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Abstract

The new CoBi2O2F4 compound was synthesized by a hydrothermal method at 230 degrees C. Single-crystal X-ray diffraction data were used to determine the crystal structure. The compound is layered and belongs to the Aurivillius family of compounds. The present compound is the first oxo-fluoride Aurivillius phase containing Co2+. Inclusion of a d-block cation with such a low oxidation state as 2+ was achieved by partially replacing O2- with F- ions. The crystal structure is best described in the tetragonal noncentrosymmetric space group I<(4)overbar> with unit-cell parameters a = 3.843(2) angstrom and c = 16.341(8) angstrom. The crystal structure consists of two main building units: [BiO4F4] distorted cubes and [CoF6] octahedra. Interestingly, since the octahedra [CoF6] tilt between four equivalent positions, the F atoms occupy a 4-fold split position at room temperature. For the investigation of the structural disorder, Raman scattering data were collected in the range from 10 K to room temperature. As the temperature decreases, sharper phonon peaks appear and several modes clearly appear, which indicates a reduction of the disorder. Magnetic susceptibility and heat capacity measurements evidence long-range antiferromagnetic ordering below the Neel temperature of similar to 50 K. The magnetic susceptibility is in agreement with the Curie-Weiss law above 75 K with a Curie-Weiss temperature of theta(cw) = -142(2) K.