title: Structural variability versus structural flexibility. A case study of Eu9Cd4+xSb9 and Ca9Mn4+xSb9 (x ≈ (1)/2).
abstract: 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.
authors.affiliation: State Key Laboratory of Crystal Materials, Institute of Crystal Materials, Shandong University , Jinan, Shandong 250100, P. R. China.
authors.forename: Xiao-Cun
authors.initials: XC
authors.lastname: Liu
authors.forename: Zhen
authors.initials: Z
authors.lastname: Wu
authors.forename: Sheng-Qing
authors.initials: SQ
authors.lastname: Xia
authors.forename: Xu-Tang
authors.initials: XT
authors.lastname: Tao
authors.forename: Svilen
authors.initials: S
authors.lastname: Bobev