On tungstates of divalent cations (III) – Pb5O2[WO6]

Stephan G. Jantz; Florian Pielnhofer; Henning A. Höppe

doi:10.1515/zkri-2020-0041

Published by De Gruyter (O) July 12, 2020

On tungstates of divalent cations (III) – Pb₅O₂[WO₆]

Stephan G. Jantz , Florian Pielnhofer and Henning A. Höppe

From the journal Zeitschrift für Kristallographie - Crystalline Materials

https://doi.org/10.1515/zkri-2020-0041

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Abstract

Pb5O2[WO6] was discovered as a frequently observed side phase during our investigation on lead tungstates. Its crystal structure was solved by single-crystal X-ray diffraction (P21/n, a=7.4379(2) Å, b=12.1115(4) Å, c=10.6171(3) Å, β=90.6847(8)°, Z=4, Rint=0.038, R1=0.020, ωR2=0.029, 4188 data, 128 param.) and is isotypic with Pb5O2[Te6]. Pb5O2[WO6] comprises a layered structure built up by non-condensed [WO₆]6− octahedra and [O4Pb10]12+ oligomers. The compound was characterised by spectroscopic measurements (Infrared (IR), Raman and Ultraviolet–visible (UV/Vis) spectra) as well as quantum chemical and electrostatic calculations (density functional theory (DFT), MAPLE) yielding a band gap of 2.9 eV fitting well with the optical one of 2.8 eV. An estimation of the refractive index based on the Gladstone-Dale relationship yielded n≈2.31. Furthermore first results of the thermal analysis are presented.

Keywords: crystal structure; lead; optical spectroscopy; tungstates; vibrational spectroscopy

Dedicated to Professor Dr. Ulrich Müller on the occasion of his 80th birthday.

Corresponding author: Henning A. Höppe, Lehrstuhl für Festkörperchemie, Universität Augsburg, Universitätsstraße 1, 86159 Augsburg, Germany, E-mail: henning@ak-hoeppe.de

Acknowledgement

F.P. thanks Prof. Bettina Lotsch, Dr. Ulrich Wedig and the Computer Service group from the Max-Planck-Institute for Solid State Research (Stuttgart, Germany) for access to CRYSTAL17 and computational facilities.

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2020-0041).

Received: 2020-04-16

Accepted: 2020-04-22

Published Online: 2020-07-12

Published in Print: 2020-09-25