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ZrI3 crystallizes in the hexagonal P6_3/mcm space group. The structure is one-dimensional and consists of one ZrI3 ribbon oriented in the (0, 0, 1) direction. Zr3+ is bonded to six equivalent I1- atoms to form face-sharing ZrI6 octahedra. All Zr–I bond lengths are 2.93 Å. I1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms.
ZrI3 crystallizes in the orthorhombic Pmmn space group. The structure is one-dimensional and consists of two ZrI3 ribbons oriented in the (1, 0, 0) direction. Zr3+ is bonded to six I1- atoms to form face-sharing ZrI6 octahedra. There are three shorter (2.90 Å) and three longer (2.96 Å) Zr–I bond lengths. There are four inequivalent I1- sites. In the first I1- site, I1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms. In the second I1- site, I1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms. In the third I1- site, I1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms. In the fourth I1- site, I1- is bonded in a 2-coordinate geometry to two equivalent Zr3+ atoms.