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Title: Synthesis and crystal structures of Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52}

Abstract

The rare earth-platinum-indides Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52} were synthesized from the elements by arc-melting of the components. Single crystals were grown using special annealing sequences. The three indides were investigated by X-ray powder and single crystal diffraction: Tb{sub 6}Pt{sub 12}In{sub 23} type, C2/m, Z=2, a=2811.9(6), b=441.60(9), c=1486.6(3)pm, {beta}=112.10(3){sup o}, wR{sub 2}=0.0629, 3645 F{sup 2} values, 126 variables for Nd{sub 6}Pt{sub 13}In{sub 22}, a=2821.9(6), b=443.06(9), c=1481.0(3)pm, {beta}=112.39(3){sup o}, wR{sub 2}=0.0543, 3679 F{sup 2} values, 127 variables for Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and a=2818.5(6), b=439.90(9), c=1480.9(3)pm, {beta}=112.29(3){sup o}, wR{sub 2}=0.0778, 3938 F{sup 2} values, 127 variables for Gd{sub 6}Pt{sub 12.48}In{sub 22.52}. Most platinum atoms in these structures have a distorted trigonal prismatic coordination by rare earth metal and indium atoms. Together, the platinum and indium atoms build up a complex three-dimensional [Pt{sub 12+x}In{sub 23-x}] polyanionic network in which the rare earth metal atoms fill distorted pentagonal and hexagonal channels. The 2c Wyckoff site in these structures plays a peculiar role. This site is occupied by indium in the prototype Tb{sub 6}Pt{sub 12}In{sub 23}, while platinum atoms fill the 2c site in Nd{sub 6}Pt{sub 13}In{sub 22}, leading to a linear Pt{sub 3} chain withmore » Pt-Pt distances of 275pm. The crystals with samarium and gadolinium as rare earth metal component show mixed Pt/In occupancies.« less

Authors:
 [1];  [2];  [3];  [3];  [4]
  1. Inorganic Chemistry Department, Ivan Franko National University of Lviv, Kyryla and Mephodiya Street 6, 79005 Lviv (Ukraine). E-mail: vazar@franko.lviv.ua
  2. Inorganic Chemistry Department, Ivan Franko National University of Lviv, Kyryla and Mephodiya Street 6, 79005 Lviv (Ukraine)
  3. Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 36, D-48149 Muenster (Germany)
  4. Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 36, D-48149 Muenster (Germany). E-mail: pottgen@uni-muenster.de
Publication Date:
OSTI Identifier:
20784934
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2005.12.022; PII: S0022-4596(05)00604-3; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANNEALING; GADOLINIUM COMPOUNDS; INDIUM COMPOUNDS; INTERMETALLIC COMPOUNDS; MELTING; MONOCLINIC LATTICES; MONOCRYSTALS; NEODYMIUM COMPOUNDS; PLATINUM COMPOUNDS; SAMARIUM COMPOUNDS; SYNTHESIS; X-RAY DIFFRACTION

