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RE3Rh2Sn4 (RE = Y, Gd–Tm, Lu) – first stannides with Lu3Co2In4 type structure

  • Lars Schumacher , Simon Engelbert , Steffen Klenner , Samir F. Matar and Rainer Pöttgen EMAIL logo
Published/Copyright: February 25, 2022
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 237 Issue 1-3

Abstract

The stannides RE3Rh2Sn4 (RE = Y, Gd–Tm, Lu) were synthesized from the elements by arc-melting and subsequent annealing (1220 K for RE = Y, Gd–Tm and 1170 K for RE = Lu) in sealed silica ampoules for 11 days. X-ray powder diffraction studies confirm the hexagonal Lu3Co2In4 type structure, space group P 6 ‾ . The structure of Gd3Rh2Sn4 was refined from single crystal X-ray diffractometer data for a twinned crystal: a = 744.04(6), c = 409.23(4) pm, wR2 = 0.0288, 567 F2 values and 21 variables. The RE3Rh2Sn4 stannides derive from the well-known equiatomic stannides RERhSn (≍RE3Rh3Sn3) by Rh/Sn ordering within the RE6 trigonal prisms. The striking structural motif is the trigonal planar tin coordination of the Sn2 atoms with 288 pm Sn2–Sn1 distances. The Sn2 atoms carry substantially more negative charge than the Sn1 atoms. This is underlined by 119Sn isomer shifts of δ = 1.86(1) mm s−1 for Sn1 and δ = 2.26(1) mm s−1 for Sn2 detected in the Mössbauer spectrum of Lu3Rh2Sn4. From atoms in molecules (AIM) analysis of the charge density obtained with calculation based on density functional theory (DFT) for Y3Rh2Sn4, the charge transfer proceeds from yttrium towards more electronegative rhodium. Little departure from neutrality is observed for tin whose itinerant s-like states are little involved with the bonding. The site projected density of states (DOS) and the crystal orbital overlap population (COOP) plots further illustrate these observations and reveal major Y–Rh and Rh–Sn bonding, while Y–Sn bonding is weaker.

Keywords: COOP; DFT; Mössbauer spectroscopy; stannide; superstructure
Corresponding author: Rainer Pöttgen, Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany, E-mail:

Acknowledgements

We thank Dipl.-Ing. J. Kösters and Dr. T. Block for the intensity data collections and M. Sc. C. Paulsen for the EDX analyses.

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

  2. Research funding: None declared.

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

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Received: 2022-02-01
Accepted: 2022-02-09
Published Online: 2022-02-25
Published in Print: 2022-03-28

© 2022 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Micro Review
  4. Structural diversity among multinary pnictide oxides: a minireview focused on semiconducting and superconducting heteroanionic materials
  5. Inorganic Crystal Structures (Original Paper)
  6. The orthorhombic-to-monoclinic phase transition in NbCrP – Peierls distortion of the chromium chain
  7. Halide-sodalites: thermal expansion, decomposition and the Lindemann criterion
  8. RE3Rh2Sn4 (RE = Y, Gd–Tm, Lu) – first stannides with Lu3Co2In4 type structure
  9. Scandium–copper–indides deriving from the ZrNiAl and MnCu2Al type structures
  10. Syntheses, crystallographic characterization, and structural relations of Rb[SCN]
  11. Organic and Metalorganic Crystal Structures (Original Paper)
  12. Unique supramolecular assembly of a synthetic achiral α, γ-hybrid tripeptide
https://doi.org/10.1515/zkri-2022-0007
Keywords for this article
COOP; DFT; Mössbauer spectroscopy; stannide; superstructure

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Micro Review
  4. Structural diversity among multinary pnictide oxides: a minireview focused on semiconducting and superconducting heteroanionic materials
  5. Inorganic Crystal Structures (Original Paper)
  6. The orthorhombic-to-monoclinic phase transition in NbCrP – Peierls distortion of the chromium chain
  7. Halide-sodalites: thermal expansion, decomposition and the Lindemann criterion
  8. RE3Rh2Sn4 (RE = Y, Gd–Tm, Lu) – first stannides with Lu3Co2In4 type structure
  9. Scandium–copper–indides deriving from the ZrNiAl and MnCu2Al type structures
  10. Syntheses, crystallographic characterization, and structural relations of Rb[SCN]
  11. Organic and Metalorganic Crystal Structures (Original Paper)
  12. Unique supramolecular assembly of a synthetic achiral α, γ-hybrid tripeptide
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