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Gd(OH)3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Gd3+ is bonded in a 9-coordinate geometry to nine equivalent O2- atoms. There are six shorter (2.47 Å) and three longer (2.49 Å) Gd–O bond lengths. H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.97 Å. O2- is bonded in a single-bond geometry to three equivalent Gd3+ and one H1+ atom.
GdOOH crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. Gd3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Gd–O bond distances ranging from 2.31–2.51 Å. H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.97 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded to four equivalent Gd3+ atoms to form a mixture of edge and corner-sharing OGd4 tetrahedra. In the second O2- site, O2- is bonded in a single-bond geometry to three equivalent Gd3+ and one H1+ atom.