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Title: The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities

Abstract

This study is concerned with the ternary compounds RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1), which have been previously thought to be the stoichiometric RELiSn{sub 2} phases. These materials crystallize with the base-centered orthorhombic space group Cmcm (No. 63), and can be formally assigned with the CeNiSi{sub 2} structure type (Pearson symbol oC16). Our systematic single-crystal X-ray diffraction studies revealed substantial Li-deficiencies in all cases, with SmSn{sub 2} (space group Cmmm, ZrGa{sub 2} structure type, Pearson symbol oC12) and GdSn{sub 2} (space group Cmcm, ZrSi{sub 2} structure type, Pearson symbol oC12) being completely lithium-free. The structure refinements also uncovered positional disorder on the Sn site neighboring the vacancies. The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{sub 2} and GdSn{sub 2} structures are devoid of any disorder. Temperature-dependent studies of the magnetic response of the title compounds are also presented and discussed. -- Graphical abstract: RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) crystallize in a defect variants of the CeNiSi{sub 2} structure type (a). The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{submore » 2} (b) and GdSn{sub 2} (c) structures are devoid of any disorder. Highlights: • The crystal structures of the RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) compounds are revised using single-crystal X-ray diffraction data. • The structure is a filled derivative of the ZrSi{sub 2} structure type or defect variant of the CeNiSi{sub 2} structure type. • SmSn{sub 2} is isotypic with the ZrGa{sub 2} structure, while RESn{sub 2} (RE=Gd–Lu) are isotypic with the ZrSi{sub 2} structure.« less

Authors:
; ;  [1]; ; ;  [2];  [1]
  1. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (United States)
  2. Department of Physics, University of Maryland, College Park, MD 20742 (United States)
Publication Date:
OSTI Identifier:
22275852
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 211; Journal Issue: Complete; Other Information: Copyright (c) 2013 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; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; DEFECTS; ELECTRONIC STRUCTURE; MAGNETIC SUSCEPTIBILITY; MONOCRYSTALS; ORTHORHOMBIC LATTICES; SPACE GROUPS; SYNTHESIS; TEMPERATURE DEPENDENCE; X-RAY DIFFRACTION; ZIRCONIUM SILICIDES

