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Title: New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}

Abstract

New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Nd{sub 25}B{sub 12}C{sub 28}: space group P1-bar, a=8.3209(7) A, b=8.3231(6) A, c=29.888(2) A, {alpha}=83.730(9){sup o}, {beta}=83.294(9){sup o}, {gamma}=89.764(9){sup o}. Pr{sub 25}B{sub 14}C{sub 26}: space group P2{sub 1}/c, a=8.4243(5) A, b=8.4095(6) A, c=30.828(1) A, {beta}=105.879(4){sup o}, V=2100.6(2) A{sup 3}, (R1=0.048 (wR2=0.088) from 2961 reflections with I{sub o}>2{sigma}(I{sub o})); for Nd{sub 25}B{sub 14}C{sub 26} space group P2{sub 1}/c, Z=2, a=8.3404(6) A, b=8.3096(6) A, c=30.599(2) A, {beta}=106.065(1){sup o}. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){submore » 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Accordingly, extended Hueckel tight-binding calculations indicate that the compounds are metallic in character. - Graphical Abstract: New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms, respectively. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Highlights: > New rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}. > Structures contain 1-D finite B{sub 3}C{sub 3}, B{sub 2}C{sub 4}, BC{sub 2} units as well as isolated C atoms. > B/C distribution in the crystal structures was approved by EH-TB calculations.« less

Authors:
 [1];  [2]; ;  [1];  [3];  [3]
  1. Max-Planck-Institut fuer Festkoerperforschung, Heisenbergstrasse 1, Postfach 800665, D-70569 Stuttgart (Germany)
  2. (Ukraine)
  3. Sciences Chimiques de Rennes, UMR 6226 CNRS, Ecole Nationale Superieure de Chimie de Rennes, Universite de Rennes 1, Avenue du General Leclerc, F-35042 Rennes cedex (France)
Publication Date:
OSTI Identifier:
21580169
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 184; Journal Issue: 7; Other Information: DOI: 10.1016/j.jssc.2011.04.039; PII: S0022-4596(11)00220-9; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; BORON; CARBIDES; CARBON; CARBON IONS; ELECTRONIC STRUCTURE; MONOCLINIC LATTICES; MONOCRYSTALS; NEODYMIUM IONS; RARE EARTHS; RHENIUM IONS; SPACE GROUPS; THREE-DIMENSIONAL CALCULATIONS; X-RAY DIFFRACTION; CARBON COMPOUNDS; CHARGED PARTICLES; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; ELEMENTS; IONS; METALS; NONMETALS; SCATTERING; SEMIMETALS; SYMMETRY GROUPS

Citation Formats

Babizhetskyy, Volodymyr, E-mail: v.babizhetskyy@googlemail.com, Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv, Mattausch, Hansjuergen, Simon, Arndt, Gautier, Regis, E-mail: rgautier@ensc-rennes.fr, and Halet, Jean-Francois, E-mail: halet@univ-rennes1.fr. New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}. United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.04.039.
Babizhetskyy, Volodymyr, E-mail: v.babizhetskyy@googlemail.com, Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv, Mattausch, Hansjuergen, Simon, Arndt, Gautier, Regis, E-mail: rgautier@ensc-rennes.fr, & Halet, Jean-Francois, E-mail: halet@univ-rennes1.fr. New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}. United States. doi:10.1016/j.jssc.2011.04.039.
Babizhetskyy, Volodymyr, E-mail: v.babizhetskyy@googlemail.com, Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv, Mattausch, Hansjuergen, Simon, Arndt, Gautier, Regis, E-mail: rgautier@ensc-rennes.fr, and Halet, Jean-Francois, E-mail: halet@univ-rennes1.fr. Fri . "New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}". United States. doi:10.1016/j.jssc.2011.04.039.
@article{osti_21580169,
title = {New members of ternary rare-earth metal boride carbides containing finite boron-carbon chains: RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}},
author = {Babizhetskyy, Volodymyr, E-mail: v.babizhetskyy@googlemail.com and Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya Street 6, UA-79005 Lviv and Mattausch, Hansjuergen and Simon, Arndt and Gautier, Regis, E-mail: rgautier@ensc-rennes.fr and Halet, Jean-Francois, E-mail: halet@univ-rennes1.fr},
abstractNote = {New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Nd{sub 25}B{sub 12}C{sub 28}: space group P1-bar, a=8.3209(7) A, b=8.3231(6) A, c=29.888(2) A, {alpha}=83.730(9){sup o}, {beta}=83.294(9){sup o}, {gamma}=89.764(9){sup o}. Pr{sub 25}B{sub 14}C{sub 26}: space group P2{sub 1}/c, a=8.4243(5) A, b=8.4095(6) A, c=30.828(1) A, {beta}=105.879(4){sup o}, V=2100.6(2) A{sup 3}, (R1=0.048 (wR2=0.088) from 2961 reflections with I{sub o}>2{sigma}(I{sub o})); for Nd{sub 25}B{sub 14}C{sub 26} space group P2{sub 1}/c, Z=2, a=8.3404(6) A, b=8.3096(6) A, c=30.599(2) A, {beta}=106.065(1){sup o}. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Accordingly, extended Hueckel tight-binding calculations indicate that the compounds are metallic in character. - Graphical Abstract: New ternary rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28} were synthesized by co-melting the elements. Nd{sub 25}B{sub 12}C{sub 28} is stable up to 1440 K. RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) exist above 1270 K. The crystal structures were investigated by means of single-crystal X-ray diffraction. Their structures consist of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with cumulene-like molecules [B{sub 2}C{sub 4}]{sup 6-} and [B{sub 3}C{sub 3}]{sup 7-}, nearly linear [BC{sub 2}]{sup 5-} and bent [BC{sub 2}]{sup 7-} units and isolated carbon atoms, respectively. Structural and theoretical analysis suggests the ionic formulation for RE{sub 25}B{sub 14}C{sub 26}: (RE{sup 3+}){sub 25}[B{sub 2}C{sub 4}]{sup 6-}([B{sub 3}C{sub 3}]{sup 7-}){sub 2}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.5e{sup -} and for Nd{sub 25}B{sub 12}C{sub 28}: (Nd{sup 3+}){sub 25}([B{sub 2}C{sub 4}]{sup 6-}){sub 3}([BC{sub 2}]{sup 5-}){sub 4}([BC{sub 2}]{sup 7-}){sub 2}(C{sup 4-}){sub 4}.7e{sup -}. Highlights: > New rare-earth metal boride carbides RE{sub 25}B{sub 14}C{sub 26} (RE=Pr, Nd) and Nd{sub 25}B{sub 12}C{sub 28}. > Structures contain 1-D finite B{sub 3}C{sub 3}, B{sub 2}C{sub 4}, BC{sub 2} units as well as isolated C atoms. > B/C distribution in the crystal structures was approved by EH-TB calculations.},
doi = {10.1016/j.jssc.2011.04.039},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 7,
volume = 184,
place = {United States},
year = {2011},
month = {7}
}