Sw. Keller et al., A NEW SERIES OF MAGNETIC RARE-EARTH CUPRATES - RCU(2)O(4) (R=LA, ND, SM, AND EU), Journal of the American Chemical Society, 116(18), 1994, pp. 8070-8076
The synthesis, crystal structure, and magnetic properties of a new ser
ies of isostructural rare earth cuprates, RCu(2)O(4) (R = La, Nd, Sm,
and Eu), are reported. The highly oxidized materials with an average f
ormal copper oxidation state of Cu-2.5+ were isolated by precipitation
from molten NaOH at 400 OC. Powder X-ray diffraction data for EuCu2O4
combined with neutron diffraction data for NdCu2O4 were used to deter
mine the crystal structure and refine the structure by Rietveld profil
e analysis. The lattice parameters for NdCu2O4 in the non-standard mon
oclinic space group 12/a derived from the neutron data set are the fol
lowing: a 5.826(1) Angstrom, b = 9.703(1) Angstrom, c - 5.753(1) Angst
rom, and beta = 92.341(1)degrees. The copper-oxygen network consists o
f a three-dimensional array of CuO4 distorted square planes that are c
ornered-shared; the Cu-O-Cu bond angle is similar to 115 degrees. Thes
e phases exhibit magnetic ordering of the copper spins as determined b
y a large increase in the magnetization as the temperature is lowered,
the onset of which varies between 18 and 28 K, depending on R. While
the negative Weiss constants for LaCu2O4 and NdCu2O4 indicate that the
predominant interaction is antiferromagnetic, the saturation moments
of similar to 0.13 mu(B) per mol of RCu(2)O(4) indicate that there is
a significant ferromagnetic component, possibly due to canting of the
ordered copper moments.