Citation Formats

Zaremba, Vasyl I., Dubenskiy, Vitaliy P., Rodewald, Ute Ch., Heying, Birgit, and Poettgen, Rainer. Synthesis and crystal structures of Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52}. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.12.022.
Zaremba, Vasyl I., Dubenskiy, Vitaliy P., Rodewald, Ute Ch., Heying, Birgit, & Poettgen, Rainer. Synthesis and crystal structures of Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52}. United States. doi:10.1016/j.jssc.2005.12.022.
Zaremba, Vasyl I., Dubenskiy, Vitaliy P., Rodewald, Ute Ch., Heying, Birgit, and Poettgen, Rainer. Wed . "Synthesis and crystal structures of Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52}". United States. doi:10.1016/j.jssc.2005.12.022.
@article{osti_20784934,
title = {Synthesis and crystal structures of Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52}},
author = {Zaremba, Vasyl I. and Dubenskiy, Vitaliy P. and Rodewald, Ute Ch. and Heying, Birgit and Poettgen, Rainer},
abstractNote = {The rare earth-platinum-indides Nd{sub 6}Pt{sub 13}In{sub 22}, Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and Gd{sub 6}Pt{sub 12.48}In{sub 22.52} were synthesized from the elements by arc-melting of the components. Single crystals were grown using special annealing sequences. The three indides were investigated by X-ray powder and single crystal diffraction: Tb{sub 6}Pt{sub 12}In{sub 23} type, C2/m, Z=2, a=2811.9(6), b=441.60(9), c=1486.6(3)pm, {beta}=112.10(3){sup o}, wR{sub 2}=0.0629, 3645 F{sup 2} values, 126 variables for Nd{sub 6}Pt{sub 13}In{sub 22}, a=2821.9(6), b=443.06(9), c=1481.0(3)pm, {beta}=112.39(3){sup o}, wR{sub 2}=0.0543, 3679 F{sup 2} values, 127 variables for Sm{sub 6}Pt{sub 12.30}In{sub 22.70}, and a=2818.5(6), b=439.90(9), c=1480.9(3)pm, {beta}=112.29(3){sup o}, wR{sub 2}=0.0778, 3938 F{sup 2} values, 127 variables for Gd{sub 6}Pt{sub 12.48}In{sub 22.52}. Most platinum atoms in these structures have a distorted trigonal prismatic coordination by rare earth metal and indium atoms. Together, the platinum and indium atoms build up a complex three-dimensional [Pt{sub 12+x}In{sub 23-x}] polyanionic network in which the rare earth metal atoms fill distorted pentagonal and hexagonal channels. The 2c Wyckoff site in these structures plays a peculiar role. This site is occupied by indium in the prototype Tb{sub 6}Pt{sub 12}In{sub 23}, while platinum atoms fill the 2c site in Nd{sub 6}Pt{sub 13}In{sub 22}, leading to a linear Pt{sub 3} chain with Pt-Pt distances of 275pm. The crystals with samarium and gadolinium as rare earth metal component show mixed Pt/In occupancies.},
doi = {10.1016/j.jssc.2005.12.022},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 179,
place = {United States},
year = {Wed Mar 15 00:00:00 EST 2006},
month = {Wed Mar 15 00:00:00 EST 2006}
}
  • Reaction of 3 equiv of 2,6-diisopropylphenol with Ln[N(SiMe{sub 3}){sub 2}]{sub 3}(Ln=Nd, Sm, Er) in refluxing toluene and subsequent crystallization yield pale blue (Nd), deep yellow (Sm), or light pink (Er) crystals of the tris(aryloxide) complexes Ln{sub 2}(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 6}(Ln = Nd(1), Sm(2), Er(3)) in good yield. X-ray crystallographic studies of 1 and 2 reveal centrosymmetric, dimeric units bridged by {eta}{sup 6}-{pi}-arene interactions of a unique aryloxide ligand. Ln-O bond lengths average 2.122(9) (1,Nd) and 2.101(6) {Angstrom} (2,Sm) for terminal ligands and 2.211(8) (1) and 2.198(5) {Angstrom} (2) for bridging aryloxide ligands. {eta}{sup 6}-Arene bridges hold the dimeric unitsmore » together with an average Ln-C distance of 3.035 {Angstrom} for 1 and 2.986 and 3.016 {Angstrom} for the two independent molecules in the asymmetric unit of 2. Compounds 1-3 react with THF in toluene solution to give the THF bisadducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln=Nd(4), Sm(5), Er (6)) in essentially quantitative yield. In a related fashion, Lu(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2} (7) was prepared following the reaction of Lu[N(SiMe{sub 3}){sub 2}]{sub 3} with 3 equiv of diisopropylphenol in the presence of THF. The anhydrous trichlorides of Sm, Pr, Gd, and Yb react with 3 equiv of potassium 2,6-diisopropylphenoxide in THF solution to give the 5-coordinate THF bisadducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln=Sm(5), Pr (8), Gd (9), Yb (10)). X-ray crystal structures have been obtained for Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln = Er (6), Lu (7), Pr (8), Gd(9)). The four compounds are isostructural, and the molecular structure consists of a distorted trigonal bipyramidal lanthanide metal center with two axial THF and three equatorial aryloxide ligands.« less
