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K2Se is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. K1+ is bonded to four equivalent Se2- atoms to form a mixture of edge and corner-sharing KSe4 tetrahedra. All K–Se bond lengths are 3.36 Å. Se2- is bonded in a body-centered cubic geometry to eight equivalent K1+ atoms.
K2SeS2O6 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional and consists of four selen molecules and one KSO3 framework. In the KSO3 framework, there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of K–O bond distances ranging from 2.71–3.03 Å. In the second K1+ site, K1+ is bonded in a distorted pentagonal pyramidal geometry to six O2- atoms. There are a spread of K–O bond distances ranging from 2.72–2.88 Å. There are two inequivalent S2+ sites. In the first S2+ site, S2+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. All S–O bond lengths are 1.47 Å. In the second S2+ site, S2+ is bonded in a trigonal non-coplanar geometry to three O2- atoms. There are a spread of S–O bond distances ranging from 1.46–1.48 Å. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted linear geometry to one K1+ and one S2+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to three K1+ and one S2+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to three K1+ and one S2+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S2+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two K1+ and one S2+ atom. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to two K1+ and one S2+ atom.