Startseite New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)
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New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)

  • Michael Schwarz , Pirmin Stüble , Katharina Köhler und Caroline Röhr EMAIL logo
Veröffentlicht/Copyright: 4. September 2020
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Zeitschrift für Kristallographie - Crystalline Materials
Aus der Zeitschrift Zeitschrift für Kristallographie - Crystalline Materials Band 235 Heft 8-9

Abstract

Four new mixed-valent chain alkali metal (A) sulfido ferrates of the general structure family A1+xFexIIFe1−xIIIS2 were synthesized in the form of tiny green-metallic needles from nearly stoichiometric melts reacting elemental potassium with natural pyrite (A = K) or previously prepared Rb2S/Cs2S2 with elemental iron and sulfur (A = Rb/Cs). The crystal structures of the compounds were determined by means of single crystal X-ray diffraction: In the (3+1)D modulated structure of K7.15[FeS2]4 (space group Ccce(00σ3)0s0, a = 1363.87(5), b = 2487.23(13), c = 583.47(3) pm, q = 0,0,0.444, R1 = 0.055/0.148, x = 0.787), a position modulation of the two crystallographically different undulated [FeS4/2]∞1 tetrahedra chains and the surrounding K cations is associated with an occupation modulation of one of the three potassium sites. In the case of the new monoclinic rubidium ferrate Rb4[FeS2]3 (x = 13; space group P21/c, a = 1640.49(12), b = 1191.94(9), c = 743.33(6) pm, β = 94.759(4)°, Z = 4, R1 = 0.1184) the undulation of the tetrahedra chain is commensurate, the repetition unit consists of six tetrahedra. In the second new Rb ferrate, Rb7[FeS2]5 (x = 0.4; monoclinic, space group C2/c, K7[FeS2]5-type; a = 2833.9(2), b = 1197.36(9), c = 744.63(6) pm, β = 103.233(4)°, Z = 4, R1 = 0.1474) and its isotypic mixed Rb/Cs-analog Rb3.6Cs3.4[FeS2]5 (a = 2843.57(5), b = 1226.47(2), c = 759.890(10) pm, β = 103.7170(9)°, R1 = 0.0376) the chain buckling leads to a further increased repetition unit of 10 tetrahedra. For all mixed-valent ferrates, the Fe–S bond lengths continuously increase with the amount (x) of Fe(II). The buckling of the chains is controlled through the local coordination of the S atoms by the variable number of A cations of different sizes.

Keywords: alkali metals; (3+1)D modulated structure; sulfido ferrates; tetrahedra chains

Dedicated to Professor Dr. Ulrich Müller on the occasion of his 80th birthday.

Corresponding author: Caroline Röhr, Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstrasse 21, D-79104Freiburg, Germany, E-mail:

Funding source: Deutsche Forschungsgemeinschaft

Acknowledgments

We would like to thank the Deutsche Forschungsgemeinschaft for financial support and Miriam Haas for contributing in the preparative work.

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

  2. Research funding: Deutsche Forschungsgemeinschaft

  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/zkri-2020-0023).

Received: 2020-02-29
Accepted: 2020-04-03
Published Online: 2020-09-04
Published in Print: 2020-09-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. In this issue
  3. Original papers
  4. Ulrich Müller zum 80. Geburtstag gewidmet
  5. Laboratory synthesis and characterization of Knasibfite K3Na4[SiF6]3[BF4] and the homologous Ge compound K3Na4[GeF6]3[BF4]
  6. The crystal structures of α-Rb7Sb3Br16, α- and β-Tl7Bi3Br16 and their relationship to close packings of spheres
  7. Beryllium triflates: synthesis and structure of BeL2(OTf)2 (L=H2O, THF, nBu2O)
  8. Synthesis and crystal structures of two layered Cu(I) and Ag(I) iodidometalates
  9. New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)
  10. Structure solution of incommensurately modulated La6MnSb15
  11. Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited
  12. On tungstates of divalent cations (III) – Pb5O2[WO6]
  13. Hydrogen order in hydrides of Laves phases
  14. High-pressure synthesis of SmGe3
  15. The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) Na2RE3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu)
  16. Structural diversity of salts of terpyridine derivatives with europium(III) located in both, cation and anion, in comparison to molecular complexes
  17. Elucidating structure–property relationships in imidazolium-based halide ionic liquids: crystal structures and thermal behavior
  18. Syntheses and crystal structures of the manganese hydroxide halides Mn5(OH)6Cl4, Mn5(OH)7I3, and Mn7(OH)10I4
  19. Site-preferential copper substitution for silicon leads to Cu-chains in the new ternary silicide Ir4−xCuSi2
  20. Syntheses and crystal structures of solvate complexes of alkaline earth and lanthanoid metal iodides with N,N-dimethylformamide
https://doi.org/10.1515/zkri-2020-0023
Schlagwörter für diesen Artikel
alkali metals; (3+1)D modulated structure; sulfido ferrates; tetrahedra chains

Artikel in diesem Heft

  1. Frontmatter
  2. In this issue
  3. Original papers
  4. Ulrich Müller zum 80. Geburtstag gewidmet
  5. Laboratory synthesis and characterization of Knasibfite K3Na4[SiF6]3[BF4] and the homologous Ge compound K3Na4[GeF6]3[BF4]
  6. The crystal structures of α-Rb7Sb3Br16, α- and β-Tl7Bi3Br16 and their relationship to close packings of spheres
  7. Beryllium triflates: synthesis and structure of BeL2(OTf)2 (L=H2O, THF, nBu2O)
  8. Synthesis and crystal structures of two layered Cu(I) and Ag(I) iodidometalates
  9. New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)
  10. Structure solution of incommensurately modulated La6MnSb15
  11. Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited
  12. On tungstates of divalent cations (III) – Pb5O2[WO6]
  13. Hydrogen order in hydrides of Laves phases
  14. High-pressure synthesis of SmGe3
  15. The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) Na2RE3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu)
  16. Structural diversity of salts of terpyridine derivatives with europium(III) located in both, cation and anion, in comparison to molecular complexes
  17. Elucidating structure–property relationships in imidazolium-based halide ionic liquids: crystal structures and thermal behavior
  18. Syntheses and crystal structures of the manganese hydroxide halides Mn5(OH)6Cl4, Mn5(OH)7I3, and Mn7(OH)10I4
  19. Site-preferential copper substitution for silicon leads to Cu-chains in the new ternary silicide Ir4−xCuSi2
  20. Syntheses and crystal structures of solvate complexes of alkaline earth and lanthanoid metal iodides with N,N-dimethylformamide
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