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PuCl3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Pu3+ is bonded in a 9-coordinate geometry to nine equivalent Cl1- atoms. There are six shorter (2.88 Å) and three longer (2.94 Å) Pu–Cl bond lengths. Cl1- is bonded in a trigonal non-coplanar geometry to three equivalent Pu3+ atoms.
PuCl2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Pu is bonded to six equivalent Cl atoms to form a mixture of edge and corner-sharing PuCl6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are four shorter (2.84 Å) and two longer (2.85 Å) Pu–Cl bond lengths. Cl is bonded in a distorted T-shaped geometry to three equivalent Pu atoms.