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PuO4(SO4)2 is Silicon tetrafluoride-derived structured and crystallizes in the orthorhombic Fddd space group. The structure is zero-dimensional and consists of sixteen sulfuric acid molecules and eight PuO4 clusters. In each PuO4 cluster, Pu is bonded in a distorted rectangular see-saw-like geometry to four equivalent O atoms. All Pu–O bond lengths are 1.80 Å. O is bonded in a single-bond geometry to one Pu atom.
PuH8(SO6)2 crystallizes in the orthorhombic Pnma space group. The structure is two-dimensional and consists of two PuH8(SO6)2 sheets oriented in the (0, 0, 1) direction. Pu4+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pu–O bond distances ranging from 2.32–2.41 Å. There are four inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 1.00 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. S6+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of S–O bond distances ranging from 1.47–1.50 Å. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to one S6+ atom. In the second O2- site, O2- is bonded in a water-like geometry to one Pu4+ and two H1+ atoms. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one S6+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Pu4+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a water-like geometry to one Pu4+ and two equivalent H1+ atoms. In the sixth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Pu4+ and one S6+ atom. In the seventh O2- site, O2- is bonded in a water-like geometry to one Pu4+ and two equivalent H1+ atoms.