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The crystal structure of camerolaite and structural variation in the cyanotrichite family of merotypes

Published online by Cambridge University Press:  05 July 2018

S. J. Mills ,
A. G. Christy ,
C. Schnyder ,
G. Favreau  and
J. R. Price
S. J. Mills*
Affiliation:
Geosciences, Museum Victoria, GPO Box 666, Melbourne, Victoria 3001, Australia
A. G. Christy
Affiliation:
Centre for Advanced Microscopy, Australian National University, Canberra, ACT 0200, Australia
C. Schnyder
Affiliation:
Département de minéralogie et de pétrographie, Muséum d’histoire naturelle, 1 rte de Malagnou, Case postale 6434, CH - 1211 Gene`ve 6, Switzerland
G. Favreau
Affiliation:
421 Avenue Jean Monnet, 13090 Aix-en-Provence, France
J. R. Price
Affiliation:
Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168, Australia
*
* E-mail: smills@museum.vic.gov.au
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Abstract

We present Raman data for camerolaite, cyanotrichite and carbonatecyanotrichite, and using synchrotron single-crystal X-ray diffraction have solved the structure of camerolaite from the Tistoulet Mine, Padern, Aude Department, France. Camerolaite crystallizes in space group P1 with the unit-cell parameters: a = 6.3310(13) Å, b = 2.9130(6) Å, c = 10.727(2) Å, α = 93.77(3)°, β = 96.34(3)°, γ =79.03(3)º, V = 192.82(7) Å3 and Z = ⅓, with respect to the ideal formula from the refinement, Cu6Al3(OH)18(H2O)2[Sb(OH)6](SO4). The crystal structure was solved to R1 = 0.0890 for all 1875 observed reflections [Fo > 4σFo] and 0.0946 for all 2019 unique reflections. The P cell has been transformed into a C-centred cell that aids comparison with that of the structurally related khaidarkanite by aC = 2aP – bP, giving parameters a = 12.441(3), b = 2.9130(6), c = 10.727(2) Å, α = 93.77(3), β = 95.57(3), γ = 92.32(3)º and Z = ⅔ in C1. Edge-sharing octahedral ribbons Cu2Al(O,OH,H2O)8 form hydrogen-bonded layers || (001), as in khaidarkanite. The partially occupied interlayer Sb and S sites of the average structure are in octahedral and tetrahedral coordination by oxygen, respectively. They cannot be occupied simultaneously, which leads to regular alternation of [Sb(OH)6]– and SO42– groups in rods || y, resulting in local tripling of the periodicity along y for the Sb(OH)6–SO4 rods. Thus, camerolaite has a ‘host–guest’ structure in which an invariant host module (layers of Cu–Al ribbons) has embedded rod-like guest modules with a longer periodicity. Coupling between the phases of these rods is only short-range, resulting in diffuse X-ray scattering rather than sharp superstructure reflections. Similar disorder is known for parnauite, and is deduced for other members of the cyanotrichite group (cyanotrichite, carbonatecyanotrichite and khaidarkanite). Group members all share the Cu–Al ribbon module but have interlayer rods of different compositions and topologies; thus, they form a merotypic family. The low symmetry of the camerolaite average structure suggests other possibilities for structure variation in the group, which are discussed.

Keywords

camerolaitecyanotrichitecarbonatecyanotrichitekhaidarkanitemerotypesuperstructurecrystal structuresynchrotron
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 7 , December 2014 , pp. 1527 - 1552
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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