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HgO2 crystallizes in the monoclinic C2/m space group. The structure is one-dimensional and consists of two HgO2 ribbons oriented in the (1, 0, 1) direction. Hg is bonded in a linear geometry to two equivalent O atoms. Both Hg–O bond lengths are 2.11 Å. O is bonded in a distorted water-like geometry to one Hg and one O atom. The O–O bond length is 1.48 Å.
Re2(HgO2)5 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Re5+ is bonded in a tetrahedral geometry to four O2- atoms. There is two shorter (1.75 Å) and two longer (1.76 Å) Re–O bond length. There are three inequivalent Hg2+ sites. In the first Hg2+ site, Hg2+ is bonded in a 1-coordinate geometry to four O2- atoms. There are a spread of Hg–O bond distances ranging from 2.25–2.84 Å. In the second Hg2+ site, Hg2+ is bonded in a 1-coordinate geometry to one O2- atom. The Hg–O bond length is 2.21 Å. In the third Hg2+ site, Hg2+ is bonded in a 2-coordinate geometry to six O2- atoms. There are a spread of Hg–O bond distances ranging from 2.09–3.01 Å. There are five inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one Re5+ atom. In the second O2- site, O2- is bonded to four Hg2+ atoms to form a mixture of distorted edge and corner-sharing OHg4 tetrahedra. In the third O2- site, O2- is bonded in a distorted single-bond geometry to one Re5+ and two Hg2+ atoms. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Re5+ and one Hg2+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to one Re5+ and one Hg2+ atom.