Crystal structure of the compound Bi₂Zn_2/3Nb_4/3O₇

The crystal structure of Bi₂Zn_2/3Nb_4/3O₇ was determined using a combination of electron, x-ray, and neutron powder diffraction. The compound crystallizes with a monoclinic zirconolite-like structure [C2/c (No. 15) space group, a = 13.1037(9) Å, b = 7.6735(3) Å, c = 12.1584(6) Å, β = 101.318(5)°]. According to structural refinement using neutron diffraction data, Nb preferentially occupies six-fold coordinated sites in octahedral sheets parallel to the (001) planes, while Zn is statistically distributed between two half-occupied (5 + 1)-fold coordinated sites near the centers of six-membered rings of [Nb(Zn)O₆] octahedra. The Nb/Zn cation layers alternate along the c-axis with Bi-layers, in which Bi cations occupy both eight- and seven-fold coordinated sites. The eight-fold coordinated Bi atoms exhibited strongly anisotropic thermal displacements with an abnormally large component directed approximately along the c-axis (normal to the octahedral layers).