Skip to main content Accessibility help

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

  • Nikita V. Chukanov (a1), Sergey N. Britvin (a2), Gerhard Möhn (a3), Igor V. Pekov (a4), Natalia V. Zubkova (a4), Fabrizio Nestola (a5), Anatoly V. Kasatkin (a6) and Maurizio Dini (a7)...


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).


Corresponding author


Hide All
Agilent Technologies (2013) CrysAlisPro, Version Yarnton, Oxfordshire, UK.
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, 32863294.
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, 28942900.
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, 121131.
Bojar, H.-P. and Walter, F. (2012) Joanneumite, IMA 2012-001. CNMNC Newsletter No. 13, June 2012, page 814; Mineralogical Magazine, 76, 807817.
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, 13591371.
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. 521. 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].
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, 641647.
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, 29973005.
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, 797804.
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, 523526. [in Russian].
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, 12011203.
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, 23162327.
Leskelä, M. and Valkonen, J. (1978) The crystal structure, thermal behaviour and IR spectrum of copper tetraammine dithionate. Acta Chemica Scandinavica, A32, 805809.
Morosin, B. (1969) The crystal structures of copper tetrammine complexes A. Cu(NH3)4(SO4)6H2O and Cu(NH3)4SeO4. Acta Crystallographica, B25, 1930.
Morosin, B. (1976) The crystal structure of copper(II) tetraammine nitrate. Acta Crystallographica, B32, 12371240.
Nakamoto, K. (2008) Infrared and Raman Spectra of Inorganic and Coordination Compounds, Theory and Applications in Inorganic Chemistry. John Wiley and Sons, New York.
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.
Oxford Instruments Analytical (2006) INCA Energy Operator Manual, Issue 2.1. High Wycombe, UK.
Pankhurst, R.J. and Herve, F. (2007) Introduction and overview. Pp. 14. in: The Geology of Chile (T. Moreno and W. Gibbons, editors). The Geological Society, London.
Seferiadis, N., Dubler, E. and Oswald, H.R. (1986) Structure of tetraamminecopper(II) dipermanganate. Acta Crystallographica, C42, 942945.
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112122.
Von Meyeren, W.A. and Brennecke, E. (1965) Gmelins Handbuch der Anorganischen Chemie: Kupfer. Verlag Chemie Gmbh., Weinheim, Germany.



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed