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Title: Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}]

Abstract

The orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB{sub 3}S{sub 6}, PrB{sub 5}S{sub 9} and NdB{sub 3}S{sub 6}. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS{sub 3}] and Nd[BS{sub 3}] were also obtained from rare earth chlorides RECl{sub 3} and sodium thioborate Na{sub 2}B{sub 2}S{sub 5} by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna2{sub 1} (No. 33; Z=4; Ce: a=7.60738(6)A, b=6.01720(4)A, c=8.93016(6)A; Pr: a=7.56223(4)A, b=6.00876(2)A, c=8.89747(4)A; Nd: a=7.49180(3)A, b=6.00823(2)A, c=8.86197(3)A) . The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.more » - Abstract: Graphical Abstract Legend (TOC Figure): Table of Contents Figure The isotypic orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared using different preparation routes. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of corrugated kagome nets (sketched with blue dotted lines), which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.« less

Authors:
;  [1];  [1]
  1. Max Planck Institute for Chemical Physics of Solids, Noethnitzer Strasse 40, D-01187 Dresden (Germany)
Publication Date:
OSTI Identifier:
21372542
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2010.01.002; PII: S0022-4596(10)00003-4; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORATES; BORON; CERIUM COMPOUNDS; CHLORIDES; NEODYMIUM COMPOUNDS; ORTHORHOMBIC LATTICES; PRASEODYMIUM COMPOUNDS; PRESSURE RANGE GIGA PA; SODIUM COMPOUNDS; SULFUR COMPOUNDS; SYNTHESIS; TEMPERATURE RANGE 1000-4000 K; X-RAY DIFFRACTION; ALKALI METAL COMPOUNDS; BORON COMPOUNDS; CHLORINE COMPOUNDS; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; ELEMENTS; HALIDES; HALOGEN COMPOUNDS; OXYGEN COMPOUNDS; PRESSURE RANGE; RARE EARTH COMPOUNDS; SCATTERING; SEMIMETALS; TEMPERATURE RANGE

Citation Formats

Hunger, Jens, Borna, Marija, and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}]. United States: N. p., 2010. Web. doi:10.1016/j.jssc.2010.01.002.
Hunger, Jens, Borna, Marija, & Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}]. United States. doi:10.1016/j.jssc.2010.01.002.
Hunger, Jens, Borna, Marija, and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. Mon . "Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}]". United States. doi:10.1016/j.jssc.2010.01.002.
@article{osti_21372542,
title = {Synthesis and crystal structure of the isotypic rare earth thioborates Ce[BS{sub 3}], Pr[BS{sub 3}], and Nd[BS{sub 3}]},
author = {Hunger, Jens and Borna, Marija and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d},
abstractNote = {The orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB{sub 3}S{sub 6}, PrB{sub 5}S{sub 9} and NdB{sub 3}S{sub 6}. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS{sub 3}] and Nd[BS{sub 3}] were also obtained from rare earth chlorides RECl{sub 3} and sodium thioborate Na{sub 2}B{sub 2}S{sub 5} by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna2{sub 1} (No. 33; Z=4; Ce: a=7.60738(6)A, b=6.01720(4)A, c=8.93016(6)A; Pr: a=7.56223(4)A, b=6.00876(2)A, c=8.89747(4)A; Nd: a=7.49180(3)A, b=6.00823(2)A, c=8.86197(3)A) . The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species. - Abstract: Graphical Abstract Legend (TOC Figure): Table of Contents Figure The isotypic orthothioborates Ce[BS{sub 3}], Pr[BS{sub 3}] and Nd[BS{sub 3}] were prepared using different preparation routes. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The crystal structures contain isolated [BS{sub 3}]{sup 3-} groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of corrugated kagome nets (sketched with blue dotted lines), which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.},
doi = {10.1016/j.jssc.2010.01.002},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 183,
place = {United States},
year = {Mon Mar 15 00:00:00 EDT 2010},
month = {Mon Mar 15 00:00:00 EDT 2010}
}
  • 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 structuremore » 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].« less
  • Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 deg. C. In the La-Ti-Sb system, the previously known compound La{sub 3}TiSb{sub 5} was confirmed and the new compound La{sub 2}Ti{sub 7}Sb{sub 12} (own type, Cmmm, Z=2, a=10.5446(10) A, b=20.768(2) A, and c=4.4344(4) A) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La{sub 2}Ti{sub 7}Sb{sub 12} consists of a complex arrangement of TiSb{sub 6}more » octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi{sub 3}(Sn{sub x}Sb{sub 1-x}){sub 4} for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) A, b=10.0846(7) A, and c=24.2260(16) A for NdTi{sub 3}(Sn{sub 0.1}Sb{sub 0.9}){sub 4}; a=5.7590(4) A, b=10.0686(6) A, and c=24.1167(14) A for SmTi{sub 3}(Sn{sub 0.1}Sb{sub 0.9}){sub 4}). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets. - Graphical abstract: La{sub 2}Ti{sub 7}Sb{sub 12} contains sectioned layers consisting of Ti-centred octahedra linked by corner- and face-sharing.« less
  • Rare earth tin antimonides, RESn{sub x}Sb{sub 2} (RE = La, Ce, Pr, Nd, Sm) were synthesized by stoichiometric combination of the elements at high temperature. For the La compound, Sn content was varied from 0.1 {le} x {le} 0.8 and the crystal structure of x = 0.75 is reported. LaSn{sub 0.75}Sb{sub 2} crystallizes in the orthorhombic space group D{sup 17}{sub 2h}-Cmcm.
  • A series of double perovskites Ba{sub 2}MBiO{sub 6} (M=Ce to Lu) was prepared and characterized chemically and by powder X-ray diffraction. Crystal structures of Ba{sub 2}MBiO{sub 6}(M = Ce, Pr, Nd, Tb, Yb) were determined by neutron diffraction and magnetic susceptibilities were measured for M = Ce, Pr, Nd, and Tb. 26 refs., 11 figs., 11 tabs.
  • The rare-earth dicyanamides Ln[N(China){sub 2}]{sub 3} (Ln=La, Ce, Pr, Nd, Sm, Eu) were obtained via ion exchange in aqueous medium and subsequent drying: The crystal structures were solved and refined based on X-ray powder diffraction data and they were found to be isotypic: Ln[N(China){sub 2}]{sub 3}; Cmcm (no. 63), Z=4, Ln=La: a=799.88(9)pm, b=1158.2(1)pm, c=1026.7(1)pm; Ce: a=794.94(3)pm, b=1152.15(4)pm, c=1020.96(4)pm; Pr: a=790.45(5)pm, b=1146.19(6)pm, c=1016.74(6)pm; Nd: a=787.79(3)pm, b=1144.59(4)pm, c=1015.54(4)pm; Sm: a=781.30(5)pm, b=1138.64(6)pm, c=1012.04(5)pm; Eu: a=776.7(1)pm, b=1135.1(1)pm, c=1013.7(1)pm). The compounds represent the first dicyanamides with trivalent cations. The Ln{sup 3+} ions are coordinated by three bridging N atoms and six terminal N atoms ofmore » the dicyanamide ions forming a three capped trigonal prism. The structure type is related to that of PuBr{sub 3}. The novel compounds Ln[N(China){sub 2}]{sub 3} have been characterized by IR and Raman spectroscopy (Ln=La) and the thermal behavior has been monitored by differential scanning calorimetry (Ln=Ce, Nd, Eu)« less