Ce4Lu11S22 crystallizes in the monoclinic C2/m space group. There are six inequivalent Lu sites. In the first Lu site, Lu(1) is bonded to one S(2), one S(3), two equivalent S(11), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the second Lu site, Lu(2) is bonded to one S(5), one S(8), two equivalent S(10), and two equivalent S(2) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. In the third Lu site, Lu(3) is bonded to one S(10), one S(7), two equivalent S(4), and two equivalent S(8) atoms to form LuS6 octahedra that share corners with three equivalent Lu(4)S6 octahedra, corners with two equivalent Lu(5)S7 pentagonal bipyramids, edges with two equivalent Lu(2)S6 octahedra, and edges with two equivalent Lu(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. In the fourth Lu site, Lu(4) is bonded to one S(1), two equivalent S(9), and three equivalent S(7) atoms to form LuS6 octahedra that share corners with three equivalent Lu(3)S6 octahedra,  a cornercorner with one Lu(5)S7 pentagonal bipyramid, edges with four equivalent Lu(4)S6 octahedra, and edges with two equivalent Lu(5)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 50-63°. In the fifth Lu site, Lu(5) is bonded to one S(4), one S(9), two equivalent S(6), and three equivalent S(1) atoms to form distorted LuS7 pentagonal bipyramids that share  a cornercorner with one Lu(4)S6 octahedra, corners with two equivalent Lu(3)S6 octahedra, edges with two equivalent Lu(4)S6 octahedra, and edges with four equivalent Lu(5)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-50°. In the sixth Lu site, Lu(6) is bonded to two equivalent S(5) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to one S(11), one S(4), two equivalent S(10), two equivalent S(3), and two equivalent S(6) atoms. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to one S(2), one S(6), two equivalent S(11), two equivalent S(8), and two equivalent S(9) atoms. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to one Lu(4) and three equivalent Lu(5) atoms to form distorted SLu4 trigonal pyramids that share  a cornercorner with one S(9)Ce2Lu3 trigonal bipyramid, corners with four equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(1)Lu4 trigonal pyramids, corners with three equivalent S(4)CeLu3 trigonal pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, and edges with two equivalent S(1)Lu4 trigonal pyramids. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Lu(1), two equivalent Lu(2), and one Ce(2) atom. In the third S site, S(3) is bonded to one Lu(1), two equivalent Lu(6), and two equivalent Ce(1) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(4)CeLu3 trigonal pyramids,  an edgeedge with one S(10)Ce2Lu3 square pyramid, edges with three equivalent S(3)Ce2Lu3 square pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, and edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Lu(5), two equivalent Lu(3), and one Ce(1) atom to form SCeLu3 trigonal pyramids that share corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids,  a cornercorner with one S(9)Ce2Lu3 trigonal bipyramid,  a cornercorner with one S(11)Ce3Lu2 trigonal bipyramid, corners with two equivalent S(4)CeLu3 trigonal pyramids, corners with three equivalent S(1)Lu4 trigonal pyramids,  an edgeedge with one S(8)Ce2Lu3 square pyramid, edges with two equivalent S(10)Ce2Lu3 square pyramids, and edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Lu(2), one Lu(6), and two equivalent Lu(1) atoms. In the sixth S site, S(6) is bonded to two equivalent Lu(5), one Ce(2), and two equivalent Ce(1) atoms to form distorted SCe3Lu2 trigonal bipyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with four equivalent S(1)Lu4 trigonal pyramids,  an edgeedge with one S(10)Ce2Lu3 square pyramid,  an edgeedge with one S(3)Ce2Lu3 square pyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids, edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids,  an edgeedge with one S(1)Lu4 trigonal pyramid, and edges with two equivalent S(4)CeLu3 trigonal pyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Lu(3) and three equivalent Lu(4) atoms. In the eighth S site, S(8) is bonded to one Lu(2), two equivalent Lu(3), and two equivalent Ce(2) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(9)Ce2Lu3 trigonal bipyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(4)CeLu3 trigonal pyramids, edges with two equivalent S(10)Ce2Lu3 square pyramids, edges with two equivalent S(8)Ce2Lu3 square pyramids,  an edgeedge with one S(9)Ce2Lu3 trigonal bipyramid,  an edgeedge with one S(11)Ce3Lu2 trigonal bipyramid, and  an edgeedge with one S(4)CeLu3 trigonal pyramid. In the ninth S site, S(9) is bonded to one Lu(5), two equivalent Lu(4), and two equivalent