{Ca, Eu, Yb}₂₃Cu₇Mg₄ as a Step towards the Structural Generalization of Rare Earth-Rich Intermetallics

Abstract

The R23Cu7Mg4 (R = Ca, Eu) intermetallics, studied by single-crystal X-ray diffraction, were found to be isostructural with the Yb23Cu7Mg4 prototype (hP68, k4h2fca, space group P63/mmc), forming a small group inside the bigger 23:7:4 family, otherwise adopting the hP68-Pr23Ir7Mg4 crystal structure. The observed structural peculiarity is connected with the divalent character of the R component and with a noticeable volume contraction, resulting in the clear clustering of title compounds inside the whole 23:7:4 family. The occurrence of fragments typical of similar compounds, particularly Cu-centered trigonal prisms and Mg-centered core–shell polyicosahedral clusters with R at vertices, induced the search of significant structural relationships. In this work, a description of the hexagonal crystal structure of the studied compounds is proposed as a linear intergrowth along the c-direction of the two types of slabs, R10CuMg3 (parent type: hP28-kh2ca, SG 194) and R13Cu6Mg (parent type: hR60-b6a2, SG 160). The ratio of these slabs in the studied structure is 2:2 per unit cell, corresponding to the simple equation, 2 × R10CuMg3 + 2 × R13Cu6Mg = 2 × R23Cu7Mg4. This description assimilates the studied compounds to the {Ca, Eu, Yb}4CuMg ones, where the same slabs (of p3m1 layer symmetry) are stacked in a different way/ratio and constitutes a further step towards a structural generalization of R-rich ternary intermetallics.

Keywords

• Mg-containing intermetallics
• rare earth metals
• polyicosahedral units
• linear intergrowth concept
• volume effects
• structural generalization