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MgO2 is Calaverite structured and crystallizes in the monoclinic C2/m space group. The structure is two-dimensional and consists of one MgO2 sheet oriented in the (0, 0, 1) direction. Mg is bonded to six equivalent O atoms to form distorted edge-sharing MgO6 octahedra. There are four shorter (2.07 Å) and two longer (2.16 Å) Mg–O bond lengths. O is bonded in a trigonal non-coplanar geometry to three equivalent Mg atoms.
MgO2 is Pyrite-like structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Mg is bonded to six equivalent O atoms to form MgO6 octahedra that share corners with twelve equivalent MgO6 octahedra and corners with six equivalent OMg3O tetrahedra. The corner-sharing octahedral tilt angles are 69°. All Mg–O bond lengths are 2.11 Å. O is bonded to three equivalent Mg and one O atom to form OMg3O tetrahedra that share corners with three equivalent MgO6 octahedra and corners with fifteen equivalent OMg3O tetrahedra. The corner-sharing octahedral tilt angles are 72°. The O–O bond length is 1.51 Å.
MgO2 is pyrite-like structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Mg is bonded to six equivalent O atoms to form edge-sharing MgO6 octahedra. All Mg–O bond lengths are 2.11 Å. O is bonded in a 4-coordinate geometry to three equivalent Mg and one O atom. The O–O bond length is 1.49 Å.