Licensed Unlicensed Requires Authentication Published online by De Gruyter March 21, 2022

An unusual member of the solid solution series between cristobalite and potassium ferrate(III) obtained from hydroflux

Ralf Albrecht and Michael Ruck
From the journal Zeitschrift für Naturforschung B
https://doi.org/10.1515/znb-2022-0016

Abstract

Dark octahedral crystals of K1−x[Fe1−xSi x O2] with x ≈ 0.2 were synthesized under ultra-alkaline conditions in a KOH hydroflux at 200 °C. The compound is a member of the solid solution series between SiO2 and K[FeO2]. Due to its SiO2 content, K0.8[Fe0.8Si0.2O2] is much less sensitive to moisture than K[FeO2]. The crystal structure is a stuffed cristobalite with a charged framework of vertex-sharing [MO4/2] tetrahedra (M = Fe3+, Si4+) and potassium counter ions in the large voids of the framework. It has the pseudo-symmetry and metrics of the cubic space group F d 3 ‾ m , but adopts the tetragonal space group I41md with four formula units in the cell. Unlike other tectosilicates of this type, the [MO4/2]− tetrahedra are not regular but distorted to disphenoids. The O atom can be modeled by a huge disk-shaped ellipsoid or, better, by split atom positions forming a six-membered ring with a diameter of 1.1 Å. The M–O distances range from 1.66(2) to 1.96(2) Å, the M–O–M angles are 135(2)°, 137(1)°, and 151(1)°.

Keywords: cristobalite; crystal structure; hydroflux; oxoferrates(III); pseudosymmetry; twin crystals

Dedicated to Professor Martin Lerch on the Occasion of his 60th Birthday.

Corresponding author: Michael Ruck, Fakultät Chemie und Lebensmittelchemie, Technische Universität Dresden, 01062 Dresden, Germany; and Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Straße 40, 01187 Dresden, Germany, E-mail:

Funding source: Deutsche Forschungsgemeinschaft

Award Identifier / Grant number: 438795198

Acknowledgment

We acknowledge technical support by M. Münch (TU Dresden).

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was financially supported by the Deutsche Forschungsgemeinschaft (project-id: 438795198).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/znb-2022-0016).

Received: 2022-02-24
Accepted: 2022-03-04
Published Online: 2022-03-21

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From the journal
Zeitschrift für Naturforschung B
Zeitschrift für Naturforschung B

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