Crystal structures and crystallographic classification of titanium silicophosphates – with a note on structure and composition of silicophosphates “M3P5SiO19”

Robert Glaum; Marcos Schöneborn; Felix Reinauer; Halil Shaqiri; Saiful M. Islam

doi:10.1515/znb-2023-0099

Published by De Gruyter April 5, 2024

Crystal structures and crystallographic classification of titanium silicophosphates – with a note on structure and composition of silicophosphates “M₃P₅SiO₁₉”

Robert Glaum , Marcos Schöneborn , Felix Reinauer , Halil Shaqiri and Saiful M. Islam

From the journal Zeitschrift für Naturforschung B

https://doi.org/10.1515/znb-2023-0099

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Abstract

The crystal structures of Ti^III₄[Si₂O(PO₄)₆] ( P 3 ‾ , Z = 3, a = 14.733(1), c = 7.363(1) Å, R1 = 0.040, wR2 = 0.098, 7649 ind. refl., 170 variables), Fe^II_0.79Ti^III_2.42Ti^IV_0.79[Si₂O(PO₄)₆] ( P 3 ‾ , Z = 3, a = 14.6534(2), c = 7.3829(1) Å, R1 = 0.036, wR2 = 0.088, 4026 ind. refl., 171 variables), and Ti^III₂Ti^IV₆(PO₄)₆[Si₂O(PO₄)₆] ( R 3 ‾ , Z = 1, a = 8.446(2), c = 44.21(2) Å, R1 = 0.047, wR2 = 0.120, 1373 ind. refl., 109 variables) have been refined from single-crystal data. The structures show hexagonal closest packing of phosphate groups with metal cations and [Si₂O] groups occupying octahedral voids [□(PO₄)₆]. The close relationship of these and other silicophosphate structures to the NiAs and β-Fe₂(SO₄)₃ (see also NaZr₂(PO₄)₃ “NASICON”) structure types is rationalized by group/subgroup considerations. This symmetry approach shows that systematic twinning is highly likely in silicophosphates, thus possibly leading to faulty crystal structure refinements. Our investigation strongly suggests that the proper composition of silicophosphates “M^III₃P₅SiO₁₉” (M = Cr, V, Fe, Mo) reported in literature is actually M^III₄-[Si₂O(PO₄)₆]. In the mixed-valent compounds oxidation states were assigned to the cation sites by comparison to Ti₂O₃, TiP₂O₇ and FeTiO₃. The powder reflectance spectrum of dark-blue Fe^II_0.79Ti^III_2.42Ti^IV_0.79[Si₂O(PO₄)₆] shows a strong IVCT transition at ν ˜ = 17,500 cm⁻¹, and magnetic susceptibility data agree very well with the proposed oxidation states.

Keywords: group/subgroup relations; NASICON; closest-packed structures; mixed-valent titanium; silicophosphates

Dedicated to Professor Thomas Bredow of the University of Bonn on the occasion of his 60th birthday.

Corresponding author: Robert Glaum, Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, D-53121 Bonn, Germany, E-mail: rglaum@uni-bonn.de

Funding source: Rheinische Friedrich-Wilhelms-Universität Bonn

Acknowledgment

We thank Dr. Jörg Daniels, Axel Pelka (both Universität Bonn, Germany) and Chun-Yu Chen (NTHU Hsinchu, Taiwan) for measuring the single-crystal data sets. We also thank Prof. Johannes Beck (Universität Bonn, Germany) and Prof. Sue-Lein Wang (NTHU Hsinchu, Taiwan) for the friendly provision of the instruments. M. S. thanks Profs. Sue-Lein Wang (NTHU Hsinchu, Taiwan) and Kwang-Hwa Lii (NCU Chungli, Taiwan) and all of their group members for their great hospitality and stimulating scientific support. A scholarship provided by the DAAD is gratefully acknowledged.

Research ethics: Not applicable.
Author contributions: All authors contributed equally to this manuscript.
Competing interests: The authors state no conflict of interest.
Research funding: This research was funded by Rheinische Friedrich-Wilhelms-Universität Bonn.
Data availability: The raw data can be obtained on request from the corresponding author.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/znb-2023-0099).

Received: 2023-11-13

Accepted: 2023-11-30

Published Online: 2024-04-05

Published in Print: 2024-04-25