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Int. J. Mol. Sci. 2015, 16(4), 9017-9036; doi:10.3390/ijms16049017

Crystal Structure, Chemical Bonding and Magnetism Studies for Three Quinary Polar Intermetallic Compounds in the (Eu1−xCax)9In8(Ge1−ySny)8 (x = 0.66, y = 0.03) and the (Eu1−xCax)3In(Ge3−ySn1+y) (x = 0.66, 0.68; y = 0.13, 0.27) Phases

1
Department of Chemistry, Chungbuk National University, Cheongju, Chungbuk 362-763, Korea
2
Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea
3
Department of Chemistry, Dong-A University, Busan 604-714, Korea
*
Author to whom correspondence should be addressed.
Academic Editor: Habil. Mihai V. Putz
Received: 25 February 2015 / Revised: 9 April 2015 / Accepted: 9 April 2015 / Published: 22 April 2015
(This article belongs to the Special Issue Chemical Bond and Bonding 2015)
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Abstract

Three quinary polar intermetallic compounds in the (Eu1−xCax)9In8(Ge1−ySny)8 (x = 0.66, y = 0.03) and the (Eu1−xCax)3In(Ge3-ySn1+y) (x = 0.66, 0.68; y = 0.13, 0.27) phases have been synthesized using the molten In-metal flux method, and the crystal structures are characterized by powder and single-crystal X-ray diffractions. Two orthorhombic structural types can be viewed as an assembly of polyanionic frameworks consisting of the In(Ge/Sn)4 tetrahedral chains, the bridging Ge2 dimers, either the annulene-like “12-membered rings” for the (Eu1−xCax)9In8(Ge1−ySny)8 series or the cis-trans Ge/Sn-chains for the (Eu1−xCax)3In(Ge3−ySn1+y) series, and several Eu/Ca-mixed cations. The most noticeable difference between two structural types is the amount and the location of the Sn-substitution for Ge: only a partial substitution (11%) occurs at the In(Ge/Sn)4 tetrahedron in the (Eu1−xCax)9In8(Ge1−ySny)8 series, whereas both a complete and a partial substitution (up to 27%) are observed, respectively, at the cis-trans Ge/Sn-chain and at the In(Ge/Sn)4 tetrahedron in the (Eu1−xCax)3In(Ge3−ySn1+y) series. A series of tight-binding linear muffin-tin orbital calculations is conducted to understand overall electronic structures and chemical bonding among components. Magnetic susceptibility measurement indicates a ferromagnetic ordering of Eu atoms below 5 K for Eu1.02(1)Ca1.98InGe2.87(1)Sn1.13. View Full-Text
Keywords: polar intermetallics; electronic structure; chemical bonding; single-crystal X-ray diffraction; magnetism polar intermetallics; electronic structure; chemical bonding; single-crystal X-ray diffraction; magnetism
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MDPI and ACS Style

Woo, H.; Jang, E.; Kim, J.; Lee, Y.; Kim, J.; You, T.-S. Crystal Structure, Chemical Bonding and Magnetism Studies for Three Quinary Polar Intermetallic Compounds in the (Eu1−xCax)9In8(Ge1−ySny)8 (x = 0.66, y = 0.03) and the (Eu1−xCax)3In(Ge3−ySn1+y) (x = 0.66, 0.68; y = 0.13, 0.27) Phases. Int. J. Mol. Sci. 2015, 16, 9017-9036.

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