V16Bi3O32 crystallizes in the triclinic P1 space group. There are sixteen inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(20), one O(21), one O(22), one O(24), and one O(3) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the second V site, V(2) is bonded to one O(1), one O(15), one O(25), one O(3), one O(4), and one O(5) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. In the third V site, V(3) is bonded to one O(2), one O(27), one O(29), one O(3), one O(6), and one O(7) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the fourth V site, V(4) is bonded to one O(10), one O(23), one O(4), one O(5), one O(7), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. In the fifth V site, V(5) is bonded to one O(13), one O(14), one O(31), one O(6), one O(7), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the sixth V site, V(6) is bonded to one O(1), one O(11), one O(15), one O(16), one O(32), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the seventh V site, V(7) is bonded to one O(10), one O(14), one O(17), one O(18), one O(28), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. In the eighth V site, V(8) is bonded to one O(11), one O(12), one O(17), one O(19), one O(20), and one O(21) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the ninth V site, V(9) is bonded to one O(12), one O(13), one O(14), one O(16), one O(21), and one O(22) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 51-56°. In the tenth V site, V(10) is bonded to one O(15), one O(16), one O(19), one O(23), one O(24), and one O(5) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the eleventh V site, V(11) is bonded to one O(1), one O(17), one O(18), one O(22), one O(25), and one O(32) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. In the twelfth V site, V(12) is bonded to one O(19), one O(2), one O(20), one O(25), one O(26), and one O(27) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. In the thirteenth V site, V(13) is bonded to one O(10), one O(23), one O(24), one O(26), one O(28), and one O(29) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the fourteenth V site, V(14) is bonded to one O(26), one O(27), one O(30), one O(31), one O(4), and one O(6) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the fifteenth V site, V(15) is bonded to one O(18), one O(28), one O(29), one O(30), one O(32), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the sixteenth V site, V(16) is bonded to one O(11), one O(12), one O(13), one O(30), one O(31), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(18), one O(28), and one O(6) atom. In the second Bi site, Bi(2) is bonded in a distorted rectangular see-saw-like geometry to one O(15), one O(21), one O(27), and one O(5) atom. In the third Bi site, Bi(3) is bonded in a rectangular see-saw-like geometry to one O(10), one O(2), one O(23), and one O(31) atom. There are thirty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(11), one V(2), and one V(6) atom. In the second O site, O(2) is bonded to one V(1), one V(12), one V(3), and one Bi(3) atom to form distorted corner-sharing OV3Bi trigonal pyramids. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(14), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(10), one V(2), one V(4), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(14), one V(3), one V(5), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(15), one V(5), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(16), one V(4), and one V(7) atom. In the tenth O site, O(10) is bonded to one V(13), one V(4), one V(7), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OV3Bi trigonal pyramids. