Ti10Cu7S20 crystallizes in the monoclinic Cm space group. There are ten inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(18), one S(3), two equivalent S(1), and two equivalent S(20) atoms to form distorted edge-sharing TiS6 octahedra. In the second Ti site, Ti(2) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing TiS6 octahedra. In the third Ti site, Ti(3) is bonded to one S(2), one S(7), two equivalent S(4), and two equivalent S(5) atoms to form distorted edge-sharing TiS6 octahedra. In the fourth Ti site, Ti(4) is bonded to one S(4), one S(9), two equivalent S(6), and two equivalent S(7) atoms to form distorted edge-sharing TiS6 octahedra. In the fifth Ti site, Ti(5) is bonded to one S(13), one S(8), two equivalent S(10), and two equivalent S(11) atoms to form distorted edge-sharing TiS6 octahedra. In the sixth Ti site, Ti(6) is bonded to one S(11), one S(6), two equivalent S(8), and two equivalent S(9) atoms to form edge-sharing TiS6 octahedra. In the seventh Ti site, Ti(7) is bonded to one S(10), one S(15), two equivalent S(12), and two equivalent S(13) atoms to form distorted edge-sharing TiS6 octahedra. In the eighth Ti site, Ti(8) is bonded to one S(12), one S(17), two equivalent S(14), and two equivalent S(15) atoms to form edge-sharing TiS6 octahedra. In the ninth Ti site, Ti(9) is bonded to one S(14), one S(19), two equivalent S(16), and two equivalent S(17) atoms to form distorted edge-sharing TiS6 octahedra. In the tenth Ti site, Ti(10) is bonded to one S(16), one S(20), two equivalent S(18), and two equivalent S(19) atoms to form distorted edge-sharing TiS6 octahedra. There are seven inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one S(6), one S(9), and two equivalent S(7) atoms. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(2), one S(5), and two equivalent S(4) atoms. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one S(12), one S(15), and two equivalent S(13) atoms. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one S(11), one S(8), and two equivalent S(10) atoms. In the fifth Cu site, Cu(5) is bonded in a distorted rectangular see-saw-like geometry to one S(14), one S(17), and two equivalent S(16) atoms. In the sixth Cu site, Cu(6) is bonded in a 4-coordinate geometry to one S(16), one S(19), and two equivalent S(18) atoms. In the seventh Cu site, Cu(7) is bonded in a 4-coordinate geometry to one S(18), one S(20), and two equivalent S(1) atoms. There are twenty inequivalent S sites. In the first S site, S(1) is bonded to one Ti(2), two equivalent Ti(1), and two equivalent Cu(7) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(2), and one Cu(2) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the fourth S site, S(4) is bonded to one Ti(4), two equivalent Ti(3), and two equivalent Cu(2) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(3), and one Cu(2) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ti(6), two equivalent Ti(4), and one Cu(1) atom. In the seventh S site, S(7) is bonded to one Ti(3), two equivalent Ti(4), and two equivalent Cu(1) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Ti(5), two equivalent Ti(6), and one Cu(4) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(4), two equivalent Ti(6), and one Cu(1) atom. In the tenth S site, S(10) is bonded to one Ti(7), two equivalent Ti(5), and two equivalent Cu(4) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Ti(6), two equivalent Ti(5), and one Cu(4) atom. In the twelfth S site, S(12) is bonded in a rectangular see-saw-like geometry to one Ti(8), two equivalent Ti(7), and one Cu(3) atom. In the thirteenth S site, S(13) is bonded to one Ti(5), two equivalent Ti(7), and two equivalent Cu(3) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Ti(9), two equivalent Ti(8), and one Cu(5) atom. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Ti(7), two equivalent Ti(8), and one Cu(3) atom. In the sixteenth S site, S(16) is bonded in a 6-coordinate geometry to one Ti(10), two equivalent Ti(9), one Cu(6), and two equivalent Cu(5) atoms. In the seventeenth S site, S(17) is bonded in a rectangular see-saw-like geometry to one Ti(8), two equivalent Ti(9), and one Cu(5) atom. In the eighteenth S site, S(18) is bonded in a 6-coordinate geometry to one Ti(1), two equivalent Ti(10), one Cu(7), and two equivalent Cu(6) atoms. In the nineteenth S site, S(19) is bonded in a rectangular see-saw-like geometry to one Ti(9), two equivalent Ti(10), and one Cu(6) atom. In the twentieth S site, S(20) is bonded in a rectangular see-saw-like geometry to one Ti(10), two equivalent Ti(1), and one Cu(7) atom.
