Pr3TiSb5 crystallizes in the hexagonal P6_3/mcm space group. Pr(1) is bonded in a 9-coordinate geometry to four equivalent Sb(2) and five equivalent Sb(1) atoms. Ti(1) is bonded to six equivalent Sb(1) atoms to form face-sharing TiSb6 octahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to five equivalent Pr(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner, face, and edge-sharing SbPr5Ti2 pentagonal bipyramids. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to six equivalent Pr(1) and two equivalent Sb(2) atoms.
Pr3TiSb5 crystallizes in the hexagonal P6_3/mcm space group. Pr(1) is bonded in a 9-coordinate geometry to four equivalent Sb(2) and five equivalent Sb(1) atoms. All Pr(1)-Sb(2) bond lengths are 3.38 Å. There are a spread of Pr(1)-Sb(1) bond distances ranging from 3.21-3.55 Å. Ti(1) is bonded to six equivalent Sb(1) atoms to form face-sharing TiSb6 octahedra. All Ti(1)-Sb(1) bond lengths are 2.86 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to five equivalent Pr(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner, face, and edge-sharing SbPr5Ti2 pentagonal bipyramids. In the second Sb site, Sb(2) is bonded in a 8-coordinate geometry to six equivalent Pr(1) and two equivalent Sb(2) atoms. Both Sb(2)-Sb(2) bond lengths are 3.10 Å.