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Exploratory Work in the Quaternary System of Ca?Eu?Cd?Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.


ABSTRACT: Investigation of the quaternary system, Ca?Eu?Cd?Sb, led to a discovery of the new solid solutions, Ca1-xEuxCd?Sb?, with the CaAl?Si? structure type (x ? 0.3?0.9, hP5, P 3 ¯ m1, a = 4.6632(5)?4.6934(3) Å, c = 7.630(1)?7.7062(7) Å), Ca2-xEuxCdSb? with the Yb?CdSb? type (x ? 0.6, oS20, Cmc2?, a = 4.646(2) Å, b = 17.733(7) Å, c = 7.283(3) Å), and Eu11-xCaxCd?Sb12 with the Sr11Cd?Sb12 type (x ? 1, mS58, C2/m, a = 32.407(4) Å, b = 4.7248(5) Å, c = 12.377(1) Å, ? = 109.96(1)°). Systematic crystallographic studies of the Ca1-xEuxCd?Sb? series indicated expansion of the unit cell upon an increase in the Eu content, in accordance with a larger ionic radius of Eu2+ vs. Ca2+. The Ca2-xEuxCdSb? composition with x ? 0.6 adopts the non-centrosymmetric space group, Cmc2?, although the parent ternary phase, Ca?CdSb?, crystallizes in the centrosymmetric space group, Pnma. Two non-equivalent Ca sites in the layered crystal structure of Ca2-xEuxCdSb? get unevenly occupied by Eu, with a preference for the interlayer position, which offers a larger available volume. Similar size-driven preferred occupation is observed in the Eu11-xCaxCd?Sb12 solid solution with x ? 1.

SUBMITTER: Ovchinnikov A 

PROVIDER: S-EPMC6265713 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Exploratory Work in the Quaternary System of Ca⁻Eu⁻Cd⁻Sb: Synthesis, Crystal, and Electronic Structures of New Zintl Solid Solutions.

Ovchinnikov Alexander A   Darone Gregory M GM   Saparov Bayrammurad B   Bobev Svilen S  

Materials (Basel, Switzerland) 20181031 11


Investigation of the quaternary system, Ca⁻Eu⁻Cd⁻Sb, led to a discovery of the new solid solutions, Ca<sub>1-<i>x</i></sub>Eu<i><sub>x</sub></i>Cd₂Sb₂, with the CaAl₂Si₂ structure type (<i>x</i> ≈ 0.3⁻0.9, <i>hP</i>5, <i>P</i> 3 ¯ <i>m</i>1, <i>a</i> = 4.6632(5)⁻4.6934(3) Å, <i>c</i> = 7.630(1)⁻7.7062(7) Å), Ca<sub>2-<i>x</i></sub>Eu<i><sub>x</sub></i>CdSb₂ with the Yb₂CdSb₂ type (<i>x</i> ≈ 0.6, <i>oS</i>20, <i>Cmc</i>2₁, <i>a</i> = 4.646(2) Å, <i>b</i> = 17.733(7) Å, <i>c</i> = 7.283(3) Å), an  ...[more]

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