Powder data for some new europium antimonides and bismuthides

Taylor, John; Calvert, L. D.; Wang, Y.

doi:10.1107/s0021889879012309

Cited by 24 publications

(6 citation statements)

References 7 publications

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“…27 The Al 3 triangles and rare earth sites are each partially occupied somewhat reminiscent of the Al 4 tetrahedra and Eu 2+ in this Eu 5 Al 3 Sb 6 compound. The Eu−Sb bond distances presented are very similar to other binary Eu−Sb phases such as Eu 5 Sb 3 , 28 Eu 11 Sb 10 , 28 and Eu 2 Sb 3 . 28 The rocksalt-like nature of this compound is reminiscent of that of YbSb, 29 a rare-earth antimonide compound that features the NaCl structure type as well.…”

Section: ■ Introductionsupporting

confidence: 76%

Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Shen

Wang

et al. 2022

Chem. Mater.

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The new Eu 5 Al 3 Sb 6 phase has been successfully synthesized as a pure phase through Sn flux methods yielding large, high-quality crystals. This structure type features disordered Al clusters that appear in the form of dual tetrahedra. It crystallizes in the monoclinic C2/m space group exhibiting a rock-salt-like Eu−Sb framework with [Al 4 ] tetrahedra replacing some of the cationic Eu atoms (space group: C2/m, a = 8.151(1) Å, b = 14.181(2) Å, c = 8.145(1) Å, β = 109.577(2)°). The structure models the [Al 4 ] as dual tetrahedra with the Al atom sites 37.5% occupied along with Eu present on the central site at 8% occupancy and the remainder of the site being vacant. The presence of the [Al 4 ] cluster is further supported by HRTEM. Electronic structure calculations show that this material is a semimetal with observed band crossings close to the Fermi level. Strong Al−Sb antibonding interactions were found from COHP calculations close to the Fermi level and provide the rationale for the deficiency of the Al cluster. Mossbauer spectroscopy on Eu-151 and Sb-121 provides oxidation states of 2+ and 3− along with the local environment. Magnetic susceptibility measurements can be described well with a Curie−Weiss law where an effective moment of 7.80 μ B /mol Eu is obtained, consistent with Eu 2+ , and show canted antiferromagnetic behavior below 10 K. Temperature dependent resistivity shows a Kondo-like low-temperature upturn caused by enhanced scattering of the itinerant electrons with the 4f orbitals of Eu.

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Section: ■ Introductionsupporting

confidence: 76%

Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Shen

Wang

et al. 2022

Chem. Mater.

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“…The hexagonal Mn 5 Si 3 type structure has been reported for the large rare earth elements R = La±Nd, Sm, Gd, and Tb [29±31]. Finally, the orthorhombic b-Yb 5 Sb 3 type structure has been reported for Eu 5 Bi 3 [35], Yb 5 Bi 3 [36], and here for Sc 5 Bi 3 . Thus, Gd 5 Bi 3 and Tb 5 Bi 3 seem to be dimorphic, with the Y 5 Bi 3 type compounds possibly occuring with a slightly higher rare earth content [30].…”

Section: Discussionmentioning

confidence: 71%

Preparation and Crystal Structures of some Binary Pnictides of Scandium, Zirconium, and Hafnium: Sc5Bi3, ZrBi, α-HfSb, HfBi, HfBi2, and the Compound Zr5Bi3X1-x, Possibly Stabilized by an Impurity (X)

Haase

Block

Jeitschko

2001

Z. anorg. allg. Chem.

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The title compounds were prepared by reaction of the elemental components. Of these Sc 5 Bi 3 is a new compound. Its orthorhombic b-Yb 5 Sb 3 type crystal structure was determined from single-crystal X-ray data: Pnma, a = 1124.4(1) pm, b = 888.6(1) pm, c = 777.2(1) pm, R = 0.024 for 1140 structure factors and 44 variable parameters. For the other compounds we have established the crystal structures. ZrBi has ZrSb type structure with a noticeable homogeneity range. This structure type was also found for the low temperature (a) form of HfSb and for HfBi. For a-HfSb this structure was refined from single-crystal X-ray data: Cmcm, a = 377.07(4) pm, b = 1034.7(1) pm, c = 1388.7(1) pm, R = 0.043 for 432 F values and 22 variables. HfBi 2 has TiAs 2 type structure: Pnnm, a = 1014.2(2) pm, b = 1563.9(3) pm, c = 396.7(1) pm. The structure was refined from single-crystal data to a residual of R = 0.074 for 1038 F values and 40 variables. In addition, a zirconium bismuthide, possibly stabilized by light impurity elements X and crystallizing with the hexagonal Mo 5 Si 3 C 1±x type structure, was observed: Zr 5 Bi 3 X 1±x , a = 873.51(6) pm, c = 599.08(5) pm. The positions of the heavy atoms of this structure were refined from X-ray powder film data. Various aspects of impurity stabilization of intermetallics are discussed. 1034,7(1) pm, c = 1388,7(1) pm, R = 0,043 fu È r 432 F-Werte und 22 Variable. HfBi 2 ist mit TiAs 2 isotyp: Pnnm, a = 1014,2(2) pm, b = 1563,9(3) pm, c = 396,7(1) pm. Die Struktur wurde anhand von Einkristalldaten verfeinert. Es blieb ein Restwert von R = 0,074 fu È r 1038 F-Werte und 40 Variable. Auûerdem wurde ein Zirkoniumwismutid erhalten, das mo È glicherweise durch Verunreinigung mit leichten Elementen X stabilisiert ist und mit der hexagonalen Mo 5 Si 3 C 1±x -Struktur kristallisiert: Zr 5 Bi 3 X 1±x , a = 873,51(6) pm, c = 599,08(5) pm. Die Schweratom-Positionen dieser Struktur wurden durch Ro È ntgen-Guinier-Filmdaten verfeinert. Einige Gesichtspunkte zur Frage der Stabilisierung intermetallischer Phasen durch Verunreinigungen werden diskutiert.

