Startseite Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)
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Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)

  • Michael Langenmaier , Tobias Rackl , Dirk Johrendt und Caroline Röhr EMAIL logo
Veröffentlicht/Copyright: 11. September 2018
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Zeitschrift für Naturforschung B
Aus der Zeitschrift Zeitschrift für Naturforschung B Band 73 Heft 11

Abstract

The six isotypic alkali ortho chalcogenido manganates A6[MnIIQ4] (A=Rb, Cs; Q=S, Se, Te) were synthesized – in most cases in pure phase – from stoichiometric mixtures of the manganese monochalcogenides MnQ, the elemental chalcogens and Rb2S/Cs2S2 (sulfido salts) or the pure alkali elements (selenido and tellurido salts) as alkali sources at maximum temperatures between 650 and 800°C. Their hexagonal crystal structures were refined by means of X-ray single crystal data (space group P63mc, Na6ZnO4-type structure, Z=2; A/Q: Rb/S: a=1019.34(2), c=792.560(10) pm, R1=0.0166; Rb/Se: a=1055.74(2), c=821.14(2) pm, R1=0.0275; Rb/Te: a=1126.68(2), c=860.54(2) pm, R1=0.0152; Cs/S: a=1056.68(2), c=831.22(2) pm, R1=0.0168; Cs/Se: a=1096.04(3), c=858.13(2) pm, R1=0.0194; and Cs/Te: a=1167.72(3), c=896.95(2) pm, R1=0.0140). The chiral structures contain isolated C3 symmetric, but very close to ideal tetrahedral, ortho manganate(II) anions [MnIIQ4]6− with Mn–Q distances of 248.7–250.7 (Q=S), 260.7–263.0 (Q=Se) and 280.0–282.4 pm (Q=Te). The chalcogenide ions form a hexagonal closed packing with slightly puckered 36 nets, in which the A(2) cations occupy 3/4 of the octahedral interstices, whereas Mn takes 1/8 and A(1) 3/8 of the tetrahedral voids. Magnetic measurements on the three Cs compounds showed Curie-Weiss behavior down to a temperature of 1.9 K, with magnetic moments significantly reduced with respect to the expected spin-only value of a d5 ion. The electronic band structures of the four salts (Na/Rb)6Mn(S/Te)4, which were calculated within the GGA+U approach, allow a comparison of the chemical bonding characteristics and the magnetic properties within the alkali cation and the chalcogenido ligand series.

Keywords: cesium; chalcogenido manganates; crystal structure; magnetic properties; manganese; rubidium

Dedicated to: Professor Bernt Krebs on the occasion his 80th birthday.

Acknowledgments

We would like to thank the Deutsche Forschungsgemeinschaft for financial support.

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Received: 2018-07-01
Accepted: 2018-07-21
Published Online: 2018-09-11
Published in Print: 2018-11-27

©2018 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. In this Issue
  3. Preface
  4. Congratulations to Bernt Krebs
  5. Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin
  6. Cationic tri(ferrocenecarbonitrile)silver(I)
  7. Ternary indides RE3T2In4 (RE=Dy–Tm; T=Pd, Ir)
  8. Mixing SbIII and GeIV occupancy in the polyoxovanadate {V14E8} archetype
  9. Biolabeling with cobaltocinium tags
  10. Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes in solution and in the solid state
  11. Hydrothermal synthesis and structure determination of a new calcium iron ruthenium hydrogarnet
  12. 7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination
  13. Structural and magnetic investigations of the pseudo-ternary RE2TAl3 series (RE=Sc, Y, La–Nd, Sm, Gd–Lu; T=Ru, Rh, Ir) – size dependent formation of two different structure types
  14. A new stacking variant of Na2Pt(OH)6
  15. Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)
  16. Studie über den Einfluss des Fluorierungsgrades an einem tetradentaten C^N*N^C-Luminophor auf die photophysikalischen Eigenschaften seiner Platin(II)-Komplexe und deren Aggregation
  17. Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl
  18. Preface
  19. Congratulations to Werner Uhl
  20. The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm)
  21. 1H-[1,2,4]Triazolo[4,3-a]pyridin-4-ium and 3H-[1,2,4]triazolo[4,3-a]quinolin-10-ium derivatives as new intercalating agents for DNA
  22. Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion
  23. A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum
  24. (NH4)InB8O14 – a high-pressure borate combining BO3 groups with corner- and edge-sharing BO4 tetrahedra
  25. Two series of rare earth metal-rich ternary aluminium transition metallides – RE6Co2Al (RE=Sc, Y, Nd, Sm, Gd–Tm, Lu) and RE6Ni2.25Al0.75 (RE=Y, Gd–Tm, Lu)
  26. Alkylaluminum, -gallium, -magnesium, and -zinc monophenolates with bulky substituents
  27. Note
  28. Synthesis and crystal structure of the copper silylamide cluster compound [Cu9{MesSi(NPh)3}2 (PhCO2)3]
https://doi.org/10.1515/znb-2018-0138
Schlagwörter für diesen Artikel
cesium; chalcogenido manganates; crystal structure; magnetic properties; manganese; rubidium

Artikel in diesem Heft

  1. Frontmatter
  2. In this Issue
  3. Preface
  4. Congratulations to Bernt Krebs
  5. Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin
  6. Cationic tri(ferrocenecarbonitrile)silver(I)
  7. Ternary indides RE3T2In4 (RE=Dy–Tm; T=Pd, Ir)
  8. Mixing SbIII and GeIV occupancy in the polyoxovanadate {V14E8} archetype
  9. Biolabeling with cobaltocinium tags
  10. Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes in solution and in the solid state
  11. Hydrothermal synthesis and structure determination of a new calcium iron ruthenium hydrogarnet
  12. 7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination
  13. Structural and magnetic investigations of the pseudo-ternary RE2TAl3 series (RE=Sc, Y, La–Nd, Sm, Gd–Lu; T=Ru, Rh, Ir) – size dependent formation of two different structure types
  14. A new stacking variant of Na2Pt(OH)6
  15. Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)
  16. Studie über den Einfluss des Fluorierungsgrades an einem tetradentaten C^N*N^C-Luminophor auf die photophysikalischen Eigenschaften seiner Platin(II)-Komplexe und deren Aggregation
  17. Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl
  18. Preface
  19. Congratulations to Werner Uhl
  20. The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm)
  21. 1H-[1,2,4]Triazolo[4,3-a]pyridin-4-ium and 3H-[1,2,4]triazolo[4,3-a]quinolin-10-ium derivatives as new intercalating agents for DNA
  22. Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion
  23. A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum
  24. (NH4)InB8O14 – a high-pressure borate combining BO3 groups with corner- and edge-sharing BO4 tetrahedra
  25. Two series of rare earth metal-rich ternary aluminium transition metallides – RE6Co2Al (RE=Sc, Y, Nd, Sm, Gd–Tm, Lu) and RE6Ni2.25Al0.75 (RE=Y, Gd–Tm, Lu)
  26. Alkylaluminum, -gallium, -magnesium, and -zinc monophenolates with bulky substituents
  27. Note
  28. Synthesis and crystal structure of the copper silylamide cluster compound [Cu9{MesSi(NPh)3}2 (PhCO2)3]
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