High-pressure high-temperature synthesis and crystal structure of the isotypic rare earth (RE)-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu)

Journal Article · Tue Feb 15 00:00:00 EST 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.11.004· OSTI ID:21494195

Borna, Marija; Hunger, Jens; Ormeci, Alim ^[1]; Zahn, Dirk ^[2]; Burkhardt, Ulrich; Carrillo-Cabrera, Wilder; Cardoso-Gil, Raul ^[1]; Kniep, Ruediger ^[1]

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1. Max Planck Institute for Chemical Physics of Solids, Noethnitzer Strasse 40, D-01187 Dresden (Germany)
2. Computer-Chemie-Centrum, Friedrich-Alexander-Universitaet Erlangen-Nuernberg, Naegelsbach Strasse 25, D-91052 Erlangen (Germany)

Application of high-pressure high-temperature conditions (3.5 GPa at 1673 K for 5 h) to mixtures of the elements (RE:B:S=1:3:6) yielded crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu), which crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. The crystal structures were refined from X-ray powder diffraction data by applying the Rietveld method. Dy: a=9.4044(2) A, c=5.8855(3) A; Ho: a=9.3703(1) A, c=5.8826(1) A; Er: a=9.3279(12) A, c=5.8793(8) A; Tm: a=9.2869(3) A, c=5.8781(3) A; Yb: a=9.2514(5) A, c=5.8805(6) A; Lu: a=9.2162(3) A, c=5.8911(3) A. The crystal structure is characterized by the presence of two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. -- Graphical abstract: Isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) were prepared by application of high-pressure high-temperature conditions to mixtures of the elements. Their crystal structures are characterized by presence of the two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. Quantum mechanical calculations revealed the arrangement of the intrinsic vacancies. Display Omitted Research Highlights: {yields} Application of high-pressure high-temperature conditions to mixtures of the elements yields crystalline samples of the isotypic rare earth-thioborate-sulfides RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu). {yields} RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) crystallize in space group P6{sub 3} (Z=2/3) and adopt the Ce{sub 6}Al{sub 3.33}S{sub 14} structure type. {yields} The crystal structure of RE{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3}, (RE=Dy-Lu) is characterized by the presence of two isolated complex ions [BS{sub 3}]{sup 3-} and [BS{sub 4}]{sup 5-} as well as [{open_square}(S{sup 2-}){sub 3}] units. {yields} The vacancies in Lu{sub 9}[BS{sub 3}]{sub 2}[BS{sub 4}]{sub 3}S{sub 3} are located at the trigonal planar coordinated boron site with preferred ordering -B2-B2-{open_square}-B2-B2-{open_square}- along [001].

• OSTI ID: 21494195
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 2; Other Information: DOI: 10.1016/j.jssc.2010.11.004; PII: S0022-4596(10)00510-4; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
BORATES
CHEMICAL BONDS
HEXAGONAL LATTICES
PRESSURE RANGE GIGA PA
RARE EARTH COMPOUNDS
SPACE GROUPS
SULFIDES
SYNTHESIS
TEMPERATURE RANGE 1000-4000 K
VACANCIES
X-RAY DIFFRACTION
X-RAY SPECTROSCOPY
BORON COMPOUNDS
CHALCOGENIDES
COHERENT SCATTERING
CRYSTAL DEFECTS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
OXYGEN COMPOUNDS
POINT DEFECTS
PRESSURE RANGE
SCATTERING
SPECTROSCOPY
SULFUR COMPOUNDS
SYMMETRY GROUPS
TEMPERATURE RANGE