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The crystal structure of charmarite – the first case of a 11 × 11 Å superstructure mesh in layered double hydroxides

Published online by Cambridge University Press:  08 March 2024

Elena S. Zhitova Open the ORCID record for Elena S. Zhitova [Opens in a new window] ,
Andrey A. Zolotarev ,
Anatoly V. Kasatkin Open the ORCID record for Anatoly V. Kasatkin [Opens in a new window] ,
Rezeda M. Sheveleva Open the ORCID record for Rezeda M. Sheveleva [Opens in a new window] ,
Sergey V. Krivovichev ,
Igor V. Pekov  and
Vladimir N. Bocharov
Elena S. Zhitova*
Affiliation:
Institute of Volcanology and Seismology, Russian Academy of Sciences, Bulvar Piipa 9, 683006 Petropavlovsk-Kamchatsky, Russia
Andrey A. Zolotarev
Affiliation:
Institute of Volcanology and Seismology, Russian Academy of Sciences, Bulvar Piipa 9, 683006 Petropavlovsk-Kamchatsky, Russia St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
Anatoly V. Kasatkin
Affiliation:
Fersman Mineralogical Museum, Russian Academy of Science, Leninskiy Prospect 18-2, 119071 Moscow, Russia
Rezeda M. Sheveleva
Affiliation:
Institute of Volcanology and Seismology, Russian Academy of Sciences, Bulvar Piipa 9, 683006 Petropavlovsk-Kamchatsky, Russia St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
Sergey V. Krivovichev
Affiliation:
St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Nanomaterials Research Centre, Kola Science Centre, Russian Academy of Sciences, Fersman Street 14, 184209 Apatity, Russia
Igor V. Pekov
Affiliation:
Faculty of Geology, Moscow State University, Leninskie Gory 1, 119991 Moscow, Russia
Vladimir N. Bocharov
Affiliation:
St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
*
Corresponding author: Elena Zhitova; Email: zhitova_es@mail.ru
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Abstract

Charmarite, Mn4Al2(OH)12CO3⋅3H2O, is a hydrotalcite supergroup member (or layered double hydroxide, LDH) with a previously unknown crystal structure and a Mn2+-analogue of quintinite (commonly erroneously reported as ‘2:1 hydrotalcite’). The single-crystal X-ray diffraction (XRD) data were obtained from the specimen from Mont Saint-Hilaire, Québec, Canada and are best processed in the space group P$\bar{3}$, a = 10.9630(4), c = 15.0732(5) Å and V = 1568.89(12) Å3. The crystal structure has been solved by direct methods and refined to R1 = 0.0750 for 3801 unique reflections with Fo > 2σ(Fo). The charmarite structure has long-range periodicity in the xy plane due to $2\sqrt 3$a’ × $2\sqrt 3$a’ scheme (or 11 × 11 Å) determined for LDHs for the first time (where a’ is a subcell parameter ≈ 3.2 Å). This periodicity is produced by the combination of two superstructures formed by: (1) Mn2+ and Al3+ ordering in the metal-hydroxide layers [Mn4Al2(OH)12]2+ according to the $\sqrt 3$a’ × $\sqrt 3$a’ pattern and (2) the (CO3)2– ordering according to the 2a’ × 2a’ pattern in the [CO3(H2O)3]2– interlayer sheet in order to avoid close contacts between adjacent carbonate groups. The $2\sqrt 3$a’ × $2\sqrt 3$a’ superstructure is an example of the adaptability of the components of the interlayer space to the charge distribution of the metal-hydroxyl layers. The Mn2+ and Al3+ cations have a large difference in size, which apparently leads to the considerable degree of their order as di- and trivalent cations resulting in a higher degree of statistical order of the interlayer components. Both powder and single-crystal XRD data show that the samples studied belong to the hexagonal branch of two-layer polytypes (2T or 2H) with d00n ≈ 7.57 Å. The chemical composition of the samples studied is close to the ideal formula. The Raman spectrum of charmarite is reported and the band assignment is provided.

Keywords

charmaritequintinitehydrotalcitelayered double hydroxidenatural LDHcrystal structureMont Saint-Hilaire alkaline complex
Type
Article
Information
Mineralogical Magazine , First View , pp. 1 - 11
Copyright
Copyright © The Author(s), 2024. Published by Cambridge University Press on behalf of The Mineralogical Society of the United Kingdom and Ireland

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Footnotes

Associate Editor: G. Diego Gatta

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