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MnI2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one MnI2 sheet oriented in the (0, 0, 1) direction. Mn2+ is bonded to six equivalent I1- atoms to form edge-sharing MnI6 octahedra. All Mn–I bond lengths are 2.92 Å. I1- is bonded in a distorted T-shaped geometry to three equivalent Mn2+ atoms.
Mn3I is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Mn is bonded in a distorted square co-planar geometry to four equivalent I atoms. All Mn–I bond lengths are 2.77 Å. I is bonded to twelve equivalent Mn atoms to form a mixture of corner and face-sharing IMn12 cuboctahedra.