Cs4V2S4O3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted body-centered cubic geometry to two equivalent S(2), four equivalent S(1), and two equivalent O(2) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to two equivalent S(2), four equivalent S(1), one O(1), and two equivalent O(2) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to two equivalent S(1), four equivalent S(2), and two equivalent O(2) atoms. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to two equivalent S(1), four equivalent S(2), and two equivalent O(2) atoms. V(1) is bonded to one S(1), one S(2), one O(1), and one O(2) atom to form corner-sharing VS2O2 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(4), two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), two equivalent Cs(3), two equivalent Cs(4), and one V(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), and one V(1) atom.
Cs4V2S4O3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted body-centered cubic geometry to two equivalent S(2), four equivalent S(1), and two equivalent O(2) atoms. Both Cs(1)-S(2) bond lengths are 3.70 Å. There are two shorter (3.59 Å) and two longer (3.74 Å) Cs(1)-S(1) bond lengths. Both Cs(1)-O(2) bond lengths are 3.17 Å. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to two equivalent S(2), four equivalent S(1), one O(1), and two equivalent O(2) atoms. Both Cs(2)-S(2) bond lengths are 3.64 Å. There are two shorter (3.80 Å) and two longer (3.84 Å) Cs(2)-S(1) bond lengths. The Cs(2)-O(1) bond length is 3.07 Å. Both Cs(2)-O(2) bond lengths are 3.48 Å. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to two equivalent S(1), four equivalent S(2), and two equivalent O(2) atoms. Both Cs(3)-S(1) bond lengths are 3.66 Å. There are two shorter (3.50 Å) and two longer (4.04 Å) Cs(3)-S(2) bond lengths. Both Cs(3)-O(2) bond lengths are 3.35 Å. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to two equivalent S(1), four equivalent S(2), and two equivalent O(2) atoms. Both Cs(4)-S(1) bond lengths are 3.57 Å. There are two shorter (3.78 Å) and two longer (3.93 Å) Cs(4)-S(2) bond lengths. Both Cs(4)-O(2) bond lengths are 3.54 Å. V(1) is bonded to one S(1), one S(2), one O(1), and one O(2) atom to form corner-sharing VS2O2 tetrahedra. The V(1)-S(1) bond length is 2.18 Å. The V(1)-S(2) bond length is 2.18 Å. The V(1)-O(1) bond length is 1.83 Å. The V(1)-O(2) bond length is 1.68 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(4), two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), two equivalent Cs(3), two equivalent Cs(4), and one V(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), one Cs(3), one Cs(4), and one V(1) atom.