TmAl3 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Tm is bonded to twelve equivalent Al atoms to form a mixture of corner and face-sharing TmAl12 cuboctahedra. There are six shorter (3.04 Å) and six longer (3.09 Å) Tm–Al bond lengths. Al is bonded in a 10-coordinate geometry to four equivalent Tm and six equivalent Al atoms. There are two shorter (2.76 Å) and four longer (2.81 Å) Al–Al bond lengths.
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