Pr3MnBi5 crystallizes in the hexagonal P6_3/mcm space group. Pr(1) is bonded in a 9-coordinate geometry to four equivalent Bi(2) and five equivalent Bi(1) atoms. Mn(1) is bonded to six equivalent Bi(1) atoms to form face-sharing MnBi6 octahedra. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to five equivalent Pr(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner, edge, and face-sharing BiPr5Mn2 pentagonal bipyramids. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to six equivalent Pr(1) and two equivalent Bi(2) atoms.
Pr3MnBi5 crystallizes in the hexagonal P6_3/mcm space group. Pr(1) is bonded in a 9-coordinate geometry to four equivalent Bi(2) and five equivalent Bi(1) atoms. All Pr(1)-Bi(2) bond lengths are 3.45 Å. There are a spread of Pr(1)-Bi(1) bond distances ranging from 3.26-3.56 Å. Mn(1) is bonded to six equivalent Bi(1) atoms to form face-sharing MnBi6 octahedra. All Mn(1)-Bi(1) bond lengths are 2.96 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to five equivalent Pr(1) and two equivalent Mn(1) atoms to form a mixture of distorted corner, edge, and face-sharing BiPr5Mn2 pentagonal bipyramids. In the second Bi site, Bi(2) is bonded in a 8-coordinate geometry to six equivalent Pr(1) and two equivalent Bi(2) atoms. Both Bi(2)-Bi(2) bond lengths are 3.27 Å.