Tc6BiO18 crystallizes in the triclinic P1 space group. There are twelve inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(14), one O(25), one O(29), one O(30), one O(8), and one O(9) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-41°. In the second Tc site, Tc(2) is bonded to one O(14), one O(16), one O(17), one O(19), one O(21), and one O(25) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-54°. In the third Tc site, Tc(3) is bonded to one O(2), one O(23), one O(26), one O(28), one O(4), and one O(6) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. In the fourth Tc site, Tc(4) is bonded to one O(1), one O(15), one O(16), one O(29), one O(31), and one O(4) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-52°. In the fifth Tc site, Tc(5) is bonded to one O(10), one O(13), one O(32), one O(33), one O(34), and one O(7) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. In the sixth Tc site, Tc(6) is bonded to one O(1), one O(11), one O(18), one O(23), one O(35), and one O(6) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. In the seventh Tc site, Tc(7) is bonded to one O(11), one O(12), one O(2), one O(24), one O(27), and one O(34) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-52°. In the eighth Tc site, Tc(8) is bonded to one O(10), one O(12), one O(24), one O(26), one O(3), and one O(35) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-38°. In the ninth Tc site, Tc(9) is bonded to one O(13), one O(20), one O(27), one O(3), one O(32), and one O(36) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. In the tenth Tc site, Tc(10) is bonded to one O(20), one O(21), one O(22), one O(5), one O(7), and one O(8) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. In the eleventh Tc site, Tc(11) is bonded to one O(19), one O(22), one O(33), one O(36), one O(5), and one O(9) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 25-54°. In the twelfth Tc site, Tc(12) is bonded to one O(15), one O(17), one O(18), one O(28), one O(30), and one O(31) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(2), one O(27), one O(32), and one O(6) atom. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(19), one O(21), and one O(22) atom. There are thirty-six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Tc(4) and one Tc(6) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Tc(3), one Tc(7), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Tc(8) and one Tc(9) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(11) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Tc(3), one Tc(6), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(5) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(10) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(11) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Tc(5) and one Tc(8) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Tc(6) and one Tc(7) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Tc(7) and one Tc(8) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Tc(5) and one Tc(9) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(2) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one Tc(12), one Tc(4), and one Bi(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Tc(2), one Tc(4), and one Bi(2) atom. In the seventeenth O site, O(17) is bonded in a trigonal non-coplanar geometry to one Tc(12), one Tc(2), and one Bi(2) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(6) atom. In the nineteenth O site, O(19) is bonded in a trigonal non-coplanar geometry to one Tc(11), one Tc(2), and one Bi(2) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(9) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 150 degrees geometry to one Tc(10), one Tc(2), and one Bi(2) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal non-coplanar geometry to one Tc(10), one Tc(11), and one Bi(2) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Tc(7) and one Tc(8) atom. In the twenty-fifth O site, O(25) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(2) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(8) atom. In the twenty-seventh O site, O(27) is bonded in a trigonal non-coplanar geometry to one Tc(7), one Tc(9), and one Bi(1) atom. In the twenty-eighth O site, O(28) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(3) atom. In the twenty-ninth O site, O(29) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(4) atom. In the thirtieth O site, O(30) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(12) atom. In the thirty-first O site, O(31) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(4) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal non-coplanar geometry to one Tc(5), one Tc(9), and one Bi(1) atom. In the thirty-third O site, O(33) is bonded in a bent 150 degrees geometry to one Tc(11) and one Tc(5) atom. In the thirty-fourth O site, O(34) is bonded in a distorted bent 150 degrees geometry to one Tc(5) and one Tc(7) atom. In the thirty-fifth O site, O(35) is bonded in a bent 150 degrees geometry to one Tc(6) and one Tc(8) atom. In the thirty-sixth O site, O(36) is bonded in a bent 150 degrees geometry to one Tc(11) and one Tc(9) atom.
