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ErBi3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Er is bonded to twelve equivalent Bi atoms to form a mixture of corner and face-sharing ErBi12 cuboctahedra. There are six shorter (3.41 Å) and six longer (3.55 Å) Er–Bi bond lengths. Bi is bonded in a 4-coordinate geometry to four equivalent Er atoms.
ErBi3 is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Er is bonded to twelve equivalent Bi atoms to form a mixture of face and corner-sharing ErBi12 cuboctahedra. All Er–Bi bond lengths are 3.49 Å. Bi is bonded in a distorted square co-planar geometry to four equivalent Er atoms.