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The crystal structures of kidwellite and ‘laubmannite’, two complex fibrous iron phosphates

Published online by Cambridge University Press:  05 July 2018

U. Kolitsch
U. Kolitsch*
Affiliation:
Institut für Mineralogie und Kristallographie, Universität Wien, Geozentrum, Althanstrasse 14, A-1090 Wien, Austria
*
*E-mail: [email protected]
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Abstract

The previously unknown, complex crystal structures of two fibrous ferric iron phosphate minerals have been solved using single-crystal X-ray diffraction data. The structure of a slightly arsenatian kidwellite has been refined in space group P2/c (a = 20.117(4), b = 5.185(1), c = 13.978(3)Å, β = 107.07(3)°, V = 1393.8(5)Å3, Z = 2) to R1 = 5.21%; a revision of both space group symmetry and chemical formula is proposed. The idealized formula is Na(Fe3+,M)9+x(OH)11(H2O)3(PO4)6, where M = Fe3+, Cu2+ or other metal cation, and x ≈ 0.3. The structure of a slightly arsenatian ‘laubmannite’ (as defined by Moore, 1970) has been refined in space group Pbcm (a = 5.172(1), b = 13.999(3), c = 31.083(6)Å, V = 2250.5(8)Å3, Z = 4) to R1 = 3.14%. The revised, idealized formula is (Fe3+,Fe2+,M)8+x(OH,H2O)9(-H2O)2(PO4)5, where M = Fe3+, Cu2+ or other metal cation, and x ≈ 0.1. The framework structures of both minerals are similar. Dominant building units are dimers composed of face- and edge-sharing FeO6 octahedra. Whereas kidwellite contains an additional trimer built of three corner-sharing FeO6 octahedra, ‘laubmannite’ instead contains a dimer built of two corner-sharing FeO6 octahedra. Kidwellite contains only trivalent iron, while one of the Fe sites in ‘laubmannite’ is occupied by a mixture of Fe3+ and Fe2+ in a 1:1 ratio. In both structures, the FeO6-based building units are linked via corners to PO4 tetrahedra; the M sites are located in narrow channels and have very low occupancies (~2 to 7%) and strongly distorted [6]- or [5+1]-coordinations. Close structural relations between kidwellite and ‘laubmannite’, and other fibrous iron phosphates explain observations of epitaxial intergrowths of them.

Keywords

kidwellitelaubmannitecrystal structurecrystal chemistryfibrous iron phosphates
Type
Research Article
Information
Mineralogical Magazine , Volume 68 , Issue 1 , February 2004 , pp. 147 - 165
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2004

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