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PrCl3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. Pr3+ is bonded in a 9-coordinate geometry to nine equivalent Cl1- atoms. There are six shorter (2.93 Å) and three longer (2.97 Å) Pr–Cl bond lengths. Cl1- is bonded in a trigonal non-coplanar geometry to three equivalent Pr3+ atoms.
Pr3Cl crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pr is bonded in a see-saw-like geometry to four equivalent Cl atoms. There are two shorter (3.48 Å) and two longer (3.52 Å) Pr–Cl bond lengths. Cl is bonded to twelve equivalent Pr atoms to form a mixture of face and corner-sharing ClPr12 cuboctahedra.