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HgBaO2 crystallizes in the trigonal R-3m space group. The structure is three-dimensional. Ba2+ is bonded to six equivalent O2- atoms to form edge-sharing BaO6 octahedra. All Ba–O bond lengths are 2.74 Å. Hg2+ is bonded in a linear geometry to two equivalent O2- atoms. Both Hg–O bond lengths are 2.00 Å. O2- is bonded to three equivalent Ba2+ and one Hg2+ atom to form a mixture of corner and edge-sharing OBa3Hg tetrahedra.
HgBaO2 crystallizes in the hexagonal P6_322 space group. The structure is three-dimensional. there are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 6-coordinate geometry to six equivalent O2- atoms. There are three shorter (2.71 Å) and three longer (2.80 Å) Ba–O bond lengths. In the second Ba2+ site, Ba2+ is bonded in a 6-coordinate geometry to six equivalent O2- atoms. All Ba–O bond lengths are 2.71 Å. Hg2+ is bonded in a linear geometry to two equivalent O2- atoms. Both Hg–O bond lengths are 2.02 Å. O2- is bonded in a 4-coordinate geometry to three Ba2+ and one Hg2+ atom.