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Ti3Sb crystallizes in the cubic Pm-3n space group. The structure is three-dimensional. Ti is bonded in a 6-coordinate geometry to two equivalent Ti and four equivalent Sb atoms. Both Ti–Ti bond lengths are 2.61 Å. All Ti–Sb bond lengths are 2.92 Å. Sb is bonded to twelve equivalent Ti atoms to form a mixture of edge and face-sharing SbTi12 cuboctahedra.
Ti3Sb crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. there are three inequivalent Ti sites. In the first Ti site, Ti is bonded in a 4-coordinate geometry to two equivalent Ti and four equivalent Sb atoms. Both Ti–Ti bond lengths are 2.76 Å. There are two shorter (2.83 Å) and two longer (3.06 Å) Ti–Sb bond lengths. In the second Ti site, Ti is bonded in a 6-coordinate geometry to two equivalent Ti and four equivalent Sb atoms. Both Ti–Ti bond lengths are 2.63 Å. All Ti–Sb bond lengths are 2.77 Å. In the third Ti site, Ti is bonded in a distorted q6 geometry to ten Ti atoms. Both Ti–Ti bond lengths are 2.63 Å. Sb is bonded in a 10-coordinate geometry to ten Ti atoms.