Ho4MnS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. In the second Ho site, Ho(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms. In the third Ho site, Ho(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(4)S6 octahedra,  a cornercorner with one Mn(1)S6 octahedra, and edges with two equivalent Ho(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. In the fourth Ho site, Ho(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(3)S6 octahedra, corners with two equivalent Mn(1)S6 octahedra, edges with two equivalent Ho(4)S6 octahedra, and edges with three equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-52°. Mn(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form MnS6 octahedra that share  a cornercorner with one Ho(3)S6 octahedra, corners with two equivalent Ho(4)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, and edges with three equivalent Ho(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-55°. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ho(2), two equivalent Ho(4), and one Mn(1) atom to form SHo4Mn trigonal bipyramids that share  a cornercorner with one S(5)Ho3Mn tetrahedra, corners with four equivalent S(6)Ho4 tetrahedra, corners with two equivalent S(3)Ho5 trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(6)Ho4 tetrahedra,  an edgeedge with one S(4)Ho5 trigonal bipyramid, edges with two equivalent S(2)Ho3Mn2 trigonal bipyramids, and edges with two equivalent S(1)Ho4Mn trigonal bipyramids. In the second S site, S(2) is bonded to one Ho(4), two equivalent Ho(1), and two equivalent Mn(1) atoms to form SHo3Mn2 trigonal bipyramids that share  a cornercorner with one S(6)Ho4 tetrahedra, corners with four equivalent S(5)Ho3Mn tetrahedra, corners with two equivalent S(3)Ho5 trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(5)Ho3Mn tetrahedra,  an edgeedge with one S(3)Ho5 trigonal bipyramid, edges with two equivalent S(2)Ho3Mn2 trigonal bipyramids, and edges with two equivalent S(1)Ho4Mn trigonal bipyramids. In the third S site, S(3) is bonded to one Ho(2), two equivalent Ho(1), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share corners with four equivalent S(5)Ho3Mn tetrahedra, corners with two equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with two equivalent S(1)Ho4Mn trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(5)Ho3Mn tetrahedra, edges with two equivalent S(6)Ho4 tetrahedra,  an edgeedge with one S(2)Ho3Mn2 trigonal bipyramid, edges with two equivalent S(3)Ho5 trigonal bipyramids, and edges with three equivalent S(4)Ho5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ho(1), two equivalent Ho(2), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share corners with four equivalent S(6)Ho4 tetrahedra, corners with two equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with two equivalent S(1)Ho4Mn trigonal bipyramids, corners with two equivalent S(3)Ho5 trigonal bipyramids,  an edgeedge with one S(6)Ho4 tetrahedra, edges with two equivalent S(5)Ho3Mn tetrahedra,  an edgeedge with one S(1)Ho4Mn trigonal bipyramid, edges with two equivalent S(4)Ho5 trigonal bipyramids, and edges with three equivalent S(3)Ho5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ho(3), two equivalent Ho(1), and one Mn(1) atom to form SHo3Mn tetrahedra that share  a cornercorner with one S(6)Ho4 tetrahedra, corners with two equivalent S(5)Ho3Mn tetrahedra,  a cornercorner with one S(1)Ho4Mn trigonal bipyramid, corners with four equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with four equivalent S(3)Ho5 trigonal bipyramids,  an edgeedge with one S(2)Ho3Mn2 trigonal bipyramid,  an edgeedge with one S(3)Ho5 trigonal bipyramid, and edges with two equivalent S(4)Ho5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ho(3), one Ho(4), and two equivalent Ho(2) atoms to form SHo4 tetrahedra that share  a cornercorner with one S(5)Ho3Mn tetrahedra, corners with two equivalent S(6)Ho4 tetrahedra,  a cornercorner with one S(2)Ho3Mn2 trigonal bipyramid, corners with four equivalent S(1)Ho4Mn trigonal bipyramids, corners with four equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(1)Ho4Mn trigonal bipyramid,  an edgeedge with one S(4)Ho5 trigonal bipyramid, and edges with two equivalent S(3)Ho5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to two equivalent Ho(4) and two equivalent Mn(1) atoms.