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“…7 mg), or could be a sign for a secondary phase present in the sample. These could be Eu 11 Cd 6 Sb 12 , EuCd 2 Sb 2 , Eu 11 Sb 10 , or Eu 16 Sb 11 , but we have no solid crystallographic evidence to help with the identification of the side product(s).…”

Section: Resultsmentioning

confidence: 92%

Structural Variability versus Structural Flexibility. A Case Study of Eu₉Cd_4+xSb₉ and Ca₉Mn_4+xSb₉ (x ≈ ¹/₂)

Liu

Xia

et al. 2014

Inorg. Chem.

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The focus of this article is on the synthesis and structural characterization of the new ternary antimonides Eu(9)Cd(4+x)Sb(9) and Ca(9)Mn(4+x)Sb(9) (x ≈ (1)/2). Although these compounds have analogous chemical makeup and formulas, which may suggest isotypism, they actually belong to two different structure types. Eu(9)Cd(4.45(1))Sb(9) is isostructural with the previously reported Eu(9)Zn(4.5)Sb(9) (Pbam), and its structure has unit cell parameters a = 12.9178(11) Å, b = 23.025(2) Å, and c = 4.7767(4) Å. Ca(9)Mn(4.41(1))Sb(9) crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 12.490(2) Å, b = 4.6292(8) Å, and c = 44.197(8) Å and constitutes a new structure type. The two structures are compared and contrasted, and the structural relationships are discussed. Exploratory work aimed at the arsenic-based analogues of either type led to the identification of Ca(9)Zn(4.46(1))As(9), forming with the latter structure [a = 11.855(2) Å, b = 4.2747(8) Å, and c = 41.440(8) Å]. Differential thermal analysis and electrical resistivity measurements, performed on single crystals of Ca(9)Zn(4+x)As(9), indicate high thermal stability and semiconducting behavior. Magnetic susceptibility measurements on Eu(9)Cd(4+x)Sb(9) samples confirm the expected Eu(2+) ([Xe]4f(7)) ground state.

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Powder data for some new europium antimonides and bismuthides

Abstract: X-ray powder diffraction data are reported for the phases EusSb3, Eu11Sblo, Eu2Sb3, EusBi3, Eu4Bi3 and EullBilo.

Cited by 24 publications

References 7 publications

Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Preparation and Crystal Structures of some Binary Pnictides of Scandium, Zirconium, and Hafnium: Sc5Bi3, ZrBi, α-HfSb, HfBi, HfBi2, and the Compound Zr5Bi3X1-x, Possibly Stabilized by an Impurity (X)

Structural Variability versus Structural Flexibility. A Case Study of Eu₉Cd_4+xSb₉ and Ca₉Mn_4+xSb₉ (x ≈ ¹/₂)

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Powder data for some new europium antimonides and bismuthides

Abstract: X-ray powder diffraction data are reported for the phases EusSb3, Eu11Sblo, Eu2Sb3, EusBi3, Eu4Bi3 and EullBilo.

Cited by 24 publications

References 7 publications

Eu5Al3Sb6: Al4 Tetrahedra Embedded in a Rock-Salt-Like Structure

Eu5Al3Sb6: Al4 Tetrahedra Embedded in a Rock-Salt-Like Structure

Preparation and Crystal Structures of some Binary Pnictides of Scandium, Zirconium, and Hafnium: Sc5Bi3, ZrBi, α-HfSb, HfBi, HfBi2, and the Compound Zr5Bi3X1-x, Possibly Stabilized by an Impurity (X)

Structural Variability versus Structural Flexibility. A Case Study of Eu9Cd4+xSb9 and Ca9Mn4+xSb9 (x ≈ 1/2)

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Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Eu₅Al₃Sb₆: Al₄ Tetrahedra Embedded in a Rock-Salt-Like Structure

Structural Variability versus Structural Flexibility. A Case Study of Eu₉Cd_4+xSb₉ and Ca₉Mn_4+xSb₉ (x ≈ ¹/₂)