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The Crystal Structures and Raman Spectra of Three New Hydrothermally Synthesized Copper–Zinc–Oxotellurates(IV)
Author(s) -
Missen Owen P.,
Weil Matthias,
Mills Stuart J.,
Libowitzky Eugen,
Kolitsch Uwe,
Stöger Berthold
Publication year - 2020
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202000016
Subject(s) - crystallography , zinc , copper , octahedron , crystal structure , chemistry , triclinic crystal system , hydrate , raman spectroscopy , physics , organic chemistry , optics
. Three new copper–zinc–tellurites, Zn 4 Cu(Te IV O 3 ) 4 Cl 2 , Cu 2 Zn 2 (Te IV O 3 ) 2 (SO 4 )(OH) 2 · H 2 O and Cu 2 Zn(Te IV O 4 )(SO 4 ) · H 2 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 ZnO 6 and ZnO 5 Cl octahedra, linked into sheets connected via Jahn–Teller‐distorted CuO 4 Cl 2 octahedra, with Te IV O 3 trigonal pyramids and Te IV 2 O 6 dimers (composed of two edge‐sharing Te IV O 4 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)φ 6 (φ = O, OH) octahedra and Te IV O 3 trigonal pyramids extend parallel to (001) and sandwich disordered SO 4 2– anions and H 2 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 [Cu 2 ZnTe IV O 4 ] 2+ (containing Te as Te IV O 4 disphenoids) alternate with SO 4 2– anions and H 2 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.