Home Physical Sciences Synthesis, revised crystal structures, and refractive indices of ABW-type CsMTiO4 (M = Al, Fe, Ga) and ANA-type CsTi1.10Si1.90O6.50, and the determination of the electronic polarizability of 4-coordinated Ti4+
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Synthesis, revised crystal structures, and refractive indices of ABW-type CsMTiO4 (M = Al, Fe, Ga) and ANA-type CsTi1.10Si1.90O6.50, and the determination of the electronic polarizability of 4-coordinated Ti4+

  • Jan Derk Groeneveld , Manfred Burianek , Johannes Birkenstock , Lennart A. Fischer , Robert D. Shannon and Reinhard X. Fischer EMAIL logo
Published/Copyright: September 28, 2020
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 235 Issue 11

Abstract

Single crystals of ABW-type CsAlTiO4 (CAT), CsFeTiO4 (CFT), CsGaTiO4 (CGT), and ANA-type CsTi1.1Si1.9O6.5 (CST) were grown and characterized by electron microprobe analyses, single-crystal X-ray diffraction, thermal analyses, and spindle-stage optical investigations to determine the electronic polarizability of 4-coordinated Ti4+, α([4]Ti4+). The crystal structure of CAT was confirmed to crystallize in the highest possible topological symmetry Imma (a = 8.9677(2) Å, b = 5.7322(1) Å, c = 9.9612(3) Å) with tetrahedrally coordinated Al and Ti equally distributed on Wyckoff position 8i. Twinning by reticular merohedry with a twin index of 2 was observed for most of the crystals resulting in a hexagonal twin lattice (a = 11.487(3) Å, c = 8.968(2) Å) with Laue symmetry 6/mmm. Refractive indices measured by immersion methods on an untwinned specimen are nx = 1.716(5), ny = 1.725(2), and nz = 1.727(1) with 2Vz = 127.1(6)°. The diffraction patterns of CFT and CGT clearly showed superstructure reflections causing a symmetry lowering of index 4 with a transformation according to 2a, b, c from Imma to Pmab with a = 18.3054(7) Å, b = 5.8083(2) Å, c = 9.9938(4) Å for CFT, and a = 18.2921(6) Å, b = 5.7636(2) Å, c = 9.9210(3) Å for CGT. Refractive indices for CGT are nx = 1.750(3), ny = 1.772(3), and nz = 1.776(2) with 2Vz = 132(1)°. The crystal structure of the ANA-type CsTi1.1Si1.9O6.5 was confirmed to crystallize in space group Ia3¯d (a = 13.8333(4) Å). The extra 0.5 O atoms are needed for charge compensation and to allow the sum of electronic polarizabilities to give a total electronic polarizability calculated from the refractive index n = 1.718(4). The electronic polarizability of [4]Ti4+ was calculated from the difference between the observed total polarizabilities (derived from the mean refractive indices of CAT and CGT) and the sum of electronic polarizabilities of cations and anions omitting the polarizability of Ti resulting in α([4]Ti4+) = 5.15(5) Å3.

Keywords: ABW-type CsMTiO4; ANA-type CsTiSi2O6.5; crystal growth; crystal structure; electronic polarizabilities; refractive indices
Corresponding author: Reinhard X. Fischer, Universität Bremen, FB 5 Geowissenschaften, Klagenfurter Str. 2, 28359 Bremen, Germany, E-mail:

Funding source: Deutsche Forschungsgemeinschaft

Award Identifier / Grant number: FI442/21-2

Acknowledgments

We thank the Deutsche Forschungsgemeinschaft (DFG) for funding this project under grant FI442/21-2, Anne Hübner (Bremen) for the EMPA preparation, Olaf Medenbach (Bochum) for providing optical equipment, and Ruth C. Shannon (Boulder) and two anonymous referees for their comments on the manuscript.

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

  2. Research funding: We thank the Deutsche Forschungsgemeinschaft (DFG) for funding this project under grant FI442/21-2.

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

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Received: 2020-05-06
Accepted: 2020-08-21
Published Online: 2020-09-28
Published in Print: 2020-11-26

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Original Paper
  4. From the Ritter pile to the aluminum ion battery – Peter Paufler’s academic genealogy
  5. New ternary MgCo2Ga5 and MgNi2Ga5 gallides
  6. A study on the limit of application of kinematical theory of X-ray diffraction
  7. Synthesis, revised crystal structures, and refractive indices of ABW-type CsMTiO4 (M = Al, Fe, Ga) and ANA-type CsTi1.10Si1.90O6.50, and the determination of the electronic polarizability of 4-coordinated Ti4+
  8. Molecular inorganic polymers: synthesis and crystal structures of KCl72H2SeO3 and CsCl7H2SeO3
  9. Artefacts from Ban Chiang, Thailand: pottery with hematite-red geometric patterns
  10. Theoretical and experimental solid state studies of Ethyl 1-benzyl-2-(thiophen-3-yl)-1H-benzo[d]imidazole-5-carboxylate
https://doi.org/10.1515/zkri-2020-0056
Keywords for this article
ABW-type CsMTiO4; ANA-type CsTiSi2O6.5; crystal growth; crystal structure; electronic polarizabilities; refractive indices

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Original Paper
  4. From the Ritter pile to the aluminum ion battery – Peter Paufler’s academic genealogy
  5. New ternary MgCo2Ga5 and MgNi2Ga5 gallides
  6. A study on the limit of application of kinematical theory of X-ray diffraction
  7. Synthesis, revised crystal structures, and refractive indices of ABW-type CsMTiO4 (M = Al, Fe, Ga) and ANA-type CsTi1.10Si1.90O6.50, and the determination of the electronic polarizability of 4-coordinated Ti4+
  8. Molecular inorganic polymers: synthesis and crystal structures of KCl72H2SeO3 and CsCl7H2SeO3
  9. Artefacts from Ban Chiang, Thailand: pottery with hematite-red geometric patterns
  10. Theoretical and experimental solid state studies of Ethyl 1-benzyl-2-(thiophen-3-yl)-1H-benzo[d]imidazole-5-carboxylate
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