  • The orthorhombic crystal structures of the series of Ln{sub 4-x}In{sub 5-y}S{sub 13} (Ln=La, Ce, Pr and Nd; x=0.08-0.12, y=0.21-0.24) compounds were investigated by means of X-ray crystal diffraction. The crystals of La{sub 3}In{sub 1.67}S{sub 7} and Gd{sub 3}InS{sub 6} were also obtained unexpectedly from the La-In-S and Gd-In-S systems and no respective Gd{sub 4-x}In{sub 5-y}S{sub 13} was obtained. In the structures of the orthorhombic Ln{sub 4-x}In{sub 5-y}S{sub 13} series and hexagonal La{sub 3}In{sub 1.67}S{sub 7} indium atoms occupy disordered positions in the octahedral and trigonal antiprismatic arrangement of the sulphur atoms. The crystal structure of the La{sub 4}Ag{sub 2}In{sub 4}S{submore » 13} is also given and discussed as an example of quaternary sulphide related to a ternary La-In sulphide. - Graphical abstract: In the series of the Ln{sub 4-x}In{sub 5-y}S{sub 13} (Ln=La, Ce, Pr and Nd; x=0.08-0.12, y=0.21-0.24) compounds the indium atoms occupy disordered position in the octahedral arrangement of the sulphur atoms. The tetrahedral position is ordered.« less
  • Fifteen ternary rare-earth metal gallium silicides have been synthesized using molten Ga as a molten flux. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with three different structures—the early to mid-late rare-earth metals RE=La–Nd, Sm, Gd–Ho, Yb and Y form compounds with empirical formulae RE(Ga xSi 1–x)₂ (0.38≤x≤0.63), which crystallize with the tetragonal α-ThSi₂ structure type (space group I4₁/amd, No. 141; Pearson symbol tI12). The compounds of the late rare-earth crystallize with the orthorhombic α-GdSi₂ structure type (space group Imma, No. 74; Pearson symbol oI12), with refined empirical formula REGa xSi 2–x–y (RE=Ho, Er, Tm;more » 0.33≤x≤0.40, 0.10≤y≤0.18). LuGa₀.₃₂₍₁₎Si₁.₄₃₍₁₎ crystallizes with the orthorhombic YbMn₀.₁₇Si₁.₈₃ structure type (space group Cmcm, No. 63; Pearson symbol oC24). Structural trends are reviewed and analyzed; the magnetic susceptibilities of the grown single-crystals are presented. - Graphical abstract: This article details the exploration of the RE–Ga–Si ternary system with the aim to systematically investigate the structural “boundaries” between the α-ThSi₂ and α-GdSi₂-type structures, and studies of the magnetic properties of the newly synthesized single-crystalline materials. Highlights: • Light rare-earth gallium silicides crystallize in α-ThSi₂ structure type. • Heavy rare-earth gallium silicides crystallize in α-GdSi₂ structure type. • LuGaSi crystallizes in a defect variant of the YbMn₀.₁₇Si₁.₈₃ structure type.« less
  • The crystal structures of the new ternary compounds Sm{sub 4}Ir{sub 13}Ge{sub 9} and LaIr{sub 3}Ge{sub 2} were determined and refined on the basis of single-crystal X-ray diffraction data. They belong to the Ho{sub 4}Ir{sub 13}Ge{sub 9} (oP52, Pmmn) and CeCo{sub 3}B{sub 2} (hP5, P6/mmm) structure types, respectively. The formation of isotypic compounds R{sub 4}Ir{sub 13}Ge{sub 9} with R=La, Ce, Pr, Nd, and RIr{sub 3}Ge{sub 2} with R=Ce, Pr, Nd, was established by powder X-ray diffraction. The RIr{sub 3}Ge{sub 2} (R=La, Ce, Pr, Nd) compounds exist only in as-cast samples and decompose during annealing at 800 Degree-Sign C with the formationmore » of R{sub 4}Ir{sub 13}Ge{sub 9}. The structure of Sm{sub 4}Ir{sub 13}Ge{sub 9} contains intersecting, slightly puckered nets of Ir atoms (4{sup 4})(4{sup 3}.6){sub 2}(4.6{sup 2}){sub 2} and (4{sup 4}){sub 2}(4{sup 3}.6){sub 4}(4.6{sup 2}){sub 2} that are perpendicular to [0 1 1] as well as to [0 -1 1] and [0 0 1]. The Ir atoms are surrounded by Ge atoms that form tetrahedra or square pyramids (where the layers intersect). The Sm and additional Ir atoms (in trigonal-planar coordination) are situated in channels along [1 0 0] (short translation vector). In the structure of LaIr{sub 3}Ge{sub 2} the Ir atoms form planar Kagome nets (3.6.3.6) perpendicular to [0 0 1]. These nets alternate along the short translation vector with layers of La and Ge atoms. - Graphical abstract: The crystal structures contain the nets of Ir atoms as main structural motif: R{sub 4}Ir{sub 13}Ge{sub 9} contains intersecting slightly puckered nets of Ir atoms, whereas in the structure of RIr{sub 3}Ge{sub 2} the Ir atoms form planar Kagome nets. Highlights: Black-Right-Pointing-Pointer The Ir-rich ternary germanides R{sub 4}Ir{sub 13}Ge{sub 9} (R=La, Ce, Pr, Nd, Sm) and RIr{sub 3}Ge{sub 2} (R=La, Ce, Pr, Nd) have been synthesized. Black-Right-Pointing-Pointer The RIr{sub 3}Ge{sub 2} compounds exist only in as-cast samples and decompose during annealing at 800 Degree-Sign C with the formation of R{sub 4}Ir{sub 13}Ge{sub 9}. Black-Right-Pointing-Pointer The structure of R{sub 4}Ir{sub 13}Ge{sub 9} contains intersecting slightly puckered nets of Ir atoms. Black-Right-Pointing-Pointer In the structure of RIr{sub 3}Ge{sub 2} the Ir atoms form planar Kagome nets.« less
  • Crystals represented by the formula (RE){sub 2}In{sub 1-x}Ti{sub 1+x}S{sub 12} with RE/x = Nd/0.22, Sm/0.16, Gd/0.26, and Gd/0.86; Z=2. The structure of the sulfides was probed by X-ray diffraction and details of the structure and its implications on the semiconducting nature of the materials is discussed. 31 refs., 7 figs., 3 tabs.