Eu5Al3Sb6: Al-4 Tetrahedra Embedded in a Rock-Salt-Like Structure

The new Eu(5)Al(3)Sh(6) phase has been successfully synthesized as a pure phase through Sn flux methods yielding large, high-quality crystals. This structure type features disordered Al clusters that appear in the form of dual tetrahedra. It crystallizes in the monoclinic C2/m space group exhibiting a rock-salt-like Eu-Sb framework with [Al-4] tetrahedra replacing some of the cationic Eu atoms (space group: C2/m, a = 8.151(1) angstrom, b = 14.181(2) angstrom, c = 8.145(1) angstrom, beta = 109.577(2)degrees). The structure models the [Al-4] as dual tetrahedra with the Al atom sites 37.5% occupied along with Eu present on the central site at 8% occupancy and the remainder of the site being vacant. The presence of the [Al-4] cluster is further supported by HRTEM. Electronic structure calculations show that this material is a semimetal with observed band crossings close to the Fermi level. Strong Al-Sb antibonding interactions were found from COHP calculations close to the Fermi level and provide the rationale for the deficiency of the Al cluster. Mossbauer spectroscopy on Eu-151 and Sb-121 provides oxidation states of 2+ and 3- along with the local environment. Magnetic susceptibility measurements can be described well with a Curie-Weiss law where an effective moment of 7.80 mu(B)/mol Eu is obtained, consistent with Eu2+, and show canted antiferromagnetic behavior below 10 K. Temperature dependent resistivity shows a Kondo-like low-temperature upturn caused by enhanced scattering of the itinerant electrons with the 4f orbitals of Eu.