The Crystal Structures and Raman Spectra of Three New Hydrothermally Synthesized Copper–Zinc–Oxotellurates(IV). Issue 11 (10th June 2020)

• Record Type: Journal Article
• Authors: Missen, Owen P.; Weil, Matthias; Mills, Stuart J.; Libowitzky, Eugen; Kolitsch, Uwe; Stöger, Berthold
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 646:Issue 11/12(2020)
• Page Start: 476
• Page End: 488
• Publication Date: 2020-06-10
• Subjects: Tellurite -- Mixed‐anionic compound -- Structure elucidation -- Order‐disorder structure -- Hydrothermal synthesis; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.202000016
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : Abstract . Three new copper–zinc–tellurites, Zn4 Cu(Te IV O3 )4 Cl2, Cu2 Zn2 (Te IV O3 )2 (SO4 )(OH)2 · H2 O and Cu2 Zn(Te IV O4 )(SO4 )· H2 O (henceforth I, II and III ), were synthesized under mild hydrothermal conditions (473 K, in Teflon‐lined steel vessels). They were characterized in detail by a combination of crystal‐structure determination (using single‐crystal X‐ray diffraction data), single‐crystal micro‐Raman spectroscopy and chemical analyses (energy‐dispersive X‐ray spectroscopy in a scanning electron microscope). Each compound crystallizes in a new structure type, and additionally, II and III represent the first two ever reported copper–zinc–tellurite–sulfates. I [systematic name: tetrazinc copper(II) tetrakis‐oxotellurate(IV) dichloride] is triclinic, P 1, and forms a framework structure based on ZnO6 and ZnO5 Cl octahedra, linked into sheets connected via Jahn–Teller‐distorted CuO4 Cl2 octahedra, with Te IV O3 trigonal pyramids and Te IV 2 O6 dimers (composed of two edge‐sharing Te IV O4 disphenoids) filling the remaining space. II [dicopper(II) dizinc bis‐oxotellurate(IV) oxosulfate(VI) bis‐hydroxide monohydrate] is trigonal, R 3 m, with a simonkolleite‐like framework. Distinct layers formed from (Cu, Zn)φ6 (φ = O, OH) octahedra and Te IV O3 trigonal pyramids extend parallel to (001) and sandwich disordered SO4 2– anions and H2 O groups. III [dicopper(II) zinc oxotellurate(IV) oxosulfate(VI) hydrate] is orthorhombic, Pnma, and also has a layered structure [extending parallel to (100)]. Positively charged layers of composition [Cu2 ZnTe IV O4 ] 2+ (containing Te as Te IV O4 disphenoids) alternate with SO4 2– anions and H2 O groups in the interlayer space. Stacking disorder caused by the order‐disorder nature of the crystal structure is reflected by the presence of residual electron density in difference‐Fourier maps and the structure was refined as an overlay of two stacking possibilities. Abstract :