Neutron powder diffraction study of the crystal and magnetic structures of BiNiO3 at low temperature

The crystal and magnetic structures of the charge ordered perovskite BiNiO3 have been studied at temperatures from 5 to 300 K using neutron diffraction. Rietveld analysis of the data shows that the structure remains triclinic (space group P1-bar) throughout the whole temperature range. Bond-valence sum calculations based on the Bi-O and Ni-O bond distances confirm that the charge distribution is Bi3+0.5Bi5+0.5Ni2+O3 down to 5 K. The magnetic cell is identical to that of the triclinic superstructure and a G-type antiferromagnetic model gives a good fit to the magnetic intensities, with an ordered Ni2+ moment of 1.76(3) μB at 5 K. However, BiNiO3 is ferrimagnetic due to the inexact cancellation of opposing, inequivalent moments in the low symmetry cell. - Graphical abstract: A neutron diffraction study shows that the perovskite BiNiO3 retains the unusual charge distribution Bi3+0.5Bi5+0.5Ni2+O3 down to 5 K. The Ni2+ moments are ordered in the G-type antiferromagnetic arrangement shown; however, BiNiO3 is ferrimagnetic due to the inexact cancellation of the four inequivalent moments in the triclinic unit cell