Ce(2) atoms to form SCe2Lu3 trigonal bipyramids that share corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids,  a cornercorner with one S(4)CeLu3 trigonal pyramid,  a cornercorner with one S(1)Lu4 trigonal pyramid,  an edgeedge with one S(8)Ce2Lu3 square pyramid,  an edgeedge with one S(11)Ce3Lu2 trigonal bipyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids, and edges with two equivalent S(1)Lu4 trigonal pyramids. In the tenth S site, S(10) is bonded to one Lu(3), two equivalent Lu(2), and two equivalent Ce(1) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids,  an edgeedge with one S(3)Ce2Lu3 square pyramid, edges with two equivalent S(10)Ce2Lu3 square pyramids, edges with two equivalent S(8)Ce2Lu3 square pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, and edges with two equivalent S(4)CeLu3 trigonal pyramids. In the eleventh S site, S(11) is bonded to two equivalent Lu(1), one Ce(1), and two equivalent Ce(2) atoms to form distorted SCe3Lu2 trigonal bipyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with two equivalent S(9)Ce2Lu3 trigonal bipyramids,  a cornercorner with one S(4)CeLu3 trigonal pyramid,  an edgeedge with one S(8)Ce2Lu3 square pyramid, edges with two equivalent S(3)Ce2Lu3 square pyramids,  an edgeedge with one S(9)Ce2Lu3 trigonal bipyramid, edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids, and edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids.
Ce4Lu11S22 crystallizes in the monoclinic C2/m space group. There are six inequivalent Lu sites. In the first Lu site, Lu(1) is bonded to one S(2), one S(3), two equivalent S(11), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. The Lu(1)-S(2) bond length is 2.60 Å. The Lu(1)-S(3) bond length is 2.69 Å. Both Lu(1)-S(11) bond lengths are 2.72 Å. Both Lu(1)-S(5) bond lengths are 2.66 Å. In the second Lu site, Lu(2) is bonded to one S(5), one S(8), two equivalent S(10), and two equivalent S(2) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles range from 48-59°. The Lu(2)-S(5) bond length is 2.71 Å. The Lu(2)-S(8) bond length is 2.69 Å. Both Lu(2)-S(10) bond lengths are 2.72 Å. Both Lu(2)-S(2) bond lengths are 2.60 Å. In the third Lu site, Lu(3) is bonded to one S(10), one S(7), two equivalent S(4), and two equivalent S(8) atoms to form LuS6 octahedra that share corners with three equivalent Lu(4)S6 octahedra, corners with two equivalent Lu(5)S7 pentagonal bipyramids, edges with two equivalent Lu(2)S6 octahedra, and edges with two equivalent Lu(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. The Lu(3)-S(10) bond length is 2.66 Å. The Lu(3)-S(7) bond length is 2.67 Å. Both Lu(3)-S(4) bond lengths are 2.60 Å. Both Lu(3)-S(8) bond lengths are 2.73 Å. In the fourth Lu site, Lu(4) is bonded to one S(1), two equivalent S(9), and three equivalent S(7) atoms to form LuS6 octahedra that share corners with three equivalent Lu(3)S6 octahedra,  a cornercorner with one Lu(5)S7 pentagonal bipyramid, edges with four equivalent Lu(4)S6 octahedra, and edges with two equivalent Lu(5)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 50-63°. The Lu(4)-S(1) bond length is 2.62 Å. Both Lu(4)-S(9) bond lengths are 2.71 Å. There are two shorter (2.66 Å) and one longer (2.73 Å) Lu(4)-S(7) bond length. In the fifth Lu site, Lu(5) is bonded to one S(4), one S(9), two equivalent S(6), and three equivalent S(1) atoms to form distorted LuS7 pentagonal bipyramids that share  a cornercorner with one Lu(4)S6 octahedra, corners with two equivalent Lu(3)S6 octahedra, edges with two equivalent Lu(4)S6 octahedra, and edges with four equivalent Lu(5)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-50°. The Lu(5)-S(4) bond length is 2.72 Å. The Lu(5)-S(9) bond length is 2.84 Å. Both Lu(5)-S(6) bond lengths are 2.82 Å. There are two shorter (2.64 Å) and one longer (2.82 Å) Lu(5)-S(1) bond length. In the sixth Lu site, Lu(6) is bonded to two equivalent S(5) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing LuS6 octahedra. The corner-sharing octahedral tilt angles are 55°. Both Lu(6)-S(5) bond lengths are 2.71 Å. All Lu(6)-S(3) bond lengths are 2.67 Å. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 8-coordinate geometry to one S(11), one S(4), two equivalent S(10), two equivalent S(3), and two equivalent S(6) atoms. The Ce(1)-S(11) bond length is 2.98 Å. The Ce(1)-S(4) bond length is 2.92 Å. Both Ce(1)-S(10) bond lengths are 3.01 Å. Both Ce(1)-S(3) bond lengths are 2.99 Å. Both Ce(1)-S(6) bond lengths are 2.89 Å. In the second Ce site, Ce(2) is bonded in a 8-coordinate geometry to one S(2), one S(6), two equivalent S(11), two equivalent S(8), and two equivalent S(9) atoms. The Ce(2)-S(2) bond length is 3.38 Å. The Ce(2)-S(6) bond length is 2.95 Å. Both Ce(2)-S(11) bond lengths are 2.87 Å. Both Ce(2)-S(8) bond lengths are 2.96 Å. Both Ce(2)-S(9) bond lengths are 2.95 Å. There are eleven inequivalent S sites. In the first S site, S(1) is bonded to one Lu(4) and three equivalent Lu(5) atoms to form distorted SLu4 trigonal pyramids that share  a cornercorner with one S(9)Ce2Lu3 trigonal bipyramid, corners with four equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(1)Lu4 trigonal pyramids, corners with three equivalent S(4)CeLu3 trigonal pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, and edges with two equivalent S(1)Lu4 trigonal pyramids. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Lu(1), two equivalent Lu(2), and one Ce(2) atom. In the third S site, S(3) is bonded to one Lu(1), two equivalent Lu(6), and two equivalent Ce(1) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(4)CeLu3 trigonal pyramids,  an edgeedge with one S(10)Ce2Lu3 square pyramid, edges with three equivalent S(3)Ce2Lu3 square pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, and edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Lu(5), two equivalent Lu(3), and one Ce(1) atom to form SCeLu3 trigonal pyramids that share corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids,  a cornercorner with one S(9)Ce2Lu3 trigonal bipyramid,  a cornercorner with one S(11)Ce3Lu2 trigonal bipyramid, corners with two equivalent S(4)CeLu3 trigonal pyramids, corners with three equivalent S(1)Lu4 trigonal pyramids,  an edgeedge with one S(8)Ce2Lu3 square pyramid, edges with two equivalent S(10)Ce2Lu3 square pyramids, and edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Lu(2), one Lu(6), and two equivalent Lu(1) atoms. In the sixth S site, S(6) is bonded to two equivalent Lu(5), one Ce(2), and two equivalent Ce(1) atoms to form distorted SCe3Lu2 trigonal bipyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with four equivalent S(1)Lu4 trigonal pyramids,  an edgeedge with one S(10)Ce2Lu3 square pyramid,  an edgeedge with one S(3)Ce2Lu3 square pyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids, edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids,  an edgeedge with one S(1)Lu4 trigonal pyramid, and edges with two equivalent S(4)CeLu3 trigonal pyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Lu(3) and three equivalent Lu(4) atoms. In the eighth S site, S(8) is bonded to one Lu(2), two equivalent Lu(3), and two equivalent Ce(2) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(9)Ce2Lu3 trigonal bipyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(4)CeLu3 trigonal pyramids, edges with two equivalent S(10)Ce2Lu3 square pyramids, edges with two equivalent S(8)Ce2Lu3 square pyramids,  an edgeedge with one S(9)Ce2Lu3 trigonal bipyramid,  an edgeedge with one S(11)Ce3Lu2 trigonal bipyramid, and  an edgeedge with one S(4)CeLu3 trigonal pyramid. In the ninth S site, S(9) is bonded to one Lu(5), two equivalent Lu(4), and two equivalent Ce(2) atoms to form SCe2Lu3 trigonal bipyramids that share corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids,  a cornercorner with one S(4)CeLu3 trigonal pyramid,  a cornercorner with one S(1)Lu4 trigonal pyramid,  an edgeedge with one S(8)Ce2Lu3 square pyramid,  an edgeedge with one S(11)Ce3Lu2 trigonal bipyramid, edges with two equivalent S(9)Ce2Lu3 trigonal bipyramids, edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids, and edges with two equivalent S(1)Lu4 trigonal pyramids. In the tenth S site, S(10) is bonded to one Lu(3), two equivalent Lu(2), and two equivalent Ce(1) atoms to form SCe2Lu3 square pyramids that share corners with two equivalent S(3)Ce2Lu3 square pyramids, corners with two equivalent S(11)Ce3Lu2 trigonal bipyramids, corners with two equivalent S(6)Ce3Lu2 trigonal bipyramids,  an edgeedge with one S(3)Ce2Lu3 square pyramid, edges with two equivalent S(10)Ce2Lu3 square pyramids, edges with two equivalent S(8)Ce2Lu3 square pyramids,  an edgeedge with one S(6)Ce3Lu2 trigonal bipyramid, and edges with two equivalent S(4)CeLu3 trigonal pyramids. In the eleventh S site, S(11) is bonded to two equivalent Lu(1), one Ce(1), and two equivalent Ce(2) atoms to form distorted SCe3Lu2 trigonal bipyramids that share corners with two equivalent S(10)Ce2Lu3 square pyramids, corners with two equivalent S(8)Ce2Lu3 square pyramids, corners with two equivalent S(9)Ce2Lu3 trigonal bipyramids,  a cornercorner with one S(4)CeLu3 trigonal pyramid,  an edgeedge with one S(8)Ce2Lu3 square pyramid, edges with two equivalent S(3)Ce2Lu3 square pyramids,  an edgeedge with one S(9)Ce2Lu3 trigonal bipyramid, edges with two equivalent S(11)Ce3Lu2 trigonal bipyramids, and edges with two equivalent S(6)Ce3Lu2 trigonal bipyramids.