Tc6BiO18 crystallizes in the triclinic P1 space group. There are twelve inequivalent Tc sites. In the first Tc site, Tc(1) is bonded to one O(14), one O(25), one O(29), one O(30), one O(8), and one O(9) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-41°. The Tc(1)-O(14) bond length is 1.98 Å. The Tc(1)-O(25) bond length is 1.90 Å. The Tc(1)-O(29) bond length is 2.03 Å. The Tc(1)-O(30) bond length is 1.87 Å. The Tc(1)-O(8) bond length is 1.88 Å. The Tc(1)-O(9) bond length is 1.84 Å. In the second Tc site, Tc(2) is bonded to one O(14), one O(16), one O(17), one O(19), one O(21), and one O(25) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-54°. The Tc(2)-O(14) bond length is 1.81 Å. The Tc(2)-O(16) bond length is 1.89 Å. The Tc(2)-O(17) bond length is 2.10 Å. The Tc(2)-O(19) bond length is 2.12 Å. The Tc(2)-O(21) bond length is 1.86 Å. The Tc(2)-O(25) bond length is 1.86 Å. In the third Tc site, Tc(3) is bonded to one O(2), one O(23), one O(26), one O(28), one O(4), and one O(6) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. The Tc(3)-O(2) bond length is 2.07 Å. The Tc(3)-O(23) bond length is 1.86 Å. The Tc(3)-O(26) bond length is 1.96 Å. The Tc(3)-O(28) bond length is 1.87 Å. The Tc(3)-O(4) bond length is 1.84 Å. The Tc(3)-O(6) bond length is 2.03 Å. In the fourth Tc site, Tc(4) is bonded to one O(1), one O(15), one O(16), one O(29), one O(31), and one O(4) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-52°. The Tc(4)-O(1) bond length is 1.91 Å. The Tc(4)-O(15) bond length is 2.06 Å. The Tc(4)-O(16) bond length is 1.98 Å. The Tc(4)-O(29) bond length is 1.84 Å. The Tc(4)-O(31) bond length is 1.88 Å. The Tc(4)-O(4) bond length is 1.92 Å. In the fifth Tc site, Tc(5) is bonded to one O(10), one O(13), one O(32), one O(33), one O(34), and one O(7) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. The Tc(5)-O(10) bond length is 1.86 Å. The Tc(5)-O(13) bond length is 1.90 Å. The Tc(5)-O(32) bond length is 2.06 Å. The Tc(5)-O(33) bond length is 1.93 Å. The Tc(5)-O(34) bond length is 2.01 Å. The Tc(5)-O(7) bond length is 1.86 Å. In the sixth Tc site, Tc(6) is bonded to one O(1), one O(11), one O(18), one O(23), one O(35), and one O(6) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. The Tc(6)-O(1) bond length is 1.90 Å. The Tc(6)-O(11) bond length is 2.01 Å. The Tc(6)-O(18) bond length is 1.88 Å. The Tc(6)-O(23) bond length is 1.89 Å. The Tc(6)-O(35) bond length is 1.90 Å. The Tc(6)-O(6) bond length is 2.01 Å. In the seventh Tc site, Tc(7) is bonded to one O(11), one O(12), one O(2), one O(24), one O(27), and one O(34) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-52°. The Tc(7)-O(11) bond length is 1.84 Å. The Tc(7)-O(12) bond length is 1.84 Å. The Tc(7)-O(2) bond length is 2.14 Å. The Tc(7)-O(24) bond length is 1.85 Å. The Tc(7)-O(27) bond length is 2.12 Å. The Tc(7)-O(34) bond length is 1.86 Å. In the eighth Tc site, Tc(8) is bonded to one O(10), one O(12), one O(24), one O(26), one O(3), and one O(35) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 31-38°. The Tc(8)-O(10) bond length is 2.00 Å. The Tc(8)-O(12) bond length is 1.96 Å. The Tc(8)-O(24) bond length is 1.94 Å. The Tc(8)-O(26) bond length is 1.85 Å. The Tc(8)-O(3) bond length is 1.85 Å. The Tc(8)-O(35) bond length is 1.92 Å. In the ninth Tc site, Tc(9) is bonded to one O(13), one O(20), one O(27), one O(3), one O(32), and one O(36) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. The Tc(9)-O(13) bond length is 1.85 Å. The Tc(9)-O(20) bond length is 1.85 Å. The Tc(9)-O(27) bond length is 2.08 Å. The Tc(9)-O(3) bond length is 1.96 Å. The Tc(9)-O(32) bond length is 2.02 Å. The Tc(9)-O(36) bond length is 1.88 Å. In the tenth Tc site, Tc(10) is bonded to one O(20), one O(21), one O(22), one O(5), one O(7), and one O(8) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The Tc(10)-O(20) bond length is 1.90 Å. The Tc(10)-O(21) bond length is 1.98 Å. The Tc(10)-O(22) bond length is 2.01 Å. The Tc(10)-O(5) bond length is 1.91 Å. The Tc(10)-O(7) bond length is 1.87 Å. The Tc(10)-O(8) bond length is 1.96 Å. In the eleventh Tc site, Tc(11) is bonded to one O(19), one O(22), one O(33), one O(36), one O(5), and