Citation Formats

Makongo, Julien P.A., Suen, Nian-Tzu, Guo, Shengping, Saha, Shanta, Greene, Richard, Paglione, Johnpierre, and Bobev, Svilen, E-mail: bobev@udel.edu. The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities. United States: N. p., 2014. Web. doi:10.1016/J.JSSC.2013.12.010.
Makongo, Julien P.A., Suen, Nian-Tzu, Guo, Shengping, Saha, Shanta, Greene, Richard, Paglione, Johnpierre, & Bobev, Svilen, E-mail: bobev@udel.edu. The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities. United States. doi:10.1016/J.JSSC.2013.12.010.
Makongo, Julien P.A., Suen, Nian-Tzu, Guo, Shengping, Saha, Shanta, Greene, Richard, Paglione, Johnpierre, and Bobev, Svilen, E-mail: bobev@udel.edu. 2014. "The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities". United States. doi:10.1016/J.JSSC.2013.12.010.
@article{osti_22275852,
title = {The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities},
author = {Makongo, Julien P.A. and Suen, Nian-Tzu and Guo, Shengping and Saha, Shanta and Greene, Richard and Paglione, Johnpierre and Bobev, Svilen, E-mail: bobev@udel.edu},
abstractNote = {This study is concerned with the ternary compounds RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1), which have been previously thought to be the stoichiometric RELiSn{sub 2} phases. These materials crystallize with the base-centered orthorhombic space group Cmcm (No. 63), and can be formally assigned with the CeNiSi{sub 2} structure type (Pearson symbol oC16). Our systematic single-crystal X-ray diffraction studies revealed substantial Li-deficiencies in all cases, with SmSn{sub 2} (space group Cmmm, ZrGa{sub 2} structure type, Pearson symbol oC12) and GdSn{sub 2} (space group Cmcm, ZrSi{sub 2} structure type, Pearson symbol oC12) being completely lithium-free. The structure refinements also uncovered positional disorder on the Sn site neighboring the vacancies. The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{sub 2} and GdSn{sub 2} structures are devoid of any disorder. Temperature-dependent studies of the magnetic response of the title compounds are also presented and discussed. -- Graphical abstract: RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) crystallize in a defect variants of the CeNiSi{sub 2} structure type (a). The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{sub 2} (b) and GdSn{sub 2} (c) structures are devoid of any disorder. Highlights: • The crystal structures of the RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) compounds are revised using single-crystal X-ray diffraction data. • The structure is a filled derivative of the ZrSi{sub 2} structure type or defect variant of the CeNiSi{sub 2} structure type. • SmSn{sub 2} is isotypic with the ZrGa{sub 2} structure, while RESn{sub 2} (RE=Gd–Lu) are isotypic with the ZrSi{sub 2} structure.},
doi = {10.1016/J.JSSC.2013.12.010},
journal = {Journal of Solid State Chemistry},
number = Complete,
volume = 211,
place = {United States},
year = 2014,
month = 3
}
  • The (NH{sub 4})[Fe(AsO{sub 4}){sub 1-x}(PO{sub 4}){sub x}F] (x=0.3, 0.6, 0.8) series of compounds has been synthesized under mild hydrothermal conditions. The compounds crystallize in the orthorhombic Pna2{sub 1} space group, with the unit-cell parameters a=13.1718(1), b=6.5966(6), c=10.797(1) A for x=0.3; a=13.081(1), b=6.5341(6), c=10.713(1) A for x=0.6 and a=13.0329(9), b=6.4994(4), c=10.6702(6) A for x=0.8, with the volumes 938.6(1), 915.7(1) and 903.8(1) A{sup 3}, respectively, with Z=8. Single crystals of (NH{sub 4})[Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}F] heated under air atmosphere at 465 deg. C remain as single crystals, changing the composition to Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}. This later phase belongs tomore » the orthorhombic Imam space group, with the unit cell parameters a=13.328(2), b=6.5114(5), c=10.703(1) A, V=928.9(2) A{sup 3} and Z=12. The crystal structure of the ammonium phases consists of a KTP three-dimensional framework constructed by chains formed by alternating Fe(2)O{sub 4}F{sub 2} or Fe(1)O{sub 4}F{sub 2} octahedra and As/P(2)O{sub 4} or As/P(1)O{sub 4} tetrahedra, respectively. These octahedra and tetrahedra are linked by a common oxygen vertex. The chains run along the 'a' and 'b' crystallographic axes. The crystal structure of Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3} is a three-dimensional skeleton derived from that of the precursor, formed from (100) sheets stacked along the [001] direction, and interconnected by chains of alternating Fe(2)O{sub 6} octahedra and As/P(2)O{sub 4} tetrahedra sharing a vertex in the 'a' direction. Transmission electronic microscopy of this compound indicates the existence of unconnected external cavities with a BET surface area of 3.91(3) m{sup 2} g{sup -1}. The diffuse reflectance spectra in the visible region show the forbidden electronic transitions characteristic of the Fe(III) d{sup 5}-high spin cation in slightly distorted octahedral geometry, for all the compounds. The ESR spectra for all the compounds, carried out from room temperature to 4.2 K, remain isotropic with variation in temperature; the g-value is 1.99(1). Magnetic measurements indicate the predominance of antiferromagnetic interactions, with Neel temperatures near to 70.0 and 50.0 K for the ammonium phases and Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.30}, respectively. At low temperatures a spin canting phenomenon for Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.30} is detected. - Graphical abstract: The relationship between the |100| and |010| chains in (NH{sub 4})[Fe(AsO{sub 4}){sub 1-x}(PO{sub 4}){sub x}F] left and the |100| chains and the (001) sheets in Fe(AsO{sub 4}){sub 0.7}(PO{sub 4}){sub 0.3}.« less
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