Ho4MnS7 crystallizes in the monoclinic Cm space group. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(3), and two equivalent S(5) atoms. The Ho(1)-S(4) bond length is 3.06 Å. Both Ho(1)-S(2) bond lengths are 2.85 Å. Both Ho(1)-S(3) bond lengths are 2.88 Å. Both Ho(1)-S(5) bond lengths are 2.69 Å. In the second Ho site, Ho(2) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(1), two equivalent S(4), and two equivalent S(6) atoms. The Ho(2)-S(3) bond length is 2.99 Å. Both Ho(2)-S(1) bond lengths are 2.88 Å. Both Ho(2)-S(4) bond lengths are 2.85 Å. Both Ho(2)-S(6) bond lengths are 2.68 Å. In the third Ho site, Ho(3) is bonded to one S(5), one S(6), two equivalent S(3), and two equivalent S(4) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(4)S6 octahedra,  a cornercorner with one Mn(1)S6 octahedra, and edges with two equivalent Ho(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. The Ho(3)-S(5) bond length is 2.64 Å. The Ho(3)-S(6) bond length is 2.68 Å. Both Ho(3)-S(3) bond lengths are 2.70 Å. Both Ho(3)-S(4) bond lengths are 2.70 Å. In the fourth Ho site, Ho(4) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(7) atoms to form HoS6 octahedra that share  a cornercorner with one Ho(3)S6 octahedra, corners with two equivalent Mn(1)S6 octahedra, edges with two equivalent Ho(4)S6 octahedra, and edges with three equivalent Mn(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-52°. The Ho(4)-S(2) bond length is 2.69 Å. The Ho(4)-S(6) bond length is 2.70 Å. Both Ho(4)-S(1) bond lengths are 2.75 Å. Both Ho(4)-S(7) bond lengths are 2.65 Å. Mn(1) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(7) atoms to form MnS6 octahedra that share  a cornercorner with one Ho(3)S6 octahedra, corners with two equivalent Ho(4)S6 octahedra, edges with two equivalent Mn(1)S6 octahedra, and edges with three equivalent Ho(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 2-55°. The Mn(1)-S(1) bond length is 2.66 Å. The Mn(1)-S(5) bond length is 2.53 Å. Both Mn(1)-S(2) bond lengths are 2.63 Å. Both Mn(1)-S(7) bond lengths are 2.61 Å. There are seven inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ho(2), two equivalent Ho(4), and one Mn(1) atom to form SHo4Mn trigonal bipyramids that share  a cornercorner with one S(5)Ho3Mn tetrahedra, corners with four equivalent S(6)Ho4 tetrahedra, corners with two equivalent S(3)Ho5 trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(6)Ho4 tetrahedra,  an edgeedge with one S(4)Ho5 trigonal bipyramid, edges with two equivalent S(2)Ho3Mn2 trigonal bipyramids, and edges with two equivalent S(1)Ho4Mn trigonal bipyramids. In the second S site, S(2) is bonded to one Ho(4), two equivalent Ho(1), and two equivalent Mn(1) atoms to form SHo3Mn2 trigonal bipyramids that share  a cornercorner with one S(6)Ho4 tetrahedra, corners with four equivalent S(5)Ho3Mn tetrahedra, corners with two equivalent S(3)Ho5 trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(5)Ho3Mn tetrahedra,  an edgeedge with one S(3)Ho5 trigonal bipyramid, edges with two equivalent S(2)Ho3Mn2 trigonal bipyramids, and edges with two equivalent S(1)Ho4Mn trigonal bipyramids. In the third S site, S(3) is bonded to one Ho(2), two equivalent Ho(1), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share corners with four equivalent S(5)Ho3Mn tetrahedra, corners with two equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with two equivalent S(1)Ho4Mn trigonal bipyramids, corners with two equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(5)Ho3Mn tetrahedra, edges with two equivalent S(6)Ho4 tetrahedra,  an edgeedge with one S(2)Ho3Mn2 trigonal bipyramid, edges with two equivalent S(3)Ho5 trigonal bipyramids, and edges with three equivalent S(4)Ho5 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ho(1), two equivalent Ho(2), and two equivalent Ho(3) atoms to form distorted SHo5 trigonal bipyramids that share corners with four equivalent S(6)Ho4 tetrahedra, corners with two equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with two equivalent S(1)Ho4Mn trigonal bipyramids, corners with two equivalent S(3)Ho5 trigonal bipyramids,  an edgeedge with one S(6)Ho4 tetrahedra, edges with two equivalent S(5)Ho3Mn tetrahedra,  an edgeedge with one S(1)Ho4Mn trigonal bipyramid, edges with two equivalent S(4)Ho5 trigonal bipyramids, and edges with three equivalent S(3)Ho5 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ho(3), two equivalent Ho(1), and one Mn(1) atom to form SHo3Mn tetrahedra that share  a cornercorner with one S(6)Ho4 tetrahedra, corners with two equivalent S(5)Ho3Mn tetrahedra,  a cornercorner with one S(1)Ho4Mn trigonal bipyramid, corners with four equivalent S(2)Ho3Mn2 trigonal bipyramids, corners with four equivalent S(3)Ho5 trigonal bipyramids,  an edgeedge with one S(2)Ho3Mn2 trigonal bipyramid,  an edgeedge with one S(3)Ho5 trigonal bipyramid, and edges with two equivalent S(4)Ho5 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ho(3), one Ho(4), and two equivalent Ho(2) atoms to form SHo4 tetrahedra that share  a cornercorner with one S(5)Ho3Mn tetrahedra, corners with two equivalent S(6)Ho4 tetrahedra,  a cornercorner with one S(2)Ho3Mn2 trigonal bipyramid, corners with four equivalent S(1)Ho4Mn trigonal bipyramids, corners with four equivalent S(4)Ho5 trigonal bipyramids,  an edgeedge with one S(1)Ho4Mn trigonal bipyramid,  an edgeedge with one S(4)Ho5 trigonal bipyramid, and edges with two equivalent S(3)Ho5 trigonal bipyramids. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to two equivalent Ho(4) and two equivalent Mn(1) atoms.