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Cr5.7Si2.3P8N24 - a Chromium(+IV) Nitridosilicate Phosphate with Amphibole‐type structure

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Pointner, Monika M., Fisher, Katherine R., Weidemann, Martin, Wolf, Florian, Wright, Jonathan, Bright, Eleanor Lawrence, Giacobbe, Carlotta, Oeckler, Oliver and Schnick, Wolfgang (2024) Cr5.7Si2.3P8N24 - a Chromium(+IV) Nitridosilicate Phosphate with Amphibole‐type structure. Angewandte Chemie International Edition, 63 (14). pp. 1-6. ISSN 1433-7851

Abstract

The first nitridic analog of an amphibole mineral, the quaternary nitridosilicate phosphate Cr5.7Si2.3P8N24 was synthesized under high‐pressure high‐temperature conditions at 1400 °C and 12 GPa from the binary nitrides Cr2N, Si3N4 and P3N5, using NH4N3 and NH4F as additional nitrogen source and mineralizing agent, respectively. The crystal structure was elucidated by single‐crystal X‑ray diffraction with microfocused synchrotron radiation (C2/m, a = 9.6002(19), b = 17.107(3), c = 4.8530(10) Å, β = 109.65(3)°). The elemental composition was analyzed by energy dispersive X‐ray spectroscopy. The structure consists of vertex‐sharing PN4‐tetrahedra forming zweier double chains and edge‐sharing (Si,Cr)‐centered octahedra forming separated ribbons. Atomic resolution scanning transmission electron microscopy shows ordered Si and Cr sites next to a disordered Si/Cr site. Optical spectroscopy indicates a band gap of 2.1 eV. Susceptibility measurements show paramagnetic behavior and support the oxidation state Cr+IV, which is confirmed by EPR. The comprehensive analysis expands the field of Cr‐N chemistry and provides access to a nitride analog of one of the most prevalent silicate structures.

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Title:
Cr5.7Si2.3P8N24 - a Chromium(+IV) Nitridosilicate Phosphate with Amphibole‐type structure
Creators:
Pointner, Monika M., Fisher, Katherine R., Weidemann, Martin, Wolf, Florian, Wright, Jonathan, Bright, Eleanor Lawrence, Giacobbe, Carlotta, Oeckler, Oliver and Schnick, Wolfgang
Identification Number:
https://doi.org/10.1002/anie.202401421
Official URL:
https://doi.org/10.1002/anie.202401421
Date:
15 February 2024
Subjects:
500 Natural Sciences and Mathematics > 540 Chemistry & allied sciences
Department:
School of Human Sciences
Publisher:
Wiley, Gesellschaft Deutscher Chemiker
Uncontrolled Keywords:
amphibole; chromium(+IV); high-pressure chemistry; nitrides; structure elucidation
Additional Information:
Copyright © 2024 Author(s). This is the peer reviewed version of the article that has been published in final form at https://doi.org/10.1002/anie.202401421. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.
Record
URI:
https://repository.londonmet.ac.uk/id/eprint/9188
Item Type:
Article
Depositing User:
Pub Router
SWORD Depositor:
Pub Router
Date Deposited:
28 Feb 2024 09:50
Revision:
19
Last Modified:
08 Apr 2024 09:11
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