to equant crystals up to 0.15 mm in size included in massive halite. The mineral is sectile. Its Mohs hardness is 2. Dcalc is 1.92 g cm–3. The infrared spectrum shows the presence of NH3 molecules and NO3– anions. Shilovite is optically biaxial (+), α = 1.527(2), β = 1.545(5), γ = 1.610(2). The chemical composition (electron-microprobe data, H calculated from ideal formula, wt.%) is Cu 26.04, Fe 0.31, N 30.8, O 35.95, H 4.74, total 100.69. The empirical formula is H12.56(Cu1.09Fe0.01)N5.87O6.00. The idealized formula is Cu(NH3)4(NO3)2. The crystal structure was solved and refined to R = 0.029 based upon 2705 unique reflections having F > 4σ(F). Shilovite is orthorhombic, space group Pnn2, a = 23.6585(9), b = 10.8238(4), c = 6.9054(3) Å, V = 1768.3(1) Å3, Z = 8. The strongest reflections of the powder X-ray diffraction pattern [d, Å (I,%) (hkl)] are: 5.931 (41) (400), 5.841 (100) (011), 5.208 (47) (410), 4.162 (88) (411), 4.005 (62) (420), 3.462 (50) (002), 3.207 (32) (031), 2.811 (40) (412).

Keywords

shilovitenew mineraltetrammine copper complexcrystal structureguanoPabellón de PicaChile
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 3 , June 2015 , pp. 613 - 623
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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References

