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K3Na(RuO4)2 and Rb3Na(RuO4)2, two new ruthenates with glaserite structure

MPS-Authors
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Mogare,  K. M.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Klein,  W.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Peters,  E. M.
Former Scientific Facilities, Max Planck Institute for Solid State Research, Max Planck Society;

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Jansen,  M.
Abteilung Jansen, Former Departments, Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Mogare, K. M., Klein, W., Peters, E. M., & Jansen, M. (2006). K3Na(RuO4)2 and Rb3Na(RuO4)2, two new ruthenates with glaserite structure. Solid State Sciences, 8(5), 500-507.


Cite as: https://hdl.handle.net/21.11116/0000-000F-02BB-C
Abstract
K3Na(RuO4)(2) and Rb3Na(RuO4)(2) were prepared by solid state reactions
of RuO2, Na2O2, and RbO2 or KO2, respectively, at 873 K under oxygen
pressure. K3Na(RuO4)(2) performs a structural transition at 467 K and
transforms from a monoclinic form at room temperature (C2/c, a =
10.323(8), b = 5.989(4), c = 15.278(7) angstrom, beta =
90.49(5)degrees, Z = 4, single crystal data, 1231 independent
reflections, R-1 = 4.27%, wR(2) = 8.95%) into a tiigonal high
temperature modification (Rietveld refinement from X-ray powder data,
P(3) over bar m1, a = 6.0164(1), c = 7.6855(2) angstrom, Z = 1, 4053
data points, R-p = 6.63%, wR(p) = 8.65%) which is isotypic to
glaserite, K3Na(SO4)(2). The rubidium analogue, Rb3Na(RuO4)(2), does
not show a phase transition down to 100 K. According to the structure
determination from single crystal X-ray data, Rb3Na(RuO4)(2) (P(3) over
bar m1, a = 6.0784(3), c = 7.8994(6) angstrom, Z = 1, 281 independent
reflections, R-1 = 2.35%, wR(2) = 5.51%) is isotypic to glaserite and
the HT phase of K3Na(RuO4)(2). The magnetic measurements confirm the
presence of hexavalent ruthenium displaying paramagnetic behaviour
along with antiferromagnetic interactions at lower temperatures. The
Raman measurements also confirm the tetrahedral coordination of
ruthenium with oxygen. (C) 2006 Elsevier SAS. All rights reserved.