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one V(16), one V(6), and one V(8) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one V(16), one V(8), one V(9), and one Bi(1) atom. In the thirteenth O site, O(13) is bonded in a trigonal non-coplanar geometry to one V(16), one V(5), and one V(9) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one V(5), one V(7), and one V(9) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one V(10), one V(2), one V(6), and one Bi(2) atom. In the sixteenth O site, O(16) is bonded in a trigonal planar geometry to one V(10), one V(6), and one V(9) atom. In the seventeenth O site, O(17) is bonded in a trigonal planar geometry to one V(11), one V(7), and one V(8) atom. In the eighteenth O site, O(18) is bonded in a rectangular see-saw-like geometry to one V(11), one V(15), one V(7), and one Bi(1) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one V(10), one V(12), and one V(8) atom. In the twentieth O site, O(20) is bonded in a trigonal non-coplanar geometry to one V(1), one V(12), and one V(8) atom. In the twenty-first O site, O(21) is bonded to one V(1), one V(8), one V(9), and one Bi(2) atom to form distorted corner-sharing OV3Bi trigonal pyramids. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one V(1), one V(11), and one V(9) atom. In the twenty-third O site, O(23) is bonded to one V(10), one V(13), one V(4), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OV3Bi tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one V(1), one V(10), and one V(13) atom. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal planar geometry to one V(11), one V(12), and one V(2) atom. In the twenty-sixth O site, O(26) is bonded in a trigonal planar geometry to one V(12), one V(13), and one V(14) atom. In the twenty-seventh O site, O(27) is bonded in a 4-coordinate geometry to one V(12), one V(14), one V(3), and one Bi(2) atom. In the twenty-eighth O site, O(28) is bonded in a rectangular see-saw-like geometry to one V(13), one V(15), one V(7), and one Bi(1) atom. In the twenty-ninth O site, O(29) is bonded in a distorted trigonal planar geometry to one V(13), one V(15), and one V(3) atom. In the thirtieth O site, O(30) is bonded in a trigonal planar geometry to one V(14), one V(15), and one V(16) atom. In the thirty-first O site, O(31) is bonded in a distorted rectangular see-saw-like geometry to one V(14), one V(16), one V(5), and one Bi(3) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal non-coplanar geometry to one V(11), one V(15), and one V(6) atom.
V16Bi3O32 crystallizes in the triclinic P1 space group. There are sixteen inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(20), one O(21), one O(22), one O(24), and one O(3) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(20) bond length is 1.89 Å. The V(1)-O(21) bond length is 2.16 Å. The V(1)-O(22) bond length is 1.97 Å. The V(1)-O(24) bond length is 1.86 Å. The V(1)-O(3) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(1), one O(15), one O(25), one O(3), one O(4), and one O(5) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The V(2)-O(1) bond length is 2.00 Å. The V(2)-O(15) bond length is 2.07 Å. The V(2)-O(25) bond length is 2.06 Å. The V(2)-O(3) bond length is 1.96 Å. The V(2)-O(4) bond length is 2.00 Å. The V(2)-O(5) bond length is 2.12 Å. In the third V site, V(3) is bonded to one O(2), one O(27), one O(29), one O(3), one O(6), and one O(7) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The V(3)-O(2) bond length is 2.09 Å. The V(3)-O(27) bond length is 2.00 Å. The V(3)-O(29) bond length is 1.82 Å. The V(3)-O(3) bond length is 1.98 Å. The V(3)-O(6) bond length is 2.05 Å. The V(3)-O(7) bond length is 1.94 Å. In the fourth V site, V(4) is bonded to one O(10), one O(23), one O(4), one O(5), one O(7), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The V(4)-O(10) bond length is 2.09 Å. The V(4)-O(23) bond length is 2.04 Å. The V(4)-O(4) bond length is 2.05 Å. The V(4)-O(5) bond length is 2.08 Å. The V(4)-O(7) bond length is 1.95 Å. The V(4)-O(9) bond length is 2.00 Å. In the fifth V site, V(5) is bonded to one O(13), one O(14), one O(31), one O(6), one O(7), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(5)-O(13) bond length is 1.99 Å. The V(5)-O(14) bond length is 1.94 Å. The V(5)-O(31) bond length is 2.05 Å. The V(5)-O(6) bond length is 2.08 Å. The V(5)-O(7) bond length is 1.99 Å. The V(5)-O(8) bond length is 1.81 Å. In the sixth V site, V(6) is bonded to one O(1), one O(11), one O(15), one O(16), one O(32), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(6)-O(1) bond length is 1.90 Å. The V(6)-O(11) bond length is 1.90 Å. The V(6)-O(15) bond length is 2.06 Å. The V(6)-O(16) bond