one O(9) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 25-54°. The Tc(11)-O(19) bond length is 2.09 Å. The Tc(11)-O(22) bond length is 2.02 Å. The Tc(11)-O(33) bond length is 1.85 Å. The Tc(11)-O(36) bond length is 1.89 Å. The Tc(11)-O(5) bond length is 1.83 Å. The Tc(11)-O(9) bond length is 1.97 Å. In the twelfth Tc site, Tc(12) is bonded to one O(15), one O(17), one O(18), one O(28), one O(30), and one O(31) atom to form corner-sharing TcO6 octahedra. The corner-sharing octahedral tilt angles range from 30-53°. The Tc(12)-O(15) bond length is 2.02 Å. The Tc(12)-O(17) bond length is 2.04 Å. The Tc(12)-O(18) bond length is 1.86 Å. The Tc(12)-O(28) bond length is 1.87 Å. The Tc(12)-O(30) bond length is 1.93 Å. The Tc(12)-O(31) bond length is 1.87 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 4-coordinate geometry to one O(2), one O(27), one O(32), and one O(6) atom. The Bi(1)-O(2) bond length is 2.17 Å. The Bi(1)-O(27) bond length is 2.16 Å. The Bi(1)-O(32) bond length is 2.44 Å. The Bi(1)-O(6) bond length is 2.54 Å. In the second Bi site, Bi(2) is bonded in a 6-coordinate geometry to one O(15), one O(16), one O(17), one O(19), one O(21), and one O(22) atom. The Bi(2)-O(15) bond length is 2.44 Å. The Bi(2)-O(16) bond length is 2.81 Å. The Bi(2)-O(17) bond length is 2.19 Å. The Bi(2)-O(19) bond length is 2.19 Å. The Bi(2)-O(21) bond length is 2.87 Å. The Bi(2)-O(22) bond length is 2.51 Å. There are thirty-six inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Tc(4) and one Tc(6) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Tc(3), one Tc(7), and one Bi(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Tc(8) and one Tc(9) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(11) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Tc(3), one Tc(6), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(5) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(10) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(11) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Tc(5) and one Tc(8) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Tc(6) and one Tc(7) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one Tc(7) and one Tc(8) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Tc(5) and one Tc(9) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(2) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal non-coplanar geometry to one Tc(12), one Tc(4), and one Bi(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Tc(2), one Tc(4), and one Bi(2) atom. In the seventeenth O site, O(17) is bonded in a trigonal non-coplanar geometry to one Tc(12), one Tc(2), and one Bi(2) atom. In the eighteenth O site, O(18) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(6) atom. In the nineteenth O site, O(19) is bonded in a trigonal non-coplanar geometry to one Tc(11), one Tc(2), and one Bi(2) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Tc(10) and one Tc(9) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 150 degrees geometry to one Tc(10), one Tc(2), and one Bi(2) atom. In the twenty-second O site, O(22) is bonded in a distorted trigonal non-coplanar geometry to one Tc(10), one Tc(11), and one Bi(2) atom. In the twenty-third O site, O(23) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(6) atom. In the twenty-fourth O site, O(24) is bonded in a bent 150 degrees geometry to one Tc(7) and one Tc(8) atom. In the twenty-fifth O site, O(25) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(2) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one Tc(3) and one Tc(8) atom. In the twenty-seventh O site, O(27) is bonded in a trigonal non-coplanar geometry to one Tc(7), one Tc(9), and one Bi(1) atom. In the twenty-eighth O site, O(28) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(3) atom. In the twenty-ninth O site, O(29) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(4) atom. In the thirtieth O site, O(30) is bonded in a bent 150 degrees geometry to one Tc(1) and one Tc(12) atom. In the thirty-first O site, O(31) is bonded in a bent 150 degrees geometry to one Tc(12) and one Tc(4) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal non-coplanar geometry to one Tc(5), one Tc(9), and one Bi(1) atom. In the thirty-third O site, O(33) is bonded in a bent 150 degrees geometry to one Tc(11) and one Tc(5) atom. In the thirty-fourth O site, O(34) is bonded in a distorted bent 150 degrees geometry to one Tc(5) and one Tc(7) atom. In the thirty-fifth O site, O(35) is bonded in a bent 150 degrees geometry to one Tc(6) and one Tc(8) atom. In the thirty-sixth O site, O(36) is bonded in a bent 150 degrees geometry to one Tc(11) and one Tc(9) atom.