No CrossRef data available.
Article contents
Determination of the tegengrenite superstructure: another case of tetrahedral Mn3+ in spinel-type minerals?
Published online by Cambridge University Press: 02 January 2018
Abstract
The crystal structure of the spinel-related, Sb mineral tegengrenite from the Filipstad district, Värmland, Sweden, has been solved in the space group R3 [a = 16.0285(9), c = 14.8144(8) Å, V = 3296.1(3) Å3, Z = 42] and refined up to R = 0.0484 for 3589 reflections with Fo > 4σ(Fo). Tegengrenite exhibits a rhombohedrally distorted spinel-type structure with cations occupying 1/8 of the tetrahedral (T) and 1/2 of the octahedral (M) interstices of a nearly regular cubic close-packing of oxygen atoms. Due to the cation ordering, which leads to a complex superstructure with a unit-cell volume of 21/4 that of a common spinel, the M and T sites of the spinel-type structure split into ten and six independent sites, respectively. Chemical composition determined by electron microprobe led to the empirical formula Mg1.26Mn0.852+Zn0.04Mn0.193+Al0.01Si0.12Ti0.03Sb0.505+O4, on the assumption that no vacancies occur in the mineral (Σcat = 3.00 and Σcharge = 8.00 per formula unit). Crystal-chemical considerations indicate that octahedra are occupied mainly by Mg, Mn3+ and Sb5+ (+Al, + Ti), whereas tetrahedra are filled mainly by Mn2+ and Mg (+Zn) with Si ordered in a specific site. However, the structure refinement shows a low site-scattering factor for one octahedral site, implying substantial vacancies and a larger overall mean Mn valence than stated above. Long mean distances also suggest some Mn2+ on octahedral sites. Together, these observations necessitate the presence of substantial Mn3+ on tetrahedral sites.
Keywords
- Type
- Research Article
- Information
- Copyright
- Copyright © The Mineralogical Society of Great Britain and Ireland 2015
References
Bonazzi, P. and Bindi, L. (2007) The crystal structure of ingersonite, Ca3Mn
2+
Sb5+ 4 O14, and its relationships with pyrochlore. American Mineralogist, 92, 947–953.CrossRefGoogle Scholar
Bonazzi, P., Chelazzi, L. and Bindi, L. (2013) Superstructure, crystal chemistry and cation distribution in filipstadite, a Sb5+-bearing, spinel-related mineral. American Mineralogist, 98, 361–366.CrossRefGoogle Scholar
Bosi, F., Andreozzi, G.B., Ferrini, V. and Lucchesi, S. (2004) Behavior of cation vacancy in kenotetrahedral Cr-spinels from Albanian eastern belt ophiolites. American Mineralogist, 89, 1367–1373.CrossRefGoogle Scholar
Bosi, F., Hålenius, U., Andreozzi, G.B., Skogby, H. and Lucchesi, S. (2007) Structural refinement and crystal chemistry of Mn-doped spinel: A case for tetrahedrally coordinated Mn3+ in an oxygen-based structure. American Mineralogist, 92, 27–33.CrossRefGoogle Scholar
Bosi, F., Hålenius, U. and Skogby, H. (2009) Crystal chemistry of the magnetite-ulvöspinel series. American Mineralogist, 94, 181–189.CrossRefGoogle Scholar
Buessem, W.R. and Butler, S.R. (1963) Valence changes of iron and manganese in manganese ferrite. Journal of the American Ceramic Society, 46, 442–446.CrossRefGoogle Scholar
Chelazzi, L., Boffa Ballaran, T., Bindi, L. and Bonazzi, P. (2011a) In situ high-temperature X-ray powder diffraction study of the synthetic Ca2Sb2O7 weberitetype compound. Periodico di Mineralogia, 80, 145–153.Google Scholar
Chelazzi, L., Boffa Ballaran, T., Nestola, F., Bindi, L. and Bonazzi, P. (2011b) High-pressure behavior of the synthetic Ca2Sb2O7 weberite-type compound. Solid State Sciences, 13, 1092–1095.CrossRefGoogle Scholar
Chelazzi, L., Boffa Ballaran, T., Lepore, G.O., Bindi, L. and Bonazzi, P. (2013) High-pressure behaviour of synthetic weberite-type Mn
2+
2 Sb5+ 2 O7: an in situ single-crystal X-ray study. Solid State Sciences, 21, 85–90.CrossRefGoogle Scholar
Della Giusta, A. and Ottonello, G. (1993) Energy and long-range disorder in simple spinels. Physics and Chemistry of Minerals, 20, 228–241.CrossRefGoogle Scholar
Dunn, P.J., Peacor, D.R., Criddle, A.J. and Stanley, C.J. (1988) Filipstadite, a new Mn-Fe3+-Sb derivative of spinel, from Lå ngban, Sweden. American Mineralogist, 73, 413–419.Google Scholar
Fujino, K. (1974) Cation distribution and local variation of site symmetry in solid solution series, Fe3O4-Fe2TiO4. Mineralogical Journal, 7, 472–488.CrossRefGoogle Scholar
Hålenius, U., Bosi, F. and Skogby, H. (2011) A first record of strong structural relaxation of TO4 tetrahedra in a spinel solid solution. American Mineralogist, 96, 617–622.CrossRefGoogle Scholar
Hastings, J.M. and Corliss, L.M. (1956) Neutron diffraction study of manganese ferrite. Physical Review, 104, 328–331.CrossRefGoogle Scholar
Holtstam, D. (1993) A second occurrence of filipstadite in Värmland, Sweden. Geologiska Föreningens i Stockholm Förhandlingar, 115, 239–240.CrossRefGoogle Scholar
