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LaCl3 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. La3+ is bonded in a 9-coordinate geometry to nine equivalent Cl1- atoms. There are six shorter (2.96 Å) and three longer (3.00 Å) La–Cl bond lengths. Cl1- is bonded in a trigonal non-coplanar geometry to three equivalent La3+ atoms.
LaCl crystallizes in the trigonal R-3m space group. The structure is two-dimensional and consists of six LaCl sheets oriented in the (0, 0, 1) direction. La is bonded in a distorted T-shaped geometry to three equivalent Cl atoms. All La–Cl bond lengths are 2.93 Å. Cl is bonded in a distorted T-shaped geometry to three equivalent La atoms.