Bi14SO24 crystallizes in the triclinic P-1 space group. There are seven inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(7), and two equivalent O(4) atoms. In the second Bi site, Bi(2) is bonded to one O(2), one O(6), one O(8), and two equivalent O(1) atoms to form a mixture of distorted edge and corner-sharing BiO5 square pyramids. In the third Bi site, Bi(3) is bonded in a distorted body-centered cubic geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(8) atom. In the fourth Bi site, Bi(4) is bonded in a 5-coordinate geometry to one O(11), one O(4), one O(6), and two equivalent O(12) atoms. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(6) atoms. In the sixth Bi site, Bi(6) is bonded to one O(10), one O(12), one O(7), and two equivalent O(8) atoms to form a mixture of distorted edge and corner-sharing BiO5 square pyramids. In the seventh Bi site, Bi(7) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(9), and two equivalent O(7) atoms. S(1) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(9) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(2), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a single-bond geometry to one S(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(4), and two equivalent Bi(5) atoms. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(6), and two equivalent Bi(7) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(3), and two equivalent Bi(6) atoms. In the ninth O site, O(9) is bonded in a single-bond geometry to one Bi(7) and one S(1) atom. In the tenth O site, O(10) is bonded to one Bi(3), one Bi(5), one Bi(6), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eleventh O site, O(11) is bonded to one Bi(3), one Bi(4), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the twelfth O site, O(12) is bonded to one Bi(3), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra.
Bi14SO24 crystallizes in the triclinic P-1 space group. There are seven inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(7), and two equivalent O(4) atoms. The Bi(1)-O(1) bond length is 2.26 Å. The Bi(1)-O(3) bond length is 2.48 Å. The Bi(1)-O(7) bond length is 2.23 Å. There is one shorter (2.17 Å) and one longer (2.73 Å) Bi(1)-O(4) bond length. In the second Bi site, Bi(2) is bonded to one O(2), one O(6), one O(8), and two equivalent O(1) atoms to form a mixture of distorted edge and corner-sharing BiO5 square pyramids. The Bi(2)-O(2) bond length is 2.51 Å. The Bi(2)-O(6) bond length is 2.22 Å. The Bi(2)-O(8) bond length is 2.23 Å. There is one shorter (2.13 Å) and one longer (2.69 Å) Bi(2)-O(1) bond length. In the third Bi site, Bi(3) is bonded in a distorted body-centered cubic geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(8) atom. The Bi(3)-O(1) bond length is 2.80 Å. The Bi(3)-O(10) bond length is 2.36 Å. The Bi(3)-O(11) bond length is 2.36 Å. The Bi(3)-O(12) bond length is 2.74 Å. The Bi(3)-O(2) bond length is 2.40 Å. The Bi(3)-O(3) bond length is 2.37 Å. The Bi(3)-O(4) bond length is 2.74 Å. The Bi(3)-O(8) bond length is 2.78 Å. In the fourth Bi site, Bi(4) is bonded in a 5-coordinate geometry to one O(11), one O(4), one O(6), and two equivalent O(12) atoms. The Bi(4)-O(11) bond length is 2.53 Å. The Bi(4)-O(4) bond length is 2.23 Å. The Bi(4)-O(6) bond length is 2.23 Å. There is one shorter (2.17 Å) and one longer (2.66 Å) Bi(4)-O(12) bond length. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(6) atoms. The Bi(5)-O(10) bond length is 2.28 Å. The Bi(5)-O(11) bond length is 2.26 Å. The Bi(5)-O(2) bond length is 2.25 Å. The Bi(5)-O(3) bond length is 2.25 Å. There is one shorter (2.78 Å) and one longer (2.86 Å) Bi(5)-O(6) bond length. In the sixth Bi site, Bi(6) is bonded to one O(10), one O(12), one O(7), and two equivalent O(8) atoms to form a mixture of distorted edge and corner-sharing BiO5 square pyramids. The Bi(6)-O(10) bond length is 2.48 Å. The Bi(6)-O(12) bond length is 2.26 Å. The Bi(6)-O(7) bond length is 2.21 Å. There is one shorter (2.15 Å) and one longer (2.74 Å) Bi(6)-O(8) bond length. In the seventh Bi site, Bi(7) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(9), and two equivalent O(7) atoms. The Bi(7)-O(10) bond length is 2.30 Å. The Bi(7)-O(11) bond length is 2.28 Å. The Bi(7)-O(2) bond length is 2.29 Å. The Bi(7)-O(3) bond length is 2.32 Å. The Bi(7)-O(9) bond length is 2.86 Å. Both Bi(7)-O(7) bond lengths are 2.76 Å. S(1) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(9) atoms. Both S(1)-O(5) bond lengths are 1.60 Å. Both S(1)-O(9) bond lengths are 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(3), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to one Bi(2), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the third O site, O(3) is bonded to one Bi(1), one Bi(3), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the fourth O site, O(4) is bonded to one Bi(3), one Bi(4), and two equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra. In the fifth O site, O(5) is bonded in a single-bond geometry to one S(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(4), and two equivalent Bi(5) atoms. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(6), and two equivalent Bi(7) atoms. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(2), one Bi(3), and two equivalent Bi(6) atoms. In the ninth O site, O(9) is bonded in a single-bond geometry to one Bi(7) and one S(1) atom. In the tenth O site, O(10) is bonded to one Bi(3), one Bi(5), one Bi(6), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the eleventh O site, O(11) is bonded to one Bi(3), one Bi(4), one Bi(5), and one Bi(7) atom to form a mixture of edge and corner-sharing OBi4 tetrahedra. In the twelfth O site, O(12) is bonded to one Bi(3), one Bi(6), and two equivalent Bi(4) atoms to form a mixture of distorted edge and corner-sharing OBi4 tetrahedra.