Ce12(ReC3)5 crystallizes in the hexagonal P-62m space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to one C(2), one C(3), one C(4), and two equivalent C(1) atoms to form a mixture of distorted edge and corner-sharing CeC5 square pyramids. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to two equivalent C(2), two equivalent C(3), and four equivalent C(1) atoms. In the third Ce site, Ce(3) is bonded in a rectangular see-saw-like geometry to two equivalent C(1) and two equivalent C(4) atoms. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a distorted T-shaped geometry to one C(2) and two equivalent C(4) atoms. In the second Re site, Re(2) is bonded in a trigonal planar geometry to three equivalent C(1) atoms. There are four inequivalent C sites. In the first C site, C(1) is bonded to one Ce(3), two equivalent Ce(1), two equivalent Ce(2), and one Re(2) atom to form CCe5Re octahedra that share corners with five equivalent C(1)Ce5Re octahedra, edges with two equivalent C(4)Ce4Re2 octahedra, and edges with three equivalent C(1)Ce5Re octahedra. The corner-sharing octahedral tilt angles range from 3-45°. In the second C site, C(2) is bonded in a 6-coordinate geometry to two equivalent Ce(1), two equivalent Ce(2), one Re(1), and one C(3) atom. In the third C site, C(3) is bonded in a 5-coordinate geometry to two equivalent Ce(1), two equivalent Ce(2), and one C(2) atom. In the fourth C site, C(4) is bonded to two equivalent Ce(1), two equivalent Ce(3), and two equivalent Re(1) atoms to form CCe4Re2 octahedra that share corners with four equivalent C(4)Ce4Re2 octahedra and edges with four equivalent C(1)Ce5Re octahedra. The corner-sharing octahedral tilt angles range from 3-26°.
Ce12(ReC3)5 crystallizes in the hexagonal P-62m space group. There are three inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to one C(2), one C(3), one C(4), and two equivalent C(1) atoms to form a mixture of distorted edge and corner-sharing CeC5 square pyramids. The Ce(1)-C(2) bond length is 2.56 Å. The Ce(1)-C(3) bond length is 2.63 Å. The Ce(1)-C(4) bond length is 2.43 Å. Both Ce(1)-C(1) bond lengths are 2.61 Å. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to two equivalent C(2), two equivalent C(3), and four equivalent C(1) atoms. Both Ce(2)-C(2) bond lengths are 2.82 Å. Both Ce(2)-C(3) bond lengths are 2.62 Å. There are two shorter (2.78 Å) and two longer (2.86 Å) Ce(2)-C(1) bond lengths. In the third Ce site, Ce(3) is bonded in a rectangular see-saw-like geometry to two equivalent C(1) and two equivalent C(4) atoms. Both Ce(3)-C(1) bond lengths are 2.48 Å. Both Ce(3)-C(4) bond lengths are 2.61 Å. There are two inequivalent Re sites. In the first Re site, Re(1) is bonded in a distorted T-shaped geometry to one C(2) and two equivalent C(4) atoms. The Re(1)-C(2) bond length is 1.93 Å. Both Re(1)-C(4) bond lengths are 2.08 Å. In the second Re site, Re(2) is bonded in a trigonal planar geometry to three equivalent C(1) atoms. All Re(2)-C(1) bond lengths are 1.96 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded to one Ce(3), two equivalent Ce(1), two equivalent Ce(2), and one Re(2) atom to form CCe5Re octahedra that share corners with five equivalent C(1)Ce5Re octahedra, edges with two equivalent C(4)Ce4Re2 octahedra, and edges with three equivalent C(1)Ce5Re octahedra. The corner-sharing octahedral tilt angles range from 3-45°. In the second C site, C(2) is bonded in a 6-coordinate geometry to two equivalent Ce(1), two equivalent Ce(2), one Re(1), and one C(3) atom. The C(2)-C(3) bond length is 1.35 Å. In the third C site, C(3) is bonded in a 5-coordinate geometry to two equivalent Ce(1), two equivalent Ce(2), and one C(2) atom. In the fourth C site, C(4) is bonded to two equivalent Ce(1), two equivalent Ce(3), and two equivalent Re(1) atoms to form CCe4Re2 octahedra that share corners with four equivalent C(4)Ce4Re2 octahedra and edges with four equivalent C(1)Ce5Re octahedra. The corner-sharing octahedral tilt angles range from 3-26°.