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Synthesis and crystal structure of the disordered modification of Tl6Si2O7

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Abstract

A new compound β-Tl6Si2O7 has been investigated using the methods of IR spectroscopy and microprobe and X-ray diffraction analysis. The elementary unit parameters were as follows: P63/m, a = 9.673(2) Å, c = 3.9169(9) Å, and V = 317.4(1) Å3. The structure was resolved by direct methods and corrected until R 1 = 0.029 (wR 2 = 0.047) for 240 reflections [F o] ≥ 4σ F . The crystal structure of β-Tl6Si2O7 contains one symmetrically independent position of the Tl+ cation that forms three short (〈Tl-O〉 = 2.54 Å) bonds and one weak bond (2.93 Å) with the oxygen atom. One can observe a strong disordering of silicon atoms (Si-Si = 0.64 Å). The distorted tetragonal pyramids TlO4 are linked through silicate tetrahedra into a three-dimensional framework. The interesting feature of the crystal structure of β-Tl6Si2O7 is in the presence of wide channels occupied by lone electron pairs on Tl+ cations. One can also mention that in most of the structures of Tl+ oxygen-containing salts the lone pairs are associated into separate parts in the form of micelles in channels of frameworks or other structural cavities.

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Authors and Affiliations

  1. St Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199034, Russia

    O. I. Siidra, S. N. Britvin, S. V. Krivovichev & D. A. Klimov

  2. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, St. Petersburg, 199034, Russia

    S. V. Krivovichev

  3. University of Kiel, Olshausenstrasse 40, Kiel, 24117, Germany

    W. Depmeier

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  1. O. I. Siidra
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  2. S. N. Britvin
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  3. S. V. Krivovichev
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  4. D. A. Klimov
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  5. W. Depmeier
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Correspondence to O. I. Siidra.

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Original Russian Text © O.I. Siidra, S.N. Britvin, S.V. Krivovichev, D.A. Klimov, W. Depmeier, 2012, published in Fizika i Khimiya Stekla.

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Siidra, O.I., Britvin, S.N., Krivovichev, S.V. et al. Synthesis and crystal structure of the disordered modification of Tl6Si2O7 . Glass Phys Chem 38, 473–477 (2012). https://doi.org/10.1134/S1087659612060053

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  • DOI: https://doi.org/10.1134/S1087659612060053

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