Ho4CeS7 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ho sites. In the first Ho site, Ho(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form HoS6 octahedra that share  a cornercorner with one Ce(1)S6 octahedra, corners with two equivalent Ho(1)S6 octahedra, corners with six equivalent Ho(2)S7 pentagonal bipyramids, edges with five equivalent Ho(1)S6 octahedra, and  an edgeedge with one Ho(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 0-59°. In the second Ho site, Ho(2) is bonded to two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted HoS7 pentagonal bipyramids that share corners with two equivalent Ce(1)S6 octahedra, corners with six equivalent Ho(1)S6 octahedra,  an edgeedge with one Ho(1)S6 octahedra, edges with three equivalent Ce(1)S6 octahedra, edges with two equivalent Ho(2)S7 pentagonal bipyramids, and faces with two equivalent Ho(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-69°. Ce(1) is bonded to two equivalent S(3) and four equivalent S(2) atoms to form CeS6 octahedra that share corners with two equivalent Ho(1)S6 octahedra, corners with four equivalent Ho(2)S7 pentagonal bipyramids, edges with two equivalent Ce(1)S6 octahedra, and edges with six equivalent Ho(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 59°. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ho(2) and three equivalent Ho(1) atoms to form distorted SHo5 trigonal bipyramids that share corners with five equivalent S(3)CeHo3 tetrahedra, corners with four equivalent S(2)Ce2Ho3 trigonal bipyramids,  an edgeedge with one S(3)CeHo3 tetrahedra,  an edgeedge with one S(2)Ce2Ho3 trigonal bipyramid, and edges with four equivalent S(1)Ho5 trigonal bipyramids. In the second S site, S(2) is bonded to three equivalent Ho(2) and two equivalent Ce(1) atoms to form distorted SCe2Ho3 trigonal bipyramids that share corners with four equivalent S(3)CeHo3 tetrahedra, corners with two equivalent S(2)Ce2Ho3 trigonal bipyramids, corners with four equivalent S(1)Ho5 trigonal bipyramids, edges with three equivalent S(3)CeHo3 tetrahedra,  an edgeedge with one S(1)Ho5 trigonal bipyramid, and edges with five equivalent S(2)Ce2Ho3 trigonal bipyramids. In the third S site, S(3) is bonded to one Ho(1), two equivalent Ho(2), and one Ce(1) atom to form distorted SCeHo3 tetrahedra that share corners with three equivalent S(3)CeHo3 tetrahedra, corners with four equivalent S(2)Ce2Ho3 trigonal bipyramids, corners with five equivalent S(1)Ho5 trigonal bipyramids,  an edgeedge with one S(1)Ho5 trigonal bipyramid, and edges with three equivalent S(2)Ce2Ho3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a square co-planar geometry to four equivalent Ho(1) atoms.
Ho4CeS7 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ho sites. In the first Ho site, Ho(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form HoS6 octahedra that share  a cornercorner with one Ce(1)S6 octahedra, corners with two equivalent Ho(1)S6 octahedra, corners with six equivalent Ho(2)S7 pentagonal bipyramids, edges with five equivalent Ho(1)S6 octahedra, and  an edgeedge with one Ho(2)S7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 0-59°. The Ho(1)-S(3) bond length is 2.69 Å. Both Ho(1)-S(4) bond lengths are 2.69 Å. There are two shorter (2.77 Å) and one longer (2.81 Å) Ho(1)-S(1) bond length. In the second Ho site, Ho(2) is bonded to two equivalent S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted HoS7 pentagonal bipyramids that share corners with two equivalent Ce(1)S6 octahedra, corners with six equivalent Ho(1)S6 octahedra,  an edgeedge with one Ho(1)S6 octahedra, edges with three equivalent Ce(1)S6 octahedra, edges with two equivalent Ho(2)S7 pentagonal bipyramids, and faces with two equivalent Ho(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-69°. Both Ho(2)-S(1) bond lengths are 2.96 Å. Both Ho(2)-S(3) bond lengths are 2.74 Å. There are two shorter (2.79 Å) and one longer (2.98 Å) Ho(2)-S(2) bond length. Ce(1) is bonded to two equivalent S(3) and four equivalent S(2) atoms to form CeS6 octahedra that share corners with two equivalent Ho(1)S6 octahedra, corners with four equivalent Ho(2)S7 pentagonal bipyramids, edges with two equivalent Ce(1)S6 octahedra, and edges with six equivalent Ho(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 59°. Both Ce(1)-S(3) bond lengths are 2.77 Å. All Ce(1)-S(2) bond lengths are 2.82 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ho(2) and three equivalent Ho(1) atoms to form distorted SHo5 trigonal bipyramids that share corners with five equivalent S(3)CeHo3 tetrahedra, corners with four equivalent S(2)Ce2Ho3 trigonal bipyramids,  an edgeedge with one S(3)CeHo3 tetrahedra,  an edgeedge with one S(2)Ce2Ho3 trigonal bipyramid, and edges with four equivalent S(1)Ho5 trigonal bipyramids. In the second S site, S(2) is bonded to three equivalent Ho(2) and two equivalent Ce(1) atoms to form distorted SCe2Ho3 trigonal bipyramids that share corners with four equivalent S(3)CeHo3 tetrahedra, corners with two equivalent S(2)Ce2Ho3 trigonal bipyramids, corners with four equivalent S(1)Ho5 trigonal bipyramids, edges with three equivalent S(3)CeHo3 tetrahedra,  an edgeedge with one S(1)Ho5 trigonal bipyramid, and edges with five equivalent S(2)Ce2Ho3 trigonal bipyramids. In the third S site, S(3) is bonded to one Ho(1), two equivalent Ho(2), and one Ce(1) atom to form distorted SCeHo3 tetrahedra that share corners with three equivalent S(3)CeHo3 tetrahedra, corners with four equivalent S(2)Ce2Ho3 trigonal bipyramids, corners with five equivalent S(1)Ho5 trigonal bipyramids,  an edgeedge with one S(1)Ho5 trigonal bipyramid, and edges with three equivalent S(2)Ce2Ho3 trigonal bipyramids. In the fourth S site, S(4) is bonded in a square co-planar geometry to four equivalent Ho(1) atoms.