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CdO2 is Calaverite structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one CdO2 sheet oriented in the (0, 0, 1) direction. Cd is bonded to six equivalent O atoms to form distorted edge-sharing CdO6 octahedra. All Cd–O bond lengths are 2.25 Å. O is bonded in a trigonal non-coplanar geometry to three equivalent Cd atoms.
CdO2 crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Cd is bonded to six equivalent O atoms to form CdO6 octahedra that share corners with twelve equivalent CdO6 octahedra and corners with six equivalent OCd3O tetrahedra. The corner-sharing octahedral tilt angles are 71°. All Cd–O bond lengths are 2.35 Å. O is bonded to three equivalent Cd and one O atom to form OCd3O tetrahedra that share corners with three equivalent CdO6 octahedra and corners with fifteen equivalent OCd3O tetrahedra. The corner-sharing octahedral tilt angles are 70°. The O–O bond length is 1.50 Å.