Intermediate-valent CeCoAl – a commensurate modulated structure with short Ce–Co distances

Abstract

Abstract CeCoAl was synthesized by melting of the elements in a sealed niobium tube in an induction furnace. Annealing of the sample gave access to a single phase sample. Its structure was refined on the basis of single-crystal X-ray diffractometer data at different temperatures. Above 271 K CeCoAl crystallizes in its own structure type in the space group C2/m [a = 1107.4(2), b = 440.6(1) and c = 479.6(1) pm, β = 104.6(1)°]. Data obtained at 300 K lead to 511 F 2 values with 20 variables and a residual of [I ≥ 3σ(I)] wR = 0.0539. Below 271 K satellites give rise to the superspace group C2/m(α0γ)00; α = 2/3, γ = 2/5 with a temperature independent q-vector. For the 90 K data (also for 180 and 220 K) the commensurate modulated structure could be refined with 4817 F 2 values, 129 variables and residuals of wR = 0.0347 (main), wR = 0.1927 (satellites 1st order), wR = 0.1541 (satellites 2nd order) and wR = 0.1768 (satellites 3rd order) [a = 1107.5(1), b = 440.3(1) and c = 479.0(1) pm, β = 104.7(1)°]. For the three temperatures only minor variations of the modulation amplitudes are observed. The relation of the low temperature (3+1)D 3a × 5c approximant and the room temperature 3D structure is discussed on the basis of a group–subgroup relation. By investigation of the heat capacity, the phase transition could be identified as a second order one with a transition temperature of 271 K. Magnetic measurements clearly prove the intermediate cerium valence which is in line with the short Ce–Co distances.