Home The HfFe2Si2 type silicides ScT2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy
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The HfFe2Si2 type silicides ScT2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy

  • Aylin Koldemir , Josef Maximilian Gerdes , Maximilian Kai Reimann , Michael Ryan Hansen EMAIL logo and Rainer Pöttgen EMAIL logo
Published/Copyright: December 19, 2023
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 239 Issue 1-2

Abstract

The silicides ScT2Si2 (T = Ru, Rh, Os) were synthesized by arc-melting of the elements and subsequent annealing in sealed silica ampoules. They crystallize with the rarely observed HfFe2Si2 type structure, space group Pbcm. The structures of ScRu2Si2 (a = 761.64(4), b = 730.70(6), c = 521.07(6) pm, wR = 0.0314, 633 F2 values, 31 variables) and ScOs2Si2 (a = 771.10(8), b = 736.68(7), c = 521.88(5) pm, wR = 0.0479, 623 F2 values, 31 variables) were refined from single crystal X-ray diffractometer data. The refinements showed small degrees of Ru/Si respectively Os/Si mixing on one 4c site, leading to the refined compositions ScRu1.96(1)Si2.04(1) and ScOs1.91(1)Si2.09(1). The monomeric building units in both structures are two slightly distorted, crystallographically independent RuSi5 respectively OsSi5 square pyramids, which are condensed via common edges. The resulting densely packed [Ru2Si2] and [Os2Si2] networks leave voids for the scandium atoms with coordination number 18: Sc@Si8Ru8Sc2 and Sc@Si8Os8Sc2. Temperature dependent magnetic susceptibility measurements of ScRu2Si2 and ScOs2Si2 indicate Pauli paramagnetism. Solid-state 29Si and 45Sc static and MAS NMR spectroscopy reveal significant Knight shifts and a strong influence of the T/Si mixing on the experimental NMR line shapes. A larger overall 29Si magnetic shift for ScRu2Si2 compared to ScOs2Si2, although with a negative sign for one of the 29Si resonances, suggests stronger paramagnetic effects for ScRu2Si2, in agreement with the magnetic susceptibility measurements.

Keywords: scandium; crystal structure; intermetallics; solid state NMR spectroscopy
Corresponding authors: Rainer Pöttgen, Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany, E-mail: ; and Michael Ryan Hansen, Institut für Physikalische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany, E-mail:

Acknowledgments

We thank Dipl.-Ing. J. Kösters for the intensity data collections.

  1. Research ethics: Not applicable.

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

  3. Competing interests: The authors declare no conflicts of interest regarding this article.

  4. Research funding: This research was funded by Universität Münster and Deutsche Forschungsgemeinschaft (INST 211/1034-1).

  5. Data availability: Data is available from the corresponding author on well-founded request.

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Received: 2023-10-24
Accepted: 2023-11-22
Published Online: 2023-12-19
Published in Print: 2024-01-29

© 2023 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Inorganic Crystal Structures (Original Paper)
  4. Ytterbium valence ordering in the low-temperature superstructure of Yb2Pd2Cd
  5. The HfFe2Si2 type silicides ScT2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy
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https://doi.org/10.1515/zkri-2023-0048
Keywords for this article
scandium; crystal structure; intermetallics; solid state NMR spectroscopy

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Inorganic Crystal Structures (Original Paper)
  4. Ytterbium valence ordering in the low-temperature superstructure of Yb2Pd2Cd
  5. The HfFe2Si2 type silicides ScT2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy
  6. Finding the ‘Goldilocks Zone’: cationic size and tilting of carbodiimide and cyanamide anions
  7. High-pressure/high-temperature synthesis of the first walstromite-analogue borate Tm2CrB3O9
  8. Organic and Metalorganic Crystal Structures (Original Paper)
  9. A doubly mononuclear cobalt(II) complex constructed with azide anions and a new coordination mode of the 2-(2-pyridylmethylamino) ethanesulfonic acid ligands: structure, conformation comparison and Hirshfeld surface analysis
  10. Crystal structures of а series of 1-substituted imidazol-4,5-dicarboxylic acids
  11. A bibliographic survey of the structural chemistry of the Group 13 dithiophosphates and dithiophosphinates
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