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Cs2O2 is alpha boron-derived structured and crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. Cs is bonded in a 6-coordinate geometry to six equivalent O atoms. There are four shorter (2.98 Å) and two longer (3.20 Å) Cs–O bond lengths. O is bonded in a 7-coordinate geometry to six equivalent Cs and one O atom. The O–O bond length is 1.52 Å.
Cs2O2 is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cs is bonded to six equivalent O atoms to form a mixture of corner and edge-sharing CsO6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cs–O bond lengths are 3.03 Å. O is bonded to six equivalent Cs atoms to form a mixture of corner and edge-sharing OCs6 octahedra. The corner-sharing octahedral tilt angles are 0°.