Holtstam, D. and Larsson, A.K. (2000) Tegengrenite, a new, rhombohedral spinel-related Sb mineral from the Jakobsberg Fe-Mn deposit, Värmland, Sweden. American Mineralogist, 85, 1315–1320.CrossRefGoogle Scholar
Jarosch, D. (1987) Crystal structure refinement and reflectance measurements of hausmannite, Mn3O4. Mineralogy and Petrology, 37, 15–23.CrossRefGoogle Scholar
Keer, H.V., Bodas, M.G., Bhaduri, A. and Biswas, A.B. (1974) Electrical and magnetic properties of the MgMn2O4-MgAl2O4 system. Journal of Physics D: Applied Physics, 7, 2058–2062.CrossRefGoogle Scholar
Kim, J.G., Seo, J.W., Cheon, J. and Kim, Y.J. (2009) Rietveld analysis of nano-crystalline MnFe2O4 with electron powder diffraction. Bulletin of Korean Chemical Society, 30, 183–187.Google Scholar
Lavina, B., Salviulo, G. and Della Giusta, A. (2002) Cation distribution and structure modelling of spinel solid solutions. Physics and Chemistry of Minerals, 29, 10–18.CrossRefGoogle Scholar
Lavina, B., Reznitskii, L.Z. and Bosi, F. (2003) Crystal chemistry of some Mg, Cr, V normal spinels from Sludyanka (Lake Baykal, Russia): the influence of V3+ on structural stability. Physics and Chemistry of Minerals, 30, 599–605.CrossRefGoogle Scholar
Lucchesi, S., Russo, U. and Della Giusta, A. (1997) Crystal chemistry and cation distribution in some Mn-rich natural and synthetic spinels. European Journal of Mineralogy, 9, 31–42.CrossRefGoogle Scholar
Malavasi, L., Ghigna, P., Chiodelli, G., Maggi, G. and Flor, G. (2002) Structural and transport properties of Mg1-xMnxMn2O4+d. Journal of Solid State Chemistry, 166, 171–176.CrossRefGoogle Scholar
Morrish, A.H. and Clark, P.E. (1975) High-field Mössbauer study of Mn-Zn ferrites. Physical Review B, 11, 278–286.CrossRefGoogle Scholar
Navrotsky, A. and Kleppa, O.J. (1967) The thermodynamics of cation distribution in simple spinels. Journal of Inorganic and Nuclear Chemistry, 29, 2701–2714.CrossRefGoogle Scholar
O’Neill, H.St.C. and Navrotsky, A. (1983) Simple spinels: crystallographic parameters, cation radii, lattice energies and cation distributions. American Mineralogist, 68, 181–194.Google Scholar
Oxford Diffraction (2006). CrysAlis RED (Version 1.171.31.2) and ABSPACK in CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, UK.Google Scholar
Preudhomme, J., Tarte, P., Kenens, K., Grandjean, F. and Gerard, A. (1980) Studies of spinels. VIII. Synthesis and structural study of new antimonates MII 5MIII 3SbO12 by X-ray diffraction and Mössbauer spectroscopy. Académie Royale de Belgique, Bulletin de la Classe des Sciences, 66, 776–791.Google Scholar
Radhakrishnan, N.K. and Biswas, A.B. (1975) Cation distribution in the tetragonal spinel MgMn2O4. Zeitschrift für Kristallographie, 142, 121–126.Google Scholar
Radhakrishnan, N.K. and Biswas, A.B. (1976) A neutron diffraction study of the cation migration in MgMn2O4. Physica Status Solid, A37, 719–722.CrossRefGoogle Scholar
Robinson, K., Gibbs, G.V. and Ribbe, P.H. (1971) Quadratic elongation; a quantitative measure of distortion in coordination polyhedra. Science, 172, 567–570.CrossRefGoogle ScholarPubMed
Sawatzky, G.A., van der Wonde, F. and Morrish, A.H. (1967) Note on cation distribution of MnFe2O4
. Physics Letters, A25, 147–148.CrossRefGoogle Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751–767.CrossRefGoogle Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.CrossRefGoogle Scholar
Tarte, P. and Preudhomme, J. (1979) Studies of spinels. VI. Antimonates MII 4MIIISbVO8, a new, large family of spinels presenting order-disorder transitions. Journal of Solid State Chemistry, 29, 273–284.CrossRefGoogle Scholar
Tarte, P. and Rulmont, A. (1988) Factors determining the cation distribution in spinels: the case of spinels containing several high-valency cations. Journal of Materials Science Letters, 7, 551–554.CrossRefGoogle Scholar
Urusov, S.V. (1983) Interaction of cations on octahedral and tetrahedral sites in simple spinels. Physics and Chemistry of Minerals, 9, 1–5.CrossRefGoogle Scholar
Wechsler, B.A., Lindsley, D.H. and Prewitt, C.T. (1984) Crystal structure and cation distribution in titanomagnetites (Fe3-xTixO4). American Mineralogist, 69, 754–770.Google Scholar
Wilson, A.J.C. and Prince, E. (Editors) (1999) International Tables for X-ray Crystallography, Volume C: Mathematical, Physical and Chemical Tables (2nd Edition). Kluwer Academic, Dordrecht, The Netherlands. Zanazzi, P.F., Chelazzi, L., Bonazzi, P. and Bindi, L. (2009) High-pressure structural behavior of ingersonite, Ca3Mn
2+
Sb5+ 4 O14: an in situ single-crystal X-ray study. American Mineralogist, 94, 352–358.Google Scholar
Bonazzi and Bindi supplementary material
Structure factors
File
57.7 KB