Synthesis, structure, and physical properties of Ln(Cu,Al,Ga) 13-x (Ln = La-Pr, and Eu) and Eu(Cu,Al) 13-x

Ln(Cu,Al,Ga) 13-x (Ln = La-Pr, and Eu; x ∼ 0.2) were synthesized by a combined Al/Ga flux. Single crystal X-ray and neutron diffraction experiments revealed that these compounds crystallize in the NaZn 13 structure-type (space group Fm3̄c) with lattice parameters of a ∼ 12 Å, V ∼ 1600 Å, and Z ∼ 8. Our final neutron models led us to conclude that Cu is occupationally disordered on the 8b Wyckoff site while Cu, Al, and Ga are substitutionally disordered on the 96i Wyckoff site of this well-known structure-type. The magnetic susceptibility data show that Ce(Cu,Al,Ga) 13-x and Pr(Cu,Al,Ga) 13-x exhibit paramagnetic behavior down to the lowest temperatures measured while Eu(Cu,Al,Ga) 13-x displays ferromagnetic behavior below 6 K. Eu(Cu,Al) 13-x was prepared via arc-melting and orders ferromagnetically below 8 K. The magnetocaloric properties of Eu(Cu,Al,Ga) 13-x and Eu(Cu,Al) 13-x were measured and compared. Additionally, an enhanced value of the Sommerfeld coefficient (γ = 356 mJ/mol-K 2) was determined for Pr(Cu,Al,Ga) 13-x. Herein, we present the synthesis, structural refinement details, and physical properties of Ln(Cu,Al,Ga) 13-x (Ln = La-Pr, and Eu) and Eu(Cu,Al) 13-x. © 2012 American Chemical Society