Yb4CdS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 5-coordinate geometry to one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. In the second Yb site, Yb(2) is bonded to one S(7), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms to form distorted YbS7 pentagonal bipyramids that share corners with two equivalent Yb(4)S6 octahedra, corners with two equivalent S(1)Yb4CdS octahedra, corners with four equivalent Yb(3)S6 octahedra,  an edgeedge with one Yb(3)S6 octahedra, edges with two equivalent Cd(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and faces with two equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 11-105°. In the third Yb site, Yb(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(4)S6 octahedra,  a cornercorner with one Cd(1)S6 octahedra, corners with two equivalent S(1)Yb4CdS octahedra, corners with four equivalent Yb(2)S7 pentagonal bipyramids, edges with two equivalent Yb(3)S6 octahedra, and  an edgeedge with one Yb(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 66-80°. In the fourth Yb site, Yb(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Cd(1)S6 octahedra, corners with two equivalent Yb(2)S7 pentagonal bipyramids,  a cornercorner with one S(3)Yb4S trigonal bipyramid, edges with two equivalent Yb(4)S6 octahedra, edges with three equivalent Cd(1)S6 octahedra, and edges with three equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-80°. Cd(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form distorted CdS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, edges with two equivalent Cd(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and edges with two equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-77°. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Yb(2), two equivalent Yb(4), one Cd(1), and one S(4) atom to form distorted SYb4CdS octahedra that share corners with two equivalent Yb(3)S6 octahedra, corners with two equivalent S(7)Yb4Cd2 octahedra, corners with two equivalent Yb(2)S7 pentagonal bipyramids, corners with four equivalent S(6)Yb4 trigonal pyramids, edges with two equivalent S(1)Yb4CdS octahedra, edges with three equivalent S(7)Yb4Cd2 octahedra, and  an edgeedge with one S(6)Yb4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 11-66°. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Yb(4), two equivalent Yb(1), two equivalent Cd(1), and one S(3) atom. In the third S site, S(3) is bonded to two equivalent Yb(1), two equivalent Yb(3), and one S(2) atom to form distorted SYb4S trigonal bipyramids that share  a cornercorner with one Yb(4)S6 octahedra, corners with two equivalent Cd(1)S6 octahedra, corners with two equivalent S(7)Yb4Cd2 octahedra, corners with two equivalent S(6)Yb4 trigonal pyramids, and edges with two equivalent S(3)Yb4S trigonal bipyramids. The corner-sharing octahedral tilt angles range from 50-73°. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Yb(2), two equivalent Yb(3), and one S(1) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Yb(3), two equivalent Yb(1), and one Cd(1) atom. In the sixth S site, S(6) is bonded to one Yb(3), one Yb(4), and two equivalent Yb(2) atoms to form SYb4 trigonal pyramids that share corners with four equivalent S(1)Yb4CdS octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, corners with two equivalent S(6)Yb4 trigonal pyramids,  an edgeedge with one S(1)Yb4CdS octahedra, and edges with two equivalent S(7)Yb4Cd2 octahedra. The corner-sharing octahedral tilt angles range from 9-79°. In the seventh S site, S(7) is bonded to one Yb(1), one Yb(2), two equivalent Yb(4), and two equivalent Cd(1) atoms to form SYb4Cd2 octahedra that share corners with two equivalent S(1)Yb4CdS octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, edges with two equivalent S(7)Yb4Cd2 octahedra, edges with three equivalent S(1)Yb4CdS octahedra, and edges with two equivalent S(6)Yb4 trigonal pyramids. The corner-sharing octahedral tilt angles are 11°.
