Linear infinite cadmium chains in CaAu4Cd2 and other intermetallics with YbMo2Al4-type structure

Abstract

New YbMo2Al4-type cadmium compounds CaAu4Cd2, SrAu4Cd2, and EuAu4Cd2 were synthesized from the elements in sealed tantalum tubes. The structures of CaAu4Cd2 (I4/mmm, a = 710.7(1), c = 550.2(3) pm, wR2 = 0.026, 168 F 2 values, 10 variables) and EuAu4.80Cd1.20 (a = 716.6(1), c = 545.9(1) pm, wR2 = 0.024, 167 F 2 values, 11 variables) were refined from X-ray single-crystal diffractometry data. The gold and cadmium atoms show different substructures: Au4 squares (279 pm Au–Au in CaAu4Cd2) and cadmium chains (275 pm Cd–Cd in CaAu4Cd2). EuAu4Cd2 forms a solid solution EuAu4+x Cd2−x up to x ≈ 1, where almost every other cadmium atom within the chains is substituted by gold. Chemical bonding analyses on CaAu4Cd2 shows almost complete charge transfer from calcium to the [Au4Cd2] network. Bader charge analysis classifies CaAu4Cd2 as an auride. EuAu4Cd2 shows Curie–Weiss behavior above 25 K with an experimental magnetic moment of 7.86 μB/Eu atom, near to the free ion value of 7.94 μB for Eu2+ and orders ferromagnetically at T C = 16.3(5) K. 151Eu Mossbauer spectra show a single signal at an isomer shift of about −10 mm/s, compatible with divalent europium. At 5 K, and therefore clearly below T C, magnetic hyperfine splitting is observed.