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Os3O is Chromium trichloride-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is one-dimensional and consists of two Os3O ribbons oriented in the (0, 0, 1) direction. Os+0.67+ is bonded in an L-shaped geometry to two equivalent O2- atoms. Both Os–O bond lengths are 2.31 Å. O2- is bonded in a 6-coordinate geometry to six equivalent Os+0.67+ atoms.
OsOs2O is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of four osmium molecules and one Os2O framework. In the Os2O framework, Os+0.67+ is bonded to four equivalent O2- atoms to form a mixture of corner and edge-sharing OsO4 tetrahedra. All Os–O bond lengths are 2.58 Å. O2- is bonded in a body-centered cubic geometry to eight equivalent Os+0.67+ atoms.