Bi14SO24 crystallizes in the monoclinic Cm space group. There are nine inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(11), one O(3), one O(4), one O(5), and one O(8) atom. In the third Bi site, Bi(3) is bonded to one O(1), one O(10), one O(11), one O(6), and one O(8) atom to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(5), and two equivalent O(9) atoms. In the fifth Bi site, Bi(5) is bonded in a distorted body-centered cubic geometry to one O(1), one O(10), one O(11), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. In the sixth Bi site, Bi(6) is bonded in a 7-coordinate geometry to one O(12), two equivalent O(10), two equivalent O(3), and two equivalent O(5) atoms. In the seventh Bi site, Bi(7) is bonded to one O(1), one O(11), one O(2), one O(4), and one O(6) atom to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. In the eighth Bi site, Bi(8) is bonded to one O(1), one O(4), one O(5), one O(8), and one O(9) atom to form distorted corner-sharing BiO5 square pyramids. In the ninth Bi site, Bi(9) is bonded in a 7-coordinate geometry to one O(13), two equivalent O(10), two equivalent O(6), and two equivalent O(9) atoms. S(1) is bonded in a tetrahedral geometry to one O(12), one O(13), and two equivalent O(7) atoms. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to one Bi(3), one Bi(5), one Bi(7), and one Bi(8) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(4), one Bi(5), and one Bi(7) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(2), one Bi(5), and one Bi(6) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(5), one Bi(7), and one Bi(8) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Bi(2), one Bi(4), one Bi(6), and one Bi(8) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Bi(3), one Bi(7), and one Bi(9) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one S(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(3), one Bi(5), and one Bi(8) atom. In the ninth O site, O(9) is bonded to one Bi(4), one Bi(5), one Bi(8), and one Bi(9) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the tenth O site, O(10) is bonded to one Bi(3), one Bi(5), one Bi(6), and one Bi(9) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the eleventh O site, O(11) is bonded to one Bi(2), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Bi(6) and one S(1) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one Bi(9) and one S(1) atom.
Bi14SO24 crystallizes in the monoclinic Cm space group. There are nine inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Bi(1)-O(2) bond lengths are 2.23 Å. Both Bi(1)-O(3) bond lengths are 2.23 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(11), one O(3), one O(4), one O(5), and one O(8) atom. The Bi(2)-O(11) bond length is 2.24 Å. The Bi(2)-O(3) bond length is 2.47 Å. The Bi(2)-O(4) bond length is 2.12 Å. The Bi(2)-O(5) bond length is 2.18 Å. The Bi(2)-O(8) bond length is 2.67 Å. In the third Bi site, Bi(3) is bonded to one O(1), one O(10), one O(11), one O(6), and one O(8) atom to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. The Bi(3)-O(1) bond length is 2.68 Å. The Bi(3)-O(10) bond length is 2.48 Å. The Bi(3)-O(11) bond length is 2.11 Å. The Bi(3)-O(6) bond length is 2.18 Å. The Bi(3)-O(8) bond length is 2.24 Å. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(5), and two equivalent O(9) atoms. Both Bi(4)-O(2) bond lengths are 2.25 Å. Both Bi(4)-O(5) bond lengths are 2.81 Å. Both Bi(4)-O(9) bond lengths are 2.23 Å. In the fifth Bi site, Bi(5) is bonded in a distorted body-centered cubic geometry to one O(1), one O(10), one O(11), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. The Bi(5)-O(1) bond length is 2.72 Å. The Bi(5)-O(10) bond length is 2.34 Å. The Bi(5)-O(11) bond length is 2.66 Å. The Bi(5)-O(2) bond length is 2.39 Å. The Bi(5)-O(3) bond length is 2.34 Å. The Bi(5)-O(4) bond length is 2.62 Å. The Bi(5)-O(8) bond length is 2.74 Å. The Bi(5)-O(9) bond length is 2.40 Å. In the sixth Bi site, Bi(6) is bonded in a 7-coordinate geometry to one O(12), two equivalent O(10), two equivalent O(3), and two equivalent O(5) atoms. The Bi(6)-O(12) bond length is 2.70 Å. Both Bi(6)-O(10) bond lengths are 2.24 Å. Both Bi(6)-O(3) bond lengths are 2.30 Å. Both Bi(6)-O(5) bond lengths are 2.81 Å. In the seventh Bi site, Bi(7) is bonded to one O(1), one O(11), one O(2), one O(4), and one O(6) atom to form a mixture of distorted corner and edge-sharing BiO5 square pyramids. The Bi(7)-O(1) bond length is 2.12 Å. The Bi(7)-O(11) bond length is 2.70 Å. The Bi(7)-O(2) bond length is 2.48 Å. The Bi(7)-O(4) bond length is 2.24 Å. The Bi(7)-O(6) bond length is 2.17 Å. In the eighth Bi site, Bi(8) is bonded to one O(1), one O(4), one O(5), one O(8), and one O(9) atom to form distorted corner-sharing BiO5 square pyramids. The Bi(8)-O(1) bond length is 2.24 Å. The Bi(8)-O(4) bond length is 2.72 Å. The Bi(8)-O(5) bond length is 2.16 Å. The Bi(8)-O(8) bond length is 2.11 Å. The Bi(8)-O(9) bond length is 2.49 Å. In the ninth Bi site, Bi(9) is bonded in a 7-coordinate geometry to one O(13), two equivalent O(10), two equivalent O(6), and two equivalent O(9) atoms. The Bi(9)-O(13) bond length is 2.67 Å. Both Bi(9)-O(10) bond lengths are 2.31 Å. Both Bi(9)-O(6) bond lengths are 2.78 Å. Both Bi(9)-O(9) bond lengths are 2.25 Å. S(1) is bonded in a tetrahedral geometry to one O(12), one O(13), and two equivalent O(7) atoms. The S(1)-O(12) bond length is 1.49 Å. The S(1)-O(13) bond length is 1.49 Å. Both S(1)-O(7) bond lengths are 1.48 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to one Bi(3), one Bi(5), one Bi(7), and one Bi(8) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the second O site, O(2) is bonded to one Bi(1), one Bi(4), one Bi(5), and one Bi(7) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(2), one Bi(5), and one Bi(6) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(2), one Bi(5), one Bi(7), and one Bi(8) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one Bi(2), one Bi(4), one Bi(6), and one Bi(8) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Bi(3), one Bi(7), and one Bi(9) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one S(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(3), one Bi(5), and one Bi(8) atom. In the ninth O site, O(9) is bonded to one Bi(4), one Bi(5), one Bi(8), and one Bi(9) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the tenth O site, O(10) is bonded to one Bi(3), one Bi(5), one Bi(6), and one Bi(9) atom to form a mixture of corner and edge-sharing OBi4 tetrahedra. In the eleventh O site, O(11) is bonded to one Bi(2), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of distorted corner and edge-sharing OBi4 tetrahedra. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Bi(6) and one S(1) atom. In the thirteenth O site, O(13) is bonded in a distorted single-bond geometry to one Bi(9) and one S(1) atom.