length is 1.97 Å. The V(6)-O(32) bond length is 2.03 Å. The V(6)-O(8) bond length is 2.00 Å. In the seventh V site, V(7) is bonded to one O(10), one O(14), one O(17), one O(18), one O(28), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-54°. The V(7)-O(10) bond length is 2.08 Å. The V(7)-O(14) bond length is 1.93 Å. The V(7)-O(17) bond length is 2.01 Å. The V(7)-O(18) bond length is 2.09 Å. The V(7)-O(28) bond length is 2.06 Å. The V(7)-O(9) bond length is 2.04 Å. In the eighth V site, V(8) is bonded to one O(11), one O(12), one O(17), one O(19), one O(20), and one O(21) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-55°. The V(8)-O(11) bond length is 2.03 Å. The V(8)-O(12) bond length is 2.11 Å. The V(8)-O(17) bond length is 1.92 Å. The V(8)-O(19) bond length is 2.05 Å. The V(8)-O(20) bond length is 2.03 Å. The V(8)-O(21) bond length is 2.09 Å. In the ninth V site, V(9) is bonded to one O(12), one O(13), one O(14), one O(16), one O(21), and one O(22) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 51-56°. The V(9)-O(12) bond length is 2.07 Å. The V(9)-O(13) bond length is 2.07 Å. The V(9)-O(14) bond length is 1.96 Å. The V(9)-O(16) bond length is 1.97 Å. The V(9)-O(21) bond length is 2.10 Å. The V(9)-O(22) bond length is 2.09 Å. In the tenth V site, V(10) is bonded to one O(15), one O(16), one O(19), one O(23), one O(24), and one O(5) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The V(10)-O(15) bond length is 2.04 Å. The V(10)-O(16) bond length is 1.94 Å. The V(10)-O(19) bond length is 1.81 Å. The V(10)-O(23) bond length is 2.05 Å. The V(10)-O(24) bond length is 1.99 Å. The V(10)-O(5) bond length is 2.03 Å. In the eleventh V site, V(11) is bonded to one O(1), one O(17), one O(18), one O(22), one O(25), and one O(32) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The V(11)-O(1) bond length is 2.06 Å. The V(11)-O(17) bond length is 1.92 Å. The V(11)-O(18) bond length is 2.03 Å. The V(11)-O(22) bond length is 1.86 Å. The V(11)-O(25) bond length is 2.04 Å. The V(11)-O(32) bond length is 1.93 Å. In the twelfth V site, V(12) is bonded to one O(19), one O(2), one O(20), one O(25), one O(26), and one O(27) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. The V(12)-O(19) bond length is 2.00 Å. The V(12)-O(2) bond length is 2.06 Å. The V(12)-O(20) bond length is 2.01 Å. The V(12)-O(25) bond length is 1.80 Å. The V(12)-O(26) bond length is 1.95 Å. The V(12)-O(27) bond length is 2.02 Å. In the thirteenth V site, V(13) is bonded to one O(10), one O(23), one O(24), one O(26), one O(28), and one O(29) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. The V(13)-O(10) bond length is 2.06 Å. The V(13)-O(23) bond length is 2.04 Å. The V(13)-O(24) bond length is 2.06 Å. The V(13)-O(26) bond length is 1.95 Å. The V(13)-O(28) bond length is 2.11 Å. The V(13)-O(29) bond length is 2.03 Å. In the fourteenth V site, V(14) is bonded to one O(26), one O(27), one O(30), one O(31), one O(4), and one O(6) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(14)-O(26) bond length is 1.95 Å. The V(14)-O(27) bond length is 2.07 Å. The V(14)-O(30) bond length is 1.96 Å. The V(14)-O(31) bond length is 2.07 Å. The V(14)-O(4) bond length is 1.82 Å. The V(14)-O(6) bond length is 2.00 Å. In the fifteenth V site, V(15) is bonded to one O(18), one O(28), one O(29), one O(30), one O(32), and one O(8) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The V(15)-O(18) bond length is 2.06 Å. The V(15)-O(28) bond length is 2.12 Å. The V(15)-O(29) bond length is 2.02 Å. The V(15)-O(30) bond length is 1.96 Å. The V(15)-O(32) bond length is 2.00 Å. The V(15)-O(8) bond length is 2.06 Å. In the sixteenth V site, V(16) is bonded to one O(11), one O(12), one O(13), one O(30), one O(31), and one O(9) atom to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 49-53°. The V(16)-O(11) bond length is 2.00 Å. The V(16)-O(12) bond length is 2.15 Å. The V(16)-O(13) bond length is 1.89 Å. The V(16)-O(30) bond length is 1.95 Å. The V(16)-O(31) bond length is 2.09 Å. The V(16)-O(9) bond length is 1.84 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(18), one O(28), and one O(6) atom. The Bi(1)-O(12) bond length