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Zeitschrift für Kristallographie - Crystalline Materials

Editor-in-Chief: Pöttgen, Rainer

Ed. by Antipov, Evgeny / Bismayer, Ulrich / Boldyreva, Elena V. / Huppertz, Hubert / Petrícek, Václav / Tiekink, E. R. T.

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Clinotobermorite, Ca5[Si3O8(OH)]2 · 4 H2O \p=n-\ Ca5[Si6O17] · 5 H2O, a natural C\p=n-\S\p=n-\H(I) type cement mineral: determination of the substructure

C. Hoffmann / T. Armbruster
Published Online: 2010-07-28 | DOI: https://doi.org/10.1524/zkri.1997.212.12.864

Abstract

The substructure of natural clinotobermorite Ca5[Si3O8(OH)]2 · 4 H2O \p=n-\ Ca5[Si6Ol7] · 5 H2O from the Wessels mine, Kalahari manganese field, South Africa, was determined from single-crystal X-ray data. The diffraction pattern (monoclinic: a = 11.19 Å, b = 7.29 Å, c = 22.46 Å, β = 96.97°) is characterised by rather diffuse reflections of the type hkl with h, k = 2n + 1. The substructure (space group I2/m, Z = 1, a/2 = 5.593(6) Å, b/2 = 3.645(4) Å, c = 22.46(3) Å, β = 96.97(2)°) was solved from the sharp Bragg reflections (hkl, with h, k = 2n) and refined on the basis of 1877 unique reflections to R(F) = 6.7%.

The structure of clinotobermorite is closely related to the one of so called 11 Å tobermorite Ca5Si6O16(OH)2 · 2 H2O (pseudo-orthorhombic, a = 11.17 Å, b = 7.38 Å, c = 22.6 Å). In both minerals layers parallel (001), formed by seven-fold co-ordinated Ca, are flanked on either side by wollastonite-like [Si3O9] single chains (ca. 7.3 Å periodicity along b) creating a sandwich-like assemblage. The short b/2 axis (3.645 Å) and the short a/2 axis (5.593 Å) of the subcell are caused by an overlay of two half-occupied single chains of tetrahedra with one shifted by b/2 against the other. In clinotobermorite the sandwich-like layers are stacked along c yielding an interlayer distance of 4.5 Å with a free aperture of 3.2 Å where additional Ca ions and H2O molecules connect the sandwich units. Clinotobermorite with 4–5 H2O represents a much denser structure than 11 Å tobermorite with only 2 H2O or 14 Å tobermorite with ca. 6 H2O (pseudo-orthorhombic, a = 11.17 Å, b = 7.38 Å, c = 27.94 Å). The substructure of clinotobermorite can be interpreted as either composed of ‘Dreiereinfachketten’ leading to the formula Ca5[Si3O8(OH)]2 · 4 H2O, or of ‘Dreierdoppelketten’ leading to the formula Ca5[Si6O17] · 5 H2O, or of a mixture of both variants.

The surface structure of clinotobermorite was studied by atomic force microscopy (AFM) where low magnifications reveal a complex layering or twinning parallel (001). High resolutions scans parallel (100) establish enhanced contrast fringes with a periodicity of ca. 10 Å interpreted as the repeat distance of the Ca polyhedral layers parallel to c.


Published Online: 2010-07-28

Published in Print: 1997-12-01


Citation Information: Zeitschrift für Kristallographie - Crystalline Materials. Volume 212, Issue 12, Pages 864–873, ISSN (Online) 2196-7105, ISSN (Print) 2194-4946, DOI: https://doi.org/10.1524/zkri.1997.212.12.864, July 2010

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