Yb4CdS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 5-coordinate geometry to one S(7), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. The Yb(1)-S(7) bond length is 2.85 Å. Both Yb(1)-S(2) bond lengths are 3.34 Å. Both Yb(1)-S(3) bond lengths are 2.88 Å. Both Yb(1)-S(5) bond lengths are 2.71 Å. In the second Yb site, Yb(2) is bonded to one S(7), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms to form distorted YbS7 pentagonal bipyramids that share corners with two equivalent Yb(4)S6 octahedra, corners with two equivalent S(1)Yb4CdS octahedra, corners with four equivalent Yb(3)S6 octahedra,  an edgeedge with one Yb(3)S6 octahedra, edges with two equivalent Cd(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and faces with two equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 11-105°. The Yb(2)-S(7) bond length is 2.88 Å. Both Yb(2)-S(1) bond lengths are 3.13 Å. Both Yb(2)-S(4) bond lengths are 2.89 Å. Both Yb(2)-S(6) bond lengths are 2.72 Å. In the third Yb site, Yb(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(4)S6 octahedra,  a cornercorner with one Cd(1)S6 octahedra, corners with two equivalent S(1)Yb4CdS octahedra, corners with four equivalent Yb(2)S7 pentagonal bipyramids, edges with two equivalent Yb(3)S6 octahedra, and  an edgeedge with one Yb(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 66-80°. The Yb(3)-S(5) bond length is 2.71 Å. The Yb(3)-S(6) bond length is 2.68 Å. Both Yb(3)-S(3) bond lengths are 2.87 Å. Both Yb(3)-S(4) bond lengths are 2.86 Å. In the fourth Yb site, Yb(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form YbS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Cd(1)S6 octahedra, corners with two equivalent Yb(2)S7 pentagonal bipyramids,  a cornercorner with one S(3)Yb4S trigonal bipyramid, edges with two equivalent Yb(4)S6 octahedra, edges with three equivalent Cd(1)S6 octahedra, and edges with three equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-80°. The Yb(4)-S(2) bond length is 2.95 Å. The Yb(4)-S(6) bond length is 2.66 Å. Both Yb(4)-S(1) bond lengths are 2.90 Å. Both Yb(4)-S(7) bond lengths are 2.82 Å. Cd(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form distorted CdS6 octahedra that share  a cornercorner with one Yb(3)S6 octahedra, corners with two equivalent Yb(4)S6 octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, edges with two equivalent Cd(1)S6 octahedra, edges with three equivalent Yb(4)S6 octahedra, and edges with two equivalent Yb(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-77°. The Cd(1)-S(1) bond length is 3.04 Å. The Cd(1)-S(5) bond length is 2.52 Å. Both Cd(1)-S(2) bond lengths are 2.87 Å. Both Cd(1)-S(7) bond lengths are 2.77 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Yb(2), two equivalent Yb(4), one Cd(1), and one S(4) atom to form distorted SYb4CdS octahedra that share corners with two equivalent Yb(3)S6 octahedra, corners with two equivalent S(7)Yb4Cd2 octahedra, corners with two equivalent Yb(2)S7 pentagonal bipyramids, corners with four equivalent S(6)Yb4 trigonal pyramids, edges with two equivalent S(1)Yb4CdS octahedra, edges with three equivalent S(7)Yb4Cd2 octahedra, and  an edgeedge with one S(6)Yb4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 11-66°. The S(1)-S(4) bond length is 2.13 Å. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Yb(4), two equivalent Yb(1), two equivalent Cd(1), and one S(3) atom. The S(2)-S(3) bond length is 2.11 Å. In the third S site, S(3) is bonded to two equivalent Yb(1), two equivalent Yb(3), and one S(2) atom to form distorted SYb4S trigonal bipyramids that share  a cornercorner with one Yb(4)S6 octahedra, corners with two equivalent Cd(1)S6 octahedra, corners with two equivalent S(7)Yb4Cd2 octahedra, corners with two equivalent S(6)Yb4 trigonal pyramids, and edges with two equivalent S(3)Yb4S trigonal bipyramids. The corner-sharing octahedral tilt angles range from 50-73°. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Yb(2), two equivalent Yb(3), and one S(1) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Yb(3), two equivalent Yb(1), and one Cd(1) atom. In the sixth S site, S(6) is bonded to one Yb(3), one Yb(4), and two equivalent Yb(2) atoms to form SYb4 trigonal pyramids that share corners with four equivalent S(1)Yb4CdS octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, corners with two equivalent S(6)Yb4 trigonal pyramids,  an edgeedge with one S(1)Yb4CdS octahedra, and edges with two equivalent S(7)Yb4Cd2 octahedra. The corner-sharing octahedral tilt angles range from 9-79°. In the seventh S site, S(7) is bonded to one Yb(1), one Yb(2), two equivalent Yb(4), and two equivalent Cd(1) atoms to form SYb4Cd2 octahedra that share corners with two equivalent S(1)Yb4CdS octahedra, corners with two equivalent S(3)Yb4S trigonal bipyramids, edges with two equivalent S(7)Yb4Cd2 octahedra, edges with three equivalent S(1)Yb4CdS octahedra, and edges with two equivalent S(6)Yb4 trigonal pyramids. The corner-sharing octahedral tilt angles are 11°.