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Cooley, Joya A.
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article
Effect of Isovalent Substitution on the Structure and Properties of the Zintl Phase Solid Solution Eu7Cd4Sb8-xAsx (2 ≤ x ≤ 5).
Abstract
A novel Zintl phase structure type, Eu7Cd4Sb8–xAsx (x = 2, 3, 4, and 5), with the general formula Eu7Cd4Pn8 (Pn = mixed occupancy Sb and As), was synthesized by molten tin flux reaction. Its structure was determined using single-crystal X-ray diffraction methods. This structure type is only preserved for 2 ≤ x ≤ 5 under our experimental conditions, and efforts to synthesize samples with x 5 resulted in other structure types. The mixed occupancy Sb and As can be thought of as a pseudoatom whose ideal size, in this range of Sb/As ratios, fits the structure. The title phase crystallizes in the I-centered monoclinic space group I2/m (No. 12, Z = 4) with unit cell parameters ranging as follows: a = 19.7116(17)–19.4546(13) A, b = 4.6751(4)–4.6149(3) A, c = 24.157(2)–23.871(15) A, and β = 95.8798(1)–96.016(5)°, depending on the Sb/As ratio. The structure can be described as parallel double pentagonal tubes resulting from Cd–Pn and Pn–Pn bonding. These double pentagons are formed through corner sharing...