Ti5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and three equivalent Sb(1) atoms. In the second Ti site, Ti(2) is bonded to two equivalent Sb(2) and four equivalent Sb(1) atoms to form distorted corner-sharing TiSb6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. In the third Ti site, Ti(3) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. In the fourth Ti site, Ti(4) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 9-coordinate geometry to two equivalent Ti(2), two equivalent Ti(3), two equivalent Ti(4), and three equivalent Ti(1) atoms. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to one Ti(3), one Ti(4), two equivalent Ti(2), and four equivalent Ti(1) atoms.
Ti5Sb3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to two equivalent Sb(2) and three equivalent Sb(1) atoms. There is one shorter (2.75 Å) and one longer (2.77 Å) Ti(1)-Sb(2) bond length. There are two shorter (2.93 Å) and one longer (2.94 Å) Ti(1)-Sb(1) bond length. In the second Ti site, Ti(2) is bonded to two equivalent Sb(2) and four equivalent Sb(1) atoms to form distorted corner-sharing TiSb6 octahedra. The corner-sharing octahedral tilt angles range from 30-48°. There is one shorter (2.74 Å) and one longer (2.94 Å) Ti(2)-Sb(2) bond length. There are two shorter (2.83 Å) and two longer (2.88 Å) Ti(2)-Sb(1) bond lengths. In the third Ti site, Ti(3) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. The Ti(3)-Sb(2) bond length is 2.81 Å. There are two shorter (2.80 Å) and two longer (2.81 Å) Ti(3)-Sb(1) bond lengths. In the fourth Ti site, Ti(4) is bonded in a 5-coordinate geometry to one Sb(2) and four equivalent Sb(1) atoms. The Ti(4)-Sb(2) bond length is 2.73 Å. There are two shorter (2.78 Å) and two longer (2.96 Å) Ti(4)-Sb(1) bond lengths. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 9-coordinate geometry to two equivalent Ti(2), two equivalent Ti(3), two equivalent Ti(4), and three equivalent Ti(1) atoms. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to one Ti(3), one Ti(4), two equivalent Ti(2), and four equivalent Ti(1) atoms.