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Anhydrous alkali copper sulfates – a promising playground for new Cu2+ oxide complexes: new Rb-analogues of fumarolic minerals.

Published online by Cambridge University Press:  29 September 2021

Oleg I. Siidra Open the ORCID record for Oleg I. Siidra [Opens in a new window] ,
Diana O. Nekrasova ,
Dmitry O. Charkin ,
Anatoly N. Zaitsev ,
Artem S. Borisov ,
Marie Colmont ,
Olivier Mentré  and
Darya V. Spiridonova
Oleg I. Siidra*
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034St. Petersburg, Russia Kola Science Center, Russian Academy of Sciences, Apatity, 184200, Murmansk Region, Russia;
Diana O. Nekrasova
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034St. Petersburg, Russia Université Lille, CNRS, Centrale Lille, Université Artois, UMR 8181, Unité de Catalyse et Chimie du Solide, Lille, F-59000, France
Dmitry O. Charkin
Affiliation:
Department of Chemistry, Moscow State University, GSP-1, Moscow119991, Russia
Anatoly N. Zaitsev
Affiliation:
Department of Mineralogy, St. Petersburg State University, University Embankment 7/9, 199034St. Petersburg, Russia
Artem S. Borisov
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034St. Petersburg, Russia
Marie Colmont
Affiliation:
Université Lille, CNRS, Centrale Lille, Université Artois, UMR 8181, Unité de Catalyse et Chimie du Solide, Lille, F-59000, France
Olivier Mentré
Affiliation:
Université Lille, CNRS, Centrale Lille, Université Artois, UMR 8181, Unité de Catalyse et Chimie du Solide, Lille, F-59000, France
Darya V. Spiridonova
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034St. Petersburg, Russia
*
*Author for correspondence: Oleg I. Siidra, Email: o.siidra@spbu.ru
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Abstract

We report the crystal structures of eight new synthetic multinary Rb–Cu sulfates representing four new structure types: δ-Rb2Cu(SO4)2, γ-RbNaCu(SO4)2, γ-RbKCu(SO4)2, Rb2Cu2(SO4)3, Rb2Cu2(SO4)3(H2O), β-Rb2Cu(SO4)Cl2, β-Rb4Cu4O2(SO4)4⋅(Cu0.83Rb0.17Cl) and Rb2Cu5O(SO4)5. The determination of their crystal structures significantly expands the family of anhydrous copper sulfates. Some of the anhydrous rubidium copper sulfates obtained turned out to be isostructural to known compounds and minerals. Rb2Cu5O(SO4)5 is isostructural to cesiodymite, CsKCu5O(SO4)5 and cryptochalcite, K2Cu5O(SO4)5. Rb2Cu2(SO4)3 also shows an example of crystallisation in the already known structure type first observed for synthetic K2Cu2(SO4)3. ‘Hydrolangbeinite’, Rb2Cu2(SO4)3(H2O), was formed as a result of a minor hydration of the initial mixture of reagents.

The minerals and synthetic framework compounds of the A2Cu(SO4)2 series demonstrate a vivid example of morphotropism with the formation of structural types depending on the size of the cations residing in the cavities of the [Cu(SO4)2]2– open framework. To date, five types (α, β, γ, δ and ε) can be distinguished. We propose to call this series of compounds ‘saranchinaite-type’, as the stoichiometry A2Cu(SO4)2 was first encountered during the discovery and description of saranchinaite, Na2Cu(SO4)2.

The discovery of β-Rb2Cu(SO4)Cl2, a new monoclinic polymorph of chlorothionite, seems to be of particular interest considering the recently discovered interesting magnetic properties of synthetic K2Cu(SO4)X2 (X = Cl and Br) and Na2Cu(SO4)Cl2.

In these new structural architectures, a number of features have been revealed that were seldom observed previously. The first is the bidentate coordination of the sulfate tetrahedron via edge-sharing with the Cu2+-centred coordination polyhedron. Until recently, such coordination was known only for the chlorothionite structure. The second is formation of ‘high-coordinate’ CuO7 polyhedra. The structures of the new compounds suggest that such coordination is not in fact so uncommon, at least among anhydrous alkali copper sulfates. All of the described features clearly indicate the importance of further systematic studies of anhydrous copper-sulfate systems. Their exploration, particularly of the new copper-oxide substructures with new coordination environments, is highly likely to lead to new potentially interesting magnetic properties due to the unusual arrangements of magnetically active Cu2+ cations.

In addition to experimental details on the synthesis of rubidium analogues of anhydrous potassium and sodium sulfates, this work also provides an analysis and a brief review of the geochemistry of rubidium in volcanic environments.

Keywords

copperrubidiumsulfatesfumarolic mineralssolid state reactionsgas transport reactionscrystal structures
Type
Article
Information
Mineralogical Magazine , Volume 85 , Issue 6 , December 2021 , pp. 831 - 845
Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

Associate Editor: Daniel Atencio

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