Pr12(MnC3)5 crystallizes in the hexagonal P-62m space group. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a rectangular see-saw-like geometry to two equivalent C(2) and two equivalent C(4) atoms. In the second Pr site, Pr(2) is bonded in a 5-coordinate geometry to one C(1), one C(2), two equivalent C(3), and two equivalent C(4) atoms. In the third Pr site, Pr(3) is bonded to two equivalent C(1), two equivalent C(3), and four equivalent C(4) atoms to form a mixture of distorted corner and edge-sharing PrC8 hexagonal bipyramids. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted trigonal non-coplanar geometry to one C(1) and two equivalent C(2) atoms. In the second Mn site, Mn(2) is bonded in a trigonal planar geometry to three equivalent C(4) atoms. There are four inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to two equivalent Pr(2), two equivalent Pr(3), one Mn(1), and one C(3) atom. In the second C site, C(2) is bonded to two equivalent Pr(1), two equivalent Pr(2), and two equivalent Mn(1) atoms to form CPr4Mn2 octahedra that share corners with four equivalent C(2)Pr4Mn2 octahedra and edges with four equivalent C(4)Pr5Mn octahedra. The corner-sharing octahedral tilt angles range from 4-35°. In the third C site, C(3) is bonded in a 7-coordinate geometry to two equivalent Pr(3), four equivalent Pr(2), and one C(1) atom. In the fourth C site, C(4) is bonded to one Pr(1), two equivalent Pr(2), two equivalent Pr(3), and one Mn(2) atom to form distorted CPr5Mn octahedra that share corners with five equivalent C(4)Pr5Mn octahedra, edges with two equivalent C(2)Pr4Mn2 octahedra, and edges with three equivalent C(4)Pr5Mn octahedra. The corner-sharing octahedral tilt angles range from 11-36°.
Pr12(MnC3)5 crystallizes in the hexagonal P-62m space group. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a rectangular see-saw-like geometry to two equivalent C(2) and two equivalent C(4) atoms. Both Pr(1)-C(2) bond lengths are 2.70 Å. Both Pr(1)-C(4) bond lengths are 2.69 Å. In the second Pr site, Pr(2) is bonded in a 5-coordinate geometry to one C(1), one C(2), two equivalent C(3), and two equivalent C(4) atoms. The Pr(2)-C(1) bond length is 2.55 Å. The Pr(2)-C(2) bond length is 2.52 Å. There is one shorter (2.70 Å) and one longer (2.88 Å) Pr(2)-C(3) bond length. Both Pr(2)-C(4) bond lengths are 2.71 Å. In the third Pr site, Pr(3) is bonded to two equivalent C(1), two equivalent C(3), and four equivalent C(4) atoms to form a mixture of distorted corner and edge-sharing PrC8 hexagonal bipyramids. Both Pr(3)-C(1) bond lengths are 2.91 Å. Both Pr(3)-C(3) bond lengths are 2.70 Å. There are two shorter (2.78 Å) and two longer (2.84 Å) Pr(3)-C(4) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted trigonal non-coplanar geometry to one C(1) and two equivalent C(2) atoms. The Mn(1)-C(1) bond length is 1.84 Å. Both Mn(1)-C(2) bond lengths are 1.94 Å. In the second Mn site, Mn(2) is bonded in a trigonal planar geometry to three equivalent C(4) atoms. All Mn(2)-C(4) bond lengths are 1.77 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to two equivalent Pr(2), two equivalent Pr(3), one Mn(1), and one C(3) atom. The C(1)-C(3) bond length is 1.34 Å. In the second C site, C(2) is bonded to two equivalent Pr(1), two equivalent Pr(2), and two equivalent Mn(1) atoms to form CPr4Mn2 octahedra that share corners with four equivalent C(2)Pr4Mn2 octahedra and edges with four equivalent C(4)Pr5Mn octahedra. The corner-sharing octahedral tilt angles range from 4-35°. In the third C site, C(3) is bonded in a 7-coordinate geometry to two equivalent Pr(3), four equivalent Pr(2), and one C(1) atom. In the fourth C site, C(4) is bonded to one Pr(1), two equivalent Pr(2), two equivalent Pr(3), and one Mn(2) atom to form distorted CPr5Mn octahedra that share corners with five equivalent C(4)Pr5Mn octahedra, edges with two equivalent C(2)Pr4Mn2 octahedra, and edges with three equivalent C(4)Pr5Mn octahedra. The corner-sharing octahedral tilt angles range from 11-36°.