Inorganic Chemistry, Vol.51, No.8, 4802-4809, 2012
Crystal Structural, Magnetic, and Transport Properties of Layered Cobalt Oxyfluorides, Sr2CoO3+xF1-x (0 <= x <= 0.15)
The crystal structure of the layered cobalt oxyfluoride Sr2CoO3F synthesized under high-pressure and high-temperature conditions has been determined from neutron powder diffraction and synchrotron powder diffraction data collected at temperatures ranging from 320 to 3 K. This material adopts the tetragonal space group I4/mmm over the measured temperature range and the crystal structure is analogous to n = 1 Ruddlesden-Popper type layered perovskite. In contrast to related oxyhalide compounds, the present material exhibits the unique coordination environment around the Co metal center: coexistence of square pyramidal coordination around Co and anion disorder between O and F at the apical sites. Magnetic susceptibility and electrical resistivity measurements reveal that Sr2CoO3F is an antiferromagnetic insulator with the Neel temperature T-N = 323(2) K. The magnetic structure that has been determined by neutron diffraction adopts a G-type antiferromagnetic order with the propagation vector k = (1/2 1/2 0) with an ordered cobalt moment mu = 3.18(5) at mu(B) K, consistent with the high spin electron configuration for the Co3+ ions. The antiferromagnetic and electrically insulating states remain robust even against 15%-O substation for F at the apical sites. However, applying pressure exhibits the onset of the metallic state, probably coming from change in the electronic state of square-pyramidal coordinated cobalt.