is 2.27 Å. The Bi(1)-O(18) bond length is 2.51 Å. The Bi(1)-O(28) bond length is 2.30 Å. The Bi(1)-O(6) bond length is 2.66 Å. In the second Bi site, Bi(2) is bonded in a distorted rectangular see-saw-like geometry to one O(15), one O(21), one O(27), and one O(5) atom. The Bi(2)-O(15) bond length is 2.50 Å. The Bi(2)-O(21) bond length is 2.27 Å. The Bi(2)-O(27) bond length is 2.70 Å. The Bi(2)-O(5) bond length is 2.35 Å. In the third Bi site, Bi(3) is bonded in a rectangular see-saw-like geometry to one O(10), one O(2), one O(23), and one O(31) atom. The Bi(3)-O(10) bond length is 2.34 Å. The Bi(3)-O(2) bond length is 2.46 Å. The Bi(3)-O(23) bond length is 2.51 Å. The Bi(3)-O(31) bond length is 2.44 Å. There are thirty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(11), one V(2), and one V(6) atom. In the second O site, O(2) is bonded to one V(1), one V(12), one V(3), and one Bi(3) atom to form distorted corner-sharing OV3Bi trigonal pyramids. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(14), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(10), one V(2), one V(4), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(14), one V(3), one V(5), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(15), one V(5), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(16), one V(4), and one V(7) atom. In the tenth O site, O(10) is bonded to one V(13), one V(4), one V(7), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OV3Bi trigonal pyramids. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one V(16), one V(6), and one V(8) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one V(16), one V(8), one V(9), and one Bi(1) atom. In the thirteenth O site, O(13) is bonded in a trigonal non-coplanar geometry to one V(16), one V(5), and one V(9) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one V(5), one V(7), and one V(9) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one V(10), one V(2), one V(6), and one Bi(2) atom. In the sixteenth O site, O(16) is bonded in a trigonal planar geometry to one V(10), one V(6), and one V(9) atom. In the seventeenth O site, O(17) is bonded in a trigonal planar geometry to one V(11), one V(7), and one V(8) atom. In the eighteenth O site, O(18) is bonded in a rectangular see-saw-like geometry to one V(11), one V(15), one V(7), and one Bi(1) atom. In the nineteenth O site, O(19) is bonded in a distorted trigonal planar geometry to one V(10), one V(12), and one V(8) atom. In the twentieth O site, O(20) is bonded in a trigonal non-coplanar geometry to one V(1), one V(12), and one V(8) atom. In the twenty-first O site, O(21) is bonded to one V(1), one V(8), one V(9), and one Bi(2) atom to form distorted corner-sharing OV3Bi trigonal pyramids. In the twenty-second O site, O(22) is bonded in a distorted trigonal planar geometry to one V(1), one V(11), and one V(9) atom. In the twenty-third O site, O(23) is bonded to one V(10), one V(13), one V(4), and one Bi(3) atom to form a mixture of distorted edge and corner-sharing OV3Bi tetrahedra. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal planar geometry to one V(1), one V(10), and one V(13) atom. In the twenty-fifth O site, O(25) is bonded in a distorted trigonal planar geometry to one V(11), one V(12), and one V(2) atom. In the twenty-sixth O site, O(26) is bonded in a trigonal planar geometry to one V(12), one V(13), and one V(14) atom. In the twenty-seventh O site, O(27) is bonded in a 4-coordinate geometry to one V(12), one V(14), one V(3), and one Bi(2) atom. In the twenty-eighth O site, O(28) is bonded in a rectangular see-saw-like geometry to one V(13), one V(15), one V(7), and one Bi(1) atom. In the twenty-ninth O site, O(29) is bonded in a distorted trigonal planar geometry to one V(13), one V(15), and one V(3) atom. In the thirtieth O site, O(30) is bonded in a trigonal planar geometry to one V(14), one V(15), and one V(16) atom. In the thirty-first O site, O(31) is bonded in a distorted rectangular see-saw-like geometry to one V(14), one V(16), one V(5), and one Bi(3) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal non-coplanar geometry to one V(11), one V(15), and one V(6) atom.