Bi5(TeO6)3 crystallizes in the monoclinic C2 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(12), one O(18), one O(2), and one O(9) atom to form BiO6 octahedra that share corners with two equivalent Te(2)O6 octahedra and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(14), one O(15), one O(16), one O(4), and one O(8) atom. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(16), one O(2), one O(3), one O(7), and one O(8) atom. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(16), one O(17), one O(5), and one O(6) atom. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to two equivalent O(17), two equivalent O(18), and two equivalent O(6) atoms. In the sixth Bi site, Bi(6) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(1), one O(10), one O(12), one O(13), one O(17), and one O(9) atom to form TeO6 octahedra that share edges with two equivalent Bi(1)O6 octahedra. In the second Te site, Te(2) is bonded to one O(11), one O(18), one O(2), one O(4), one O(6), and one O(7) atom to form TeO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. In the third Te site, Te(3) is bonded in an octahedral geometry to one O(14), one O(15), one O(16), one O(3), one O(5), and one O(8) atom. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Bi(1), one Bi(3), and one Te(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Bi(3), one Bi(6), and one Te(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Bi(2), one Bi(6), and one Te(2) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one Bi(4) and one Te(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Bi(4), one Bi(5), and one Te(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Bi(3), one Bi(6), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Bi(2), one Bi(3), and one Te(3) atom. In the ninth O site, O(9) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the tenth O site, O(10) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Bi(4) and one Te(2) atom. In the twelfth O site, O(12) is bonded to one Bi(1), one Bi(3), one Bi(4), and one Te(1) atom to form distorted edge-sharing OBi3Te trigonal pyramids. In the thirteenth O site, O(13) is bonded in a water-like geometry to one Bi(3) and one Te(1) atom. In the fourteenth O site, O(14) is bonded in a water-like geometry to one Bi(2) and one Te(3) atom. In the fifteenth O site, O(15) is bonded in a water-like geometry to one Bi(2) and one Te(3) atom. In the sixteenth O site, O(16) is bonded to one Bi(2), one Bi(3), one Bi(4), and one Te(3) atom to form distorted edge-sharing OBi3Te tetrahedra. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Bi(4), one Bi(5), and one Te(1) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(5), and one Te(2) atom.
Bi5(TeO6)3 crystallizes in the monoclinic C2 space group. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(12), one O(18), one O(2), and one O(9) atom to form BiO6 octahedra that share corners with two equivalent Te(2)O6 octahedra and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. The Bi(1)-O(1) bond length is 2.16 Å. The Bi(1)-O(10) bond length is 2.15 Å. The Bi(1)-O(12) bond length is 2.27 Å. The Bi(1)-O(18) bond length is 2.15 Å. The Bi(1)-O(2) bond length is 2.23 Å. The Bi(1)-O(9) bond length is 2.11 Å. In the second Bi site, Bi(2) is bonded in a 5-coordinate geometry to one O(14), one O(15), one O(16), one O(4), and one O(8) atom. The Bi(2)-O(14) bond length is 2.21 Å. The Bi(2)-O(15) bond length is 2.17 Å. The Bi(2)-O(16) bond length is 2.43 Å. The Bi(2)-O(4) bond length is 2.22 Å. The Bi(2)-O(8) bond length is 2.24 Å. In the third Bi site, Bi(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(16), one O(2), one O(3), one O(7), and one O(8) atom. The Bi(3)-O(12) bond length is 2.57 Å. The Bi(3)-O(13) bond length is 2.22 Å. The Bi(3)-O(16) bond length is 2.69 Å. The Bi(3)-O(2) bond length is 2.39 Å. The Bi(3)-O(3) bond length is 2.41 Å. The Bi(3)-O(7) bond length is 2.59 Å. The Bi(3)-O(8) bond length is 2.73 Å. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(16), one O(17), one O(5), and one O(6) atom. The Bi(4)-O(11) bond length is 2.36 Å. The Bi(4)-O(12) bond length is 2.65 Å. The Bi(4)-O(16) bond length is 2.37 Å. The Bi(4)-O(17) bond length is 2.47 Å. The Bi(4)-O(5) bond length is 2.20 Å. The Bi(4)-O(6) bond length is 2.81 Å. In the fifth Bi site, Bi(5) is bonded in a 6-coordinate geometry to two equivalent O(17), two equivalent O(18), and two equivalent O(6) atoms. Both Bi(5)-O(17) bond lengths are 2.22 Å. Both Bi(5)-O(18) bond lengths are 2.64 Å. Both Bi(5)-O(6) bond lengths are 2.37 Å. In the sixth Bi site, Bi(6) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms. Both Bi(6)-O(3) bond lengths are 2.18 Å. Both Bi(6)-O(4) bond lengths are 2.64 Å. Both Bi(6)-O(7) bond lengths are 2.46 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(1), one O(10), one O(12), one O(13), one O(17), and one O(9) atom to form TeO6 octahedra that share edges with two equivalent Bi(1)O6 octahedra. The Te(1)-O(1) bond length is 1.95 Å. The Te(1)-O(10) bond length is 2.01 Å. The Te(1)-O(12) bond length is 2.08 Å. The Te(1)-O(13) bond length is 1.91 Å. The Te(1)-O(17) bond length is 1.94 Å. The Te(1)-O(9) bond length is 1.98 Å. In the second Te site, Te(2) is bonded to one O(11), one O(18), one O(2), one O(4), one O(6), and one O(7) atom to form TeO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-44°. The Te(2)-O(11) bond length is 1.96 Å. The Te(2)-O(18) bond length is 2.02 Å. The Te(2)-O(2) bond length is 2.07 Å. The Te(2)-O(4) bond length is 1.99 Å. The Te(2)-O(6) bond length is 1.91 Å. The Te(2)-O(7) bond length is 1.93 Å. In the third Te site, Te(3) is bonded in an octahedral geometry to one O(14), one O(15), one O(16), one O(3), one O(5), and one O(8) atom. The Te(3)-O(14) bond length is 1.96 Å. The Te(3)-O(15) bond length is 1.95 Å. The Te(3)-O(16) bond length is 2.07 Å. The Te(3)-O(3) bond length is 1.96 Å. The Te(3)-O(5) bond length is 1.91 Å. The Te(3)-O(8) bond length is 2.01 Å. There are eighteen inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Bi(1), one Bi(3), and one Te(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Bi(3), one Bi(6), and one Te(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Bi(2), one Bi(6), and one Te(2) atom. In the fifth O site, O(5) is bonded in a water-like geometry to one Bi(4) and one Te(3) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Bi(4), one Bi(5), and one Te(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Bi(3), one Bi(6), and one Te(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Bi(2), one Bi(3), and one Te(3) atom. In the ninth O site, O(9) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the tenth O site, O(10) is bonded in a water-like geometry to one Bi(1) and one Te(1) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Bi(4) and one Te(2) atom. In the twelfth O site, O(12) is bonded to one Bi(1), one Bi(3), one Bi(4), and one Te(1) atom to form distorted edge-sharing OBi3Te trigonal pyramids. In the thirteenth O site, O(13) is bonded in a water-like geometry to one Bi(3) and one Te(1) atom. In the fourteenth O site, O(14) is bonded in a water-like geometry to one Bi(2) and one Te(3) atom. In the fifteenth O site, O(15) is bonded in a water-like geometry to one Bi(2) and one Te(3) atom. In the sixteenth O site, O(16) is bonded to one Bi(2), one Bi(3), one Bi(4), and one Te(3) atom to form distorted edge-sharing OBi3Te tetrahedra. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one Bi(4), one Bi(5), and one Te(1) atom. In the eighteenth O site, O(18) is bonded in a 3-coordinate geometry to one Bi(1), one Bi(5), and one Te(2) atom.