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CeCl3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Ce3+ is bonded in a 9-coordinate geometry to nine equivalent Cl1- atoms. There are six shorter (2.91 Å) and three longer (3.01 Å) Ce–Cl bond lengths. Cl1- is bonded in a trigonal non-coplanar geometry to three equivalent Ce3+ atoms.
Ce3Cl is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ce is bonded in a square co-planar geometry to four equivalent Cl atoms. All Ce–Cl bond lengths are 3.17 Å. Cl is bonded to twelve equivalent Ce atoms to form a mixture of corner and face-sharing ClCe12 cuboctahedra.