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

Author(s)
Uwe Kolitsch
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(l), c - 13.978(3) A°, ß = 107.07(3)°, V = 1393.8(5) A°3, Z = 2) to RI = 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(l), b = 13.999(3), c = 31.083(6) A°, V = 2250.5(8) A°3, Z = 4) to RI = 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. Œ 2004 The Mineralogical Society.

Organisation(s)
Department of Mineralogy and Crystallography
Journal
Mineralogical Magazine
Volume
68
Pages
147-165
No. of pages
19
ISSN
0026-461X
Publication date
2004
Peer reviewed
Yes
Austrian Fields of Science 2012
1051 Geology, Mineralogy
Portal url
https://ucrisportal.univie.ac.at/en/publications/ac4e5d4d-a52d-4296-a849-617998c35be3