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Ruthenium Intermetallics Grown from La−Ni Flux: Synthesis, Structure, and Physical Properties

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Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306
Applied Superconductivity Center, National High Magnetic Field Laboratory, Tallahassee, Florida 32310
*To whom correspondence should be addressed. E-mail: [email protected]. Phone: (850) 644-4074. Fax: (850) 644-8281.
Cite this: Inorg. Chem. 2010, 49, 6, 2773–2781
Publication Date (Web):February 8, 2010
https://doi.org/10.1021/ic902151d
Copyright © 2010 American Chemical Society

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    Abstract

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    Crystals of three new intermetallic compounds were grown from reactions of ruthenium with other elements in La0.8Ni0.2 eutectic flux. The new boride LaRu2Al2B crystallizes in a filled CeMg2Si2 structure type (P4/mmm, a = 4.2105(5) Å, c = 5.6613(8); Z = 1, R1 = 0.014), with Ru atoms forming a planar square net; B atoms center alternating Ru squares, which is an unusual coordination of boron by transition metals. Al atoms connect the Ru2B layers, forming large voids where La ions reside. The chemical bonding analysis using the electron localization function (ELF) reveals two-center covalent bonding between Al atoms, an absence of direct Ru−Ru interactions, and three-centered bonds between Ru and B or Al atoms. The band structure calculation shows LaRu2Al2B to be metallic, which is in agreement with the observed temperature independent paramagnetism and heat capacity data. The crystal structure of La2Ni2−xRuxAl (HT-Pr2Co2Al-type; x = 0.21(1) and x = 0.76(1); C2/c; a = 9.9001(3) Å, b = 5.7353(1) Å, c = 7.8452(2) Å, β = 104.275(1); Z = 4, R1 = 0.016 for x = 0.76(1)) features infinite [Ni2−xRuxAl] spiral-twisted chains composed of Al2M2-rhombic units (M = Ni/Ru) seen in many La−Ni−Al intermetallics. The structure of La6SnNi3.67Ru0.76Al3.6 (Nd6Co5Ge2.2-type; Pm2, a = 9.620(1) Å, c = 4.2767(9) Å; Z = 1, R1 = 0.015) is composed of a three-dimensional [Ni3.67Ru0.76Al3.6]3 network with large hexagonal channels accommodating interconnected tin-centered lanthanum clusters Sn@La9.

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    Crystallographic data for (I), (II), (III), and (IV) in the form of CIF files. Table S1 with interatomic distances in the structures of (I), (II), (III), (IV), Table S2 summarizing information about ternary La−Ni−Al phases, and Table S3 with results of EDX analysis. Figure S1 with plots of χ versus T at different external fields for LaRu2Al2B. This material is available free of charge via the Internet at http://pubs.acs.org.

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