HoSO5 crystallizes in the orthorhombic Pccn space group. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form distorted HoO7 pentagonal bipyramids that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(1)O4 tetrahedra,  an edgeedge with one Ho(3)O7 pentagonal bipyramid, and  an edgeedge with one Ho(2)O6 pentagonal pyramid. The Ho(1)-O(1) bond length is 2.31 Å. The Ho(1)-O(2) bond length is 2.39 Å. The Ho(1)-O(3) bond length is 2.40 Å. The Ho(1)-O(4) bond length is 2.39 Å. The Ho(1)-O(5) bond length is 2.33 Å. The Ho(1)-O(6) bond length is 2.42 Å. The Ho(1)-O(7) bond length is 2.36 Å. In the second Ho site, Ho(2) is bonded to one O(1), one O(10), one O(11), one O(4), one O(8), and one O(9) atom to form distorted HoO6 pentagonal pyramids that share  a cornercorner with one S(1)O4 tetrahedra,  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra,  an edgeedge with one Ho(1)O7 pentagonal bipyramid, and  an edgeedge with one Ho(3)O7 pentagonal bipyramid. The Ho(2)-O(1) bond length is 2.32 Å. The Ho(2)-O(10) bond length is 2.34 Å. The Ho(2)-O(11) bond length is 2.31 Å. The Ho(2)-O(4) bond length is 2.37 Å. The Ho(2)-O(8) bond length is 2.40 Å. The Ho(2)-O(9) bond length is 2.32 Å. In the third Ho site, Ho(3) is bonded to one O(1), one O(12), one O(13), one O(14), one O(15), one O(3), and one O(8) atom to form distorted HoO7 pentagonal bipyramids that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent S(4)O4 tetrahedra,  an edgeedge with one Ho(1)O7 pentagonal bipyramid, and  an edgeedge with one Ho(2)O6 pentagonal pyramid. The Ho(3)-O(1) bond length is 2.43 Å. The Ho(3)-O(12) bond length is 2.36 Å. The Ho(3)-O(13) bond length is 2.31 Å. The Ho(3)-O(14) bond length is 2.33 Å. The Ho(3)-O(15) bond length is 2.34 Å. The Ho(3)-O(3) bond length is 2.39 Å. The Ho(3)-O(8) bond length is 2.32 Å. In the fourth Ho site, Ho(4) is bonded in a distorted pentagonal planar geometry to one O(17), one O(18), one O(3), one O(4), and one O(8) atom. The Ho(4)-O(17) bond length is 2.32 Å. The Ho(4)-O(18) bond length is 2.28 Å. The Ho(4)-O(3) bond length is 2.40 Å. The Ho(4)-O(4) bond length is 2.32 Å. The Ho(4)-O(8) bond length is 2.35 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one O(10), one O(16), one O(2), and one O(6) atom to form SO4 tetrahedra that share corners with two equivalent Ho(1)O7 pentagonal bipyramids and  a cornercorner with one Ho(2)O6 pentagonal pyramid. The S(1)-O(10) bond length is 1.47 Å. The S(1)-O(16) bond length is 1.46 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(6) bond length is 1.49 Å. In the second S site, S(2) is bonded to one O(11), one O(15), one O(17), and one O(5) atom to form SO4 tetrahedra that share  a cornercorner with one Ho(1)O7 pentagonal bipyramid,  a cornercorner with one Ho(3)O7 pentagonal bipyramid, and  a cornercorner with one Ho(2)O6 pentagonal pyramid. The S(2)-O(11) bond length is 1.47 Å. The S(2)-O(15) bond length is 1.46 Å. The S(2)-O(17) bond length is 1.47 Å. The S(2)-O(5) bond length is 1.47 Å. In the third S site, S(3) is bonded to one O(13), one O(19), one O(7), and one O(9) atom to form SO4 tetrahedra that share  a cornercorner with one Ho(1)O7 pentagonal bipyramid,  a cornercorner with one Ho(3)O7 pentagonal bipyramid, and  a cornercorner with one Ho(2)O6 pentagonal pyramid. The S(3)-O(13) bond length is 1.48 Å. The S(3)-O(19) bond length is 1.45 Å. The S(3)-O(7) bond length is 1.48 Å. The S(3)-O(9) bond length is 1.47 Å. In the fourth S site, S(4) is bonded to one O(12), one O(14), one O(18), and one O(20) atom to form SO4 tetrahedra that share corners with two equivalent Ho(3)O7 pentagonal bipyramids. The S(4)-O(12) bond length is 1.46 Å. The S(4)-O(14) bond length is 1.47 Å. The S(4)-O(18) bond length is 1.48 Å. The S(4)-O(20) bond length is 1.46 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Ho(1), one Ho(2), and one Ho(3) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Ho(1) and one S(1) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Ho(1), one Ho(3), and one Ho(4) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Ho(1), one Ho(2), and one Ho(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Ho(1) and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Ho(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Ho(1) and one S(3) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one Ho(2), one Ho(3), and one Ho(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ho(2) and one S(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Ho(2) and one S(1) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Ho(2) and one S(2) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Ho(3) and one S(4) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Ho(3) and one S(3) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Ho(3) and one S(4) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Ho(3) and one S(2) atom. In the sixteenth O site, O(16) is bonded in a single-bond geometry to one S(1) atom. In the seventeenth O site, O(17) is bonded in a distorted single-bond geometry to one Ho(4) and one S(2) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Ho(4) and one S(4) atom. In the nineteenth O site, O(19) is bonded in a single-bond geometry to one S(3) atom. In the twentieth O site, O(20) is bonded in a single-bond geometry to one S(4) atom. Linkers: 32 [O]S([O])(=O)=O. Metal clusters: 32 [Ho]. The MOF has largest included sphere 4.71 A, density 2.98 g/cm3, surface area 1658.68 m2/g, accessible volume 0.13 cm3/g