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Crystal structure refinement of MnTe2, MnSe2, and MnS2: cation-anion and anion–anion bonding distances in pyrite-type structures

  • Makoto Tokuda EMAIL logo , Akira Yoshiasa , Tsutomu Mashimo , Hiroshi Arima , Hidetomo Hongu , Tsubasa Tobase , Akihiko Nakatsuka and Kazumasa Sugiyama
Published/Copyright: February 1, 2019
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 234 Issue 6

Abstract

The stability of hauerite (MnS2) as compared to that of pyrite (FeS2) can be explained by the long Mn–S distance and departure from the typical pyrite-type structures. The structural differences of MnX2 compounds (X=S, Se, and Te) are the result of spin configurations that are different than those of other MX2 compounds; however, the arrangement of d-electrons and the size of the ions in MnX2 compounds do not clearly explain why Mn2+ in MnX2 does not exist as a low spin state. To investigate the structural differences of MnX2 compounds, we synthesized single-crystal MnTe2 and MnSe2 and performed single-crsytal X-ray diffraction experiments. The single-crystal X-ray diffraction experiments were conducted on MnTe2 [a=6.9513(1) Å, u-parameter=0.38554(2), space group Pa3̅, Z=4], MnSe2 [a=6.4275(2) Å, u-parameter=0.39358(2)], MnS2 [hauerite; a=6.1013(1) Å, u-parameter=0.40105(4), obtained from Osorezan, Aomori, Japan], and FeS2 [pyrite; a=5.4190(1) Å, u-parameter 0.38484(5), obtained from Kawarakoba, Nagasaki, Japan]. The X-ray intensity datasets of these compounds do not show any evidence of symmetry reduction. In MnS2, the S–S distance is 2.0915(8) Å, which is significantly shorter than that of FeS2 (2.1618(9) Å), and the mean square displacement of S (U11=0.00915(9) Å2) is smaller than that of Mn (U11=0.01137(9) Å2). The thermal vibration characteristics of MnX2 compounds are significantly different than those of FeS2. Based on structural refinement data, we discuss the low spin state of MnX2 compounds and the structural stability of pyrite-type structures.

Keywords: Debye temperature; hauerite; MnSe2; MnTe2; pyrite-type

Acknowledgments

The samples were provided kindly by Prof. Tadao Nishiyama, Mr. Mutsuo Haino, Mr. Toshiyuki Hirama, and Mr. Shinji Inoue. This study was performed under the guidance of the Photon Factory (PAC No.2015G505 and 2015G506).

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2018-2134).

Received: 2018-10-01
Accepted: 2019-01-16
Published Online: 2019-02-01
Published in Print: 2019-05-27

©2019 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Inorganic Crystal Structures
  4. Preparation, structural and spectroscopical properties of silver terbium diphosphate AgTbP2O7
  5. Crystal structure refinement of MnTe2, MnSe2, and MnS2: cation-anion and anion–anion bonding distances in pyrite-type structures
  6. The crystal structure of hibbingite, orthorhombic Fe2Cl(OH)3
  7. Mg[(UO2)2(Ge2O6(OH)2]·(H2O)4.4, a novel compound with mixed germanium coordination: cation disordering and topological features of β-U3O8 type sheets
  8. Polarized mapping Raman spectroscopy: identification of particle orientation in biominerals
  9. Organic and Metalorganic Crystal Structures
  10. Evaluation of N–H···O hydrogen bond interactions in two new phosphoric triamides with a P(O)[NHCH(CH3)2]2 segment by means of topological (AIM) calculations, Hirshfeld surface analysis and 3D energy framework approach
  11. Crystallographic Computing
  12. HKLF5Tools: a program for processing diffraction data of non-merohedrally twinned crystals
https://doi.org/10.1515/zkri-2018-2134
Keywords for this article
Debye temperature; hauerite; MnSe2; MnTe2; pyrite-type

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Inorganic Crystal Structures
  4. Preparation, structural and spectroscopical properties of silver terbium diphosphate AgTbP2O7
  5. Crystal structure refinement of MnTe2, MnSe2, and MnS2: cation-anion and anion–anion bonding distances in pyrite-type structures
  6. The crystal structure of hibbingite, orthorhombic Fe2Cl(OH)3
  7. Mg[(UO2)2(Ge2O6(OH)2]·(H2O)4.4, a novel compound with mixed germanium coordination: cation disordering and topological features of β-U3O8 type sheets
  8. Polarized mapping Raman spectroscopy: identification of particle orientation in biominerals
  9. Organic and Metalorganic Crystal Structures
  10. Evaluation of N–H···O hydrogen bond interactions in two new phosphoric triamides with a P(O)[NHCH(CH3)2]2 segment by means of topological (AIM) calculations, Hirshfeld surface analysis and 3D energy framework approach
  11. Crystallographic Computing
  12. HKLF5Tools: a program for processing diffraction data of non-merohedrally twinned crystals
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