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ZrCl3 crystallizes in the hexagonal P6_3/mcm space group. The structure is one-dimensional and consists of one ZrCl3 ribbon oriented in the (0, 0, 1) direction. Zr3+ is bonded to six equivalent Cl1- atoms to form face-sharing ZrCl6 octahedra. All Zr–Cl bond lengths are 2.57 Å. Cl1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms.
ZrCl3 is Bismuth triodide-like structured and crystallizes in the trigonal P-31m space group. The structure is two-dimensional and consists of one ZrCl3 sheet oriented in the (0, 0, 1) direction. Zr3+ is bonded to six equivalent Cl1- atoms to form edge-sharing ZrCl6 octahedra. All Zr–Cl bond lengths are 2.57 Å. Cl1- is bonded in an L-shaped geometry to two equivalent Zr3+ atoms.