The crystal structure of cesbronite, Cu3TeO4(OH)4: a novel sheet tellurate topology

• Published in: Acta crystallographica Section B, Structural science, crystal engineering and materials Structural science, crystal engineering and materials, 2018-02, Vol.74 (1), p.24-31
• Main Authors: Missen, O. P., Mills, S. J., Welch, M. D., Spratt, J., Rumsey, M. S., Birch, W. D., Brugger, J.
• Format: Article
• Language: English
• Subjects: cesbronite; Chemical bonds; Configurations; Copper; Corrugated sheet; Crystal structure; Diffraction; electron‐microprobe analysis; Hydrogen bonding; Oxidation; oxysalt; powder diffraction; Protonation; Raman spectroscopy; Sheets; Single crystals; single‐crystal X‐ray diffraction; tellurate; Tellurium; Topology; Valence; X-ray diffraction; xocomecatlite
• ISSN: 2052-5206; 2052-5192; 2052-5206
• DOI: 10.1107/S205252061701647X

The crystal structure of cesbronite has been determined using single‐crystal X‐ray diffraction and supported by electron‐microprobe analysis, powder diffraction and Raman spectroscopy. Cesbronite is orthorhombic, space group Cmcm, with a = 2.93172 (16), b = 11.8414 (6), c = 8.6047 (4) Å and V = 298.72 (3) Å3. The chemical formula of cesbronite has been revised to CuII3TeVIO4(OH)4 from CuII5(TeIVO3)2(OH)6·2H2O. This change has been accepted by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association, Proposal 17‐C. The previously reported oxidation state of tellurium has been shown to be incorrect; the crystal structure, bond valence studies and charge balance clearly show tellurium to be hexavalent. The crystal structure of cesbronite is formed from corrugated sheets of edge‐sharing CuO6 and (Cu0.5Te0.5)O6 octahedra. The structure determined here is an average structure that has underlying ordering of Cu and Te at one of the two metal sites, designated as M, which has an occupancy Cu0.5Te0.5. This averaging probably arises from an absence of correlation between adjacent polyhedral sheets, as there are two different hydrogen‐bonding configurations linking sheets that are related by a ½a offset. Randomised stacking of these two configurations results in the superposition of Cu and Te and leads to the Cu0.5Te0.5 occupancy of the M site in the average structure. Bond‐valence analysis is used to choose the most probable Cu/Te ordering scheme and also to identify protonation sites (OH). The chosen ordering scheme and its associated OH sites are shown to be consistent with the revised chemical formula. The novel crystal structure of cesbronite has been determined. It is composed of corrugated sheets of edge‐sharing CuO6 and (Cu0.5Te0.5)O6 octahedra and shows well defined ordering of Cu and Te.