Rare earth-nickel-indides Dy{sub 5}Ni{sub 2}In{sub 4} and RE{sub 4}Ni{sub 11}In{sub 20} (RE=Gd, Tb, Dy)
- Inorganic Chemistry Department, Ivan Franko National University of Lviv, Kyryla and Mephodiya Street 6, 79005 Lviv (Ukraine)
- Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster, Corrensstrasse 30, 48149 Muenster (Germany)
The new rare earth metal (RE)-nickel-indides Dy{sub 5}Ni{sub 2}In{sub 4} and RE{sub 4}Ni{sub 11}In{sub 20} (RE=Gd, Tb, Dy) were synthesized from the elements by arc-melting. Well-shaped single crystals were obtained by special annealing sequences. The four indides were investigated by X-ray diffraction on powders and single crystals: Lu{sub 5}Ni{sub 2}In{sub 4} type, Pbam, Z=2, a=1784.2(8), b=787.7(3), c=359.9(1) pm, wR{sub 2}=0.0458, 891 F{sup 2} values, 36 variables for Dy{sub 5}Ni{sub 2}In{sub 4}, U{sub 4}Ni{sub 11}Ga{sub 20} type, C2/m, a=2254.0(9), b=433.8(3), c=1658.5(8) pm, {beta}=124.59(2){sup o}, wR{sub 2}=0.0794, 2154 F{sup 2} values, 108 variables for Gd{sub 4}Ni{sub 11}In{sub 20}, a=2249.9(8), b=432.2(1), c=1657.9(5) pm, {beta}=124.59(2){sup o}, wR{sub 2}=0.0417, 2147 F{sup 2} values, 108 variables for Tb{sub 4}Ni{sub 11}In{sub 20}, and a=2252.2(5), b=430.6(1), c=1659.7(5) pm, {beta}=124.58(2){sup o}, wR{sub 2}=0.0550, 2003 F{sup 2} values, 109 variables for Dy{sub 4}Ni{sub 10.80}In{sub 20.20}. The 2d site in the dysprosium compound shows mixed Ni/In occupancy. Most nickel atoms in both series of compounds exhibit trigonal prismatic coordination by indium and rare earth atoms. Additionally, in the RE{sub 4}Ni{sub 11}In{sub 20} compounds one observes one-dimensional nickel clusters (259 pm Ni{sub 1}-Ni{sub 6} in Dy{sub 4}Ni{sub 10.80}In{sub 20.20}) that are embedded in an indium matrix. While only one short In{sub 1}-In{sub 2} contact at 324 pm is observed in Dy{sub 5}Ni{sub 2}In{sub 4}, the more indium-rich Dy{sub 4}Ni{sub 10.80}In{sub 20.20} structure exhibits a broader range in In-In interactions (291-364 pm). Together the nickel and indium atoms build up polyanionic networks, a two-dimensional one in Dy{sub 5}Ni{sub 2}In{sub 4} and a complex three-dimensional network in Dy{sub 4}Ni{sub 10.80}In{sub 20.20}. These features have a clear consequence on the dysprosium coordination, i.e. a variety of short Dy-Dy contacts (338-379 pm) in Dy{sub 5}Ni{sub 2}In{sub 4}, while the dysprosium atoms are well separated (430 pm shortest Dy-Dy distance) within the distorted hexagonal channels of the [Ni{sub 10.80}In{sub 20.20}] polyanion of Dy{sub 4}Ni{sub 10.80}In{sub 20.20}. The crystal chemistry of both structure types is comparatively discussed. - Graphical abstract: Crystal structure of Dy{sub 5}Ni{sub 2}In{sub 4}.
- OSTI ID:
- 21128260
- Journal Information:
- Journal of Solid State Chemistry, Vol. 181, Issue 4; Other Information: DOI: 10.1016/j.jssc.2008.01.035; PII: S0022-4596(08)00069-8; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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