Crystal structure, chemical bonding and magnetism studies for three quinary polar intermetallic compounds in the (Eu(1-x)Ca(x))9In8(Ge(1-y)Sn(y))8 (x = 0.66, y = 0.03) and the (Eu(1-x)Ca(x))3In(Ge(3-y)Sn(1+y)) (x = 0.66, 0.68; y = 0.13, 0.27) phases.
Three quinary polar intermetallic compounds in the (Eu(1-x)Ca(x))9In8(Ge(1-y)Sn(y))8 (x = 0.66, y = 0.03) and the (Eu(1-x)Ca(x))3In(Ge(3-y)Sn(1+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 (Eu(1-x)Ca(x))9In8(Ge(1-y)Sn(y))8 series or the cis-trans Ge/Sn-chains for the (Eu(1-x)Ca(x))3In(Ge(3-y)Sn(1+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 (Eu(1-x)Ca(x))9In8(Ge(1-y)Sn(y))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 (Eu(1-x)Ca(x))3In(Ge(3-y)Sn(1+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.
Department of Chemistry, Chungbuk National University, Cheongju, Chungbuk 362-763, Korea. hiwoo52@chungbuk.ac.kr.
Hyein
H
Woo
Department of Chemistry, Chungbuk National University, Cheongju, Chungbuk 362-763, Korea. s2jeyoung@chungbuk.ac.kr.
Eunyoung
E
Jang
Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea. kj0815@kaist.ac.kr.
Jin
J
Kim
Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Korea. yunholee@kaist.ac.kr.
Yunho
Y
Lee
Department of Chemistry, Dong-A University, Busan 604-714, Korea. jskimm@dau.ac.kr.
Jongsik
J
Kim
Department of Chemistry, Chungbuk National University, Cheongju, Chungbuk 362-763, Korea. tsyou@chungbuk.ac.kr.
Tae-Soo
TS
You
D000497:Alloys / Q000737:chemistry; D002118:Calcium / Q000737:chemistry; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005063:Europium / Q000737:chemistry; D005857:Germanium / Q000737:chemistry; D060328:Magnetic Phenomena; D008968:Molecular Conformation; D033362:Powder Diffraction; D014001:Tin / Q000737:chemistry
D000497:Alloys; D056831:Coordination Complexes; D005857:Germanium; D005063:Europium; D014001:Tin; D002118:Calcium