Cs5(SO4)4 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 14-coordinate geometry to two equivalent O(1), four equivalent O(5), and eight equivalent O(6) atoms. In the second Cs site, Cs(2) is bonded to one O(2), one O(5), two equivalent O(3), two equivalent O(6), three equivalent O(1), and three equivalent O(4) atoms to form distorted CsO12 cuboctahedra that share edges with six equivalent Cs(2)O12 cuboctahedra, edges with three equivalent S(1)O4 tetrahedra, and edges with three equivalent S(2)O4 tetrahedra. In the third Cs site, Cs(3) is bonded in a 10-coordinate geometry to one O(4), three equivalent O(2), and six equivalent O(3) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SO4 tetrahedra that share edges with three equivalent Cs(2)O12 cuboctahedra. In the second S site, S(2) is bonded to one O(4), one O(5), and two equivalent O(6) atoms to form SO4 tetrahedra that share edges with three equivalent Cs(2)O12 cuboctahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cs(1), three equivalent Cs(2), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cs(2), three equivalent Cs(3), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(2), three equivalent Cs(3), and one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Cs(3), three equivalent Cs(2), and one S(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one S(2) atom.
Cs5(SO4)4 crystallizes in the orthorhombic Cmcm space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 14-coordinate geometry to two equivalent O(1), four equivalent O(5), and eight equivalent O(6) atoms. Both Cs(1)-O(1) bond lengths are 3.81 Å. All Cs(1)-O(5) bond lengths are 3.38 Å. There are four shorter (3.35 Å) and four longer (3.37 Å) Cs(1)-O(6) bond lengths. In the second Cs site, Cs(2) is bonded to one O(2), one O(5), two equivalent O(3), two equivalent O(6), three equivalent O(1), and three equivalent O(4) atoms to form distorted CsO12 cuboctahedra that share edges with six equivalent Cs(2)O12 cuboctahedra, edges with three equivalent S(1)O4 tetrahedra, and edges with three equivalent S(2)O4 tetrahedra. The Cs(2)-O(2) bond length is 3.22 Å. The Cs(2)-O(5) bond length is 3.07 Å. Both Cs(2)-O(3) bond lengths are 3.09 Å. Both Cs(2)-O(6) bond lengths are 3.03 Å. There is one shorter (3.55 Å) and two longer (3.56 Å) Cs(2)-O(1) bond lengths. There is one shorter (3.53 Å) and two longer (3.56 Å) Cs(2)-O(4) bond lengths. In the third Cs site, Cs(3) is bonded in a 10-coordinate geometry to one O(4), three equivalent O(2), and six equivalent O(3) atoms. The Cs(3)-O(4) bond length is 3.19 Å. There are two shorter (3.19 Å) and one longer (3.20 Å) Cs(3)-O(2) bond length. There are a spread of Cs(3)-O(3) bond distances ranging from 3.14-3.28 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SO4 tetrahedra that share edges with three equivalent Cs(2)O12 cuboctahedra. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.49 Å. Both S(1)-O(3) bond lengths are 1.47 Å. In the second S site, S(2) is bonded to one O(4), one O(5), and two equivalent O(6) atoms to form SO4 tetrahedra that share edges with three equivalent Cs(2)O12 cuboctahedra. The S(2)-O(4) bond length is 1.47 Å. The S(2)-O(5) bond length is 1.48 Å. Both S(2)-O(6) bond lengths are 1.47 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cs(1), three equivalent Cs(2), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cs(2), three equivalent Cs(3), and one S(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(2), three equivalent Cs(3), and one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Cs(3), three equivalent Cs(2), and one S(2) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one S(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Cs(2), two equivalent Cs(1), and one S(2) atom.