Ternary Antimonides RE₂Ir₃Sb₄ (RE = La, Ce, Pr, Nd)

Abstract

The antimonides RE 2 Ir 3 Sb 4 (RE = La, Ce, Pr, Nd) were synthesized by arc-melting of the elements and subsequent annealing or via high-frequency melting. The samples were characterized by X-ray powder diffraction, and the four structures were refined from single-crystal X-ray diffraction data: Pr 2 Ir 3 Sb 4 type, Pnma, Z = 4, a = 1621.9(2), b = 458.60(8), c = 1099.8(1) pm, wR 2 = 0.036, 1558 F 2 values for La 2 Ir 3 Sb 4 , a = 1616.6(8), b = 456.5(2), c = 1094.8(5) pm, wR 2 = 0.092, 1080 F 2 values for Ce 2 Ir 3 Sb 4 , a = 1613.0(5), b = 454.9(2), c = 1094.1(5) pm, wR 2 = 0.057, 1428 F 2 values for Pr 2 Ir 3 Sb 4 , and a = 1609.8(6), b = 452.9(2), c = 1092.3(5) pm, wR 2 = 0.052, 1472 F 2 values for Nd 2 Ir 3 Sb 4 , with 56 parameters per refinement. The Sb1 atoms show enhanced displacement off the mirror planes at y = 1/4 and y = 3/4. A series of temperature-dependent structure refinements of Pr 2 Ir 3 Sb 4 down to 90 K are indicative of static disorder. The iridium and antimony atoms build up covalently bonded three-dimensional [Ir 3 Sb 4 ] networks with Ir-Sb distances ranging from 256 -269 pm (Nd 2 Ir 3 Sb 4 ). The two crystallographically independent rare earth sites fill cavities of coordination numbers 17 (8 Ir + 9 Sb) and 15 (6 Ir + 9 Sb) within the [Ir 3 Sb 4 ] polyanions. Temperature-dependent magnetic susceptibility measurements indicate a stable trivalent ground state for the cerium compound. No magnetic ordering was evident down to 3 K.