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Crystal and molecular structure and spectroscopic behavior of isotypic synthetic analogs of the oxalate minerals stepanovite and zhemchuzhnikovite

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Abstract

The crystal structure of synthetic stepanovite, Na[Mg(H2O)6][Fe(C2O4)3]·3H2O, and zhemchuzhnikovite, Na[Mg(H2O)6][Al0.55Fe0.45(C2O4)3]·3H2O, has been determined by single-crystal X-ray diffraction methods. The compounds are isotypic to each other and to the previously reported Na[Mg(H2O)6][M(C2O4)3]·3H2O (M: Cr, Al). They crystallize in the trigonal P3c1 space group with Z = 6 molecules per unit cell and (hexagonal axes) a = 17.0483(4), c = 12.4218(4) Å for the iron compound, and a = 16.8852(5), c = 12.5368(5) Å for the Al/Fe solid solution. Comparison of our crystallographic results with previous X-ray diffraction and chemical data of type stepanovite and zhemchuzhnikovite minerals provides compelling evidence that these natural materials possess the same crystal and molecular structure as their synthetic counterparts. It is shown that the originally reported unit cell for stepanovite represents a pronounced sub-cell and that the correct unit cell and space group are based on weak superstructure reflections. The infrared and Raman spectra of both synthetic analogs were also recorded and are briefly discussed.

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Acknowledgments

We would like to thank Dr. Takuya Echigo and Dr. Uwe Kolitsch for their thorough revisions that helped to improve our article. This work was supported by the Universidad Nacional de La Plata, by CONICET (PIP 1529) and by ANPCyT (PME06 2804 and PICT06 2315) of Argentina. OEP, GAE and AGB are research fellows of CONICET.

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Authors and Affiliations

  1. Departamento de Física, Facultad de Ciencias Exactas, Universidad Nacional de La Plata and Institute IFLP (CONICET, CCT-La Plata), 1900, La Plata, Argentina

    Oscar E. Piro & Gustavo A. Echeverría

  2. Centro de Química Inorgánica (CEQUINOR, CONICET/UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C. C. 962, 1900, La Plata, Argentina

    Ana C. González-Baró & Enrique J. Baran

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  1. Oscar E. Piro
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  2. Gustavo A. Echeverría
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  3. Ana C. González-Baró
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  4. Enrique J. Baran
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Correspondence to Enrique J. Baran.

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Piro, O.E., Echeverría, G.A., González-Baró, A.C. et al. Crystal and molecular structure and spectroscopic behavior of isotypic synthetic analogs of the oxalate minerals stepanovite and zhemchuzhnikovite. Phys Chem Minerals 43, 287–300 (2016). https://doi.org/10.1007/s00269-015-0793-2

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