Agilent Technologies (2013) CrysAlisPro, Version 1.171.36.32. Yarnton, Oxfordshire, UK.Google Scholar
Anderson, T.M., Rodriguez, M.A., Stewart, T.A., Bixler, J.N., Xu, W., Parise, J.B. and Nyman, M. (2008) Controlled assembly of [Nb6-xWxO19](8-x)-(x = 0-4). Lindqvist ions with (amine)copper complexes. European Journal of Inorganic Chemistry, 21, 3286–3294.CrossRefGoogle Scholar
Ang, H.-G., Fraenk, W., Karaghiosoff, K., Klapötke, T.M., Mayer, P., Nöth, H., Sprott, J. and Warchhold, M. (2002) Synthesis, characterization, and crystal structures of Cu, Ag, and Pd dinitramide salts. Zeitschrift für anorganische und allgemeine Chemie, 628, 2894–2900.3.0.CO;2-R>CrossRefGoogle Scholar
Appleton, J.D. and Nothold, A.J.G. (2002) Local phosphate resources for sustainable development of Central and South America. Economic Minerals and Geochemical Baseline Programme Report CR/02/ 122/N. British Geological Survey, Keyworth, UK. Armbruster, T., Simoncic, P., Döbelin, N., Malsy, A. and Yang, P. (2003) Cu2+-acetate and Cu2+-ammine exchanged heulandite: a structural comparison. Microporous and Mesoporous Materials, 57, 121–131.Google Scholar
Bojar, H.-P. and Walter, F. (2012) Joanneumite, IMA 2012-001. CNMNC Newsletter No. 13, June 2012, page 814; Mineralogical Magazine, 76, 807–817.Google Scholar
Bojar, H.-P., Walter, F., Baumgartner, J. and Färber, G. (2010) Ammineite, CuCl2(NH3)2, a new species containing an ammine complex: mineral data and crystal structure. The Canadian Mineralogist, 48, 1359–1371.CrossRefGoogle Scholar
Chesnokov, B.V., Bazhenova, L.F., Bushmakin, A.F., Vilisov, V.A., Lotova, E.V., Mikhal, T.A., Nishanbaev, T.P. and Shcherbakova, E.P. (1991) New minerals from the burned dumps of Chelyabinsk Coal Basin. Pp. 5–21. in: New data on the Mineralogy of Endogenic Localities and Zones of Technogenesis of Urals. Ural Branch of the Academy of Sciences of the USSR, Sverdlovsk, Russia [in Russian].Google Scholar
Chrappová, J., Schwendt, P., Dudášová, D., Tatiersky, J. and Marek, J. (2008) Synthesis, X-ray crystal structure and thermal decomposition of two peroxovanadium complexes with coordinated ammonia molecules: [{VO(O2) 2(NH3)}2{[m-Cu(NH3)4}] and [Zn(NH3)4][VO(O2)2(NH3)]2. Polyhedron, 27, 641–647.CrossRefGoogle Scholar
Chukanov, N.V., Zubkova, N.V., Möhn, G., Pekov, I.V., Zadov, A.E and Pushcharovsky, D.Y. (2013) Chanabayaite, IMA 2013-065. CNMNC Newsletter No. 17, October 2013, page 3004; Mineralogical Magazine, 77, 2997–3005.Google Scholar
Chukanov, N.V., Britvin, S.N., Möhn, G., Pekov, I.V., Zubkova, N.V., Nestola, F., Kasatkin, A.V. and Dini, M. (2014) Shilovite, IMA 2014-016. CNMNC Newsletter No. 21, August 2014, page 798; Mineralogical Magazine, 78, 797–804.Google Scholar
Dowty, E. (2000) ATOMS. Version 6.1. Shape Software, Hidden Valley Road, Kingsport, Tennessee, USA. Ericksen, G.E. (1981) Geology and origin of the Chilean nitrate deposits. Geological Survey Professional Paper, 1188. Gorbunov, V.V. and Shmagin, L.F. (1972) Burning of copper (II) tetrammine salts. Fizika Goreniya i Vzryva, 8, 523–526. [in Russian].Google Scholar
Karovičová, M. and Mad’ar, J. (1960) A contribution to the crystal structure of Cu(NH3)4(NO3)2. Czech Physical Journal, B10, 258. Khranenko, S.P., Shusharina, E.A., Gromilov, S.A. and Smolentsev, A.I. (2009) Crystal structure of [Cu(NH3)4](ReO4)2. Journal of Structural Chemistry, 50, 1201–1203.Google Scholar
Kótai, L., Banerji, K.K., Sajó, I., Kristóf, J., Sreedhar, B., Holly, S., Keresztury, G. and Rockenbauer, A. (2002) An unprecedented-type intramolecular redox reaction of solid tetraamminecopper(2+) bis(permanganate) ([Cu(NH3)4](MnO4)2)-a low-temperature synthesis of copper dimanganese tetraoxide-type (CuMn2O4) nanocrystalline catalyst precursors. Helvetica Chimica Acta, 85, 2316–2327.3.0.CO;2-A>CrossRefGoogle Scholar
Leskelä, M. and Valkonen, J. (1978) The crystal structure, thermal behaviour and IR spectrum of copper tetraammine dithionate. Acta Chemica Scandinavica, A32, 805–809.Google Scholar
Morosin, B. (1969) The crystal structures of copper tetrammine complexes A. Cu(NH3)4(SO4)6H2O and Cu(NH3)4SeO4. Acta Crystallographica, B25, 19–30.CrossRefGoogle Scholar
Morosin, B. (1976) The crystal structure of copper(II) tetraammine nitrate. Acta Crystallographica, B32, 1237–1240.CrossRefGoogle Scholar
Nakamoto, K. (2008) Infrared and Raman Spectra of Inorganic and Coordination Compounds, Theory and Applications in Inorganic Chemistry. John Wiley and Sons, New York.Google Scholar
Nakamoto, K. (2009) Infrared and Raman Spectra of Inorganic and Coordination Compounds, Part B, Applications in Coordination, Organometallic, and Bioinorganic Chemistry. John Wiley and Sons, Hoboken, USA.Google Scholar
Oxford Instruments Analytical (2006) INCA Energy Operator Manual, Issue 2.1. High Wycombe, UK.Google Scholar
Pankhurst, R.J. and Herve, F. (2007) Introduction and overview. Pp. 1–4. in: The Geology of Chile (T. Moreno and W. Gibbons, editors). The Geological Society, London.Google Scholar
Seferiadis, N., Dubler, E. and Oswald, H.R. (1986) Structure of tetraamminecopper(II) dipermanganate. Acta Crystallographica, C42, 942–945.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.CrossRefGoogle Scholar
Von Meyeren, W.A. and Brennecke, E. (1965) Gmelins Handbuch der Anorganischen Chemie: Kupfer. Verlag Chemie Gmbh., Weinheim, Germany.Google Scholar