Ti10Cu7S20 crystallizes in the monoclinic Cm space group. There are ten inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(18), one S(3), two equivalent S(1), and two equivalent S(20) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(1)-S(18) bond length is 2.52 Å. The Ti(1)-S(3) bond length is 2.40 Å. Both Ti(1)-S(1) bond lengths are 2.51 Å. Both Ti(1)-S(20) bond lengths are 2.45 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(5), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing TiS6 octahedra. The Ti(2)-S(1) bond length is 2.46 Å. The Ti(2)-S(5) bond length is 2.46 Å. Both Ti(2)-S(2) bond lengths are 2.45 Å. Both Ti(2)-S(3) bond lengths are 2.44 Å. In the third Ti site, Ti(3) is bonded to one S(2), one S(7), two equivalent S(4), and two equivalent S(5) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(3)-S(2) bond length is 2.47 Å. The Ti(3)-S(7) bond length is 2.44 Å. Both Ti(3)-S(4) bond lengths are 2.51 Å. Both Ti(3)-S(5) bond lengths are 2.45 Å. In the fourth Ti site, Ti(4) is bonded to one S(4), one S(9), two equivalent S(6), and two equivalent S(7) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(4)-S(4) bond length is 2.45 Å. The Ti(4)-S(9) bond length is 2.47 Å. Both Ti(4)-S(6) bond lengths are 2.44 Å. Both Ti(4)-S(7) bond lengths are 2.51 Å. In the fifth Ti site, Ti(5) is bonded to one S(13), one S(8), two equivalent S(10), and two equivalent S(11) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(5)-S(13) bond length is 2.45 Å. The Ti(5)-S(8) bond length is 2.47 Å. Both Ti(5)-S(10) bond lengths are 2.51 Å. Both Ti(5)-S(11) bond lengths are 2.45 Å. In the sixth Ti site, Ti(6) is bonded to one S(11), one S(6), two equivalent S(8), and two equivalent S(9) atoms to form edge-sharing TiS6 octahedra. The Ti(6)-S(11) bond length is 2.47 Å. The Ti(6)-S(6) bond length is 2.47 Å. Both Ti(6)-S(8) bond lengths are 2.44 Å. Both Ti(6)-S(9) bond lengths are 2.44 Å. In the seventh Ti site, Ti(7) is bonded to one S(10), one S(15), two equivalent S(12), and two equivalent S(13) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(7)-S(10) bond length is 2.45 Å. The Ti(7)-S(15) bond length is 2.47 Å. Both Ti(7)-S(12) bond lengths are 2.45 Å. Both Ti(7)-S(13) bond lengths are 2.51 Å. In the eighth Ti site, Ti(8) is bonded to one S(12), one S(17), two equivalent S(14), and two equivalent S(15) atoms to form edge-sharing TiS6 octahedra. The Ti(8)-S(12) bond length is 2.46 Å. The Ti(8)-S(17) bond length is 2.48 Å. Both Ti(8)-S(14) bond lengths are 2.44 Å. Both Ti(8)-S(15) bond lengths are 2.44 Å. In the ninth Ti site, Ti(9) is bonded to one S(14), one S(19), two equivalent S(16), and two equivalent S(17) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(9)-S(14) bond length is 2.48 Å. The Ti(9)-S(19) bond length is 2.45 Å. Both Ti(9)-S(16) bond lengths are 2.50 Å. Both Ti(9)-S(17) bond lengths are 2.44 Å. In the tenth Ti site, Ti(10) is bonded to one S(16), one S(20), two equivalent S(18), and two equivalent S(19) atoms to form distorted edge-sharing TiS6 octahedra. The Ti(10)-S(16) bond length is 2.51 Å. The Ti(10)-S(20) bond length is 2.45 Å. Both Ti(10)-S(18) bond lengths are 2.50 Å. Both Ti(10)-S(19) bond lengths are 2.44 Å. There are seven inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 4-coordinate geometry to one S(6), one S(9), and two equivalent S(7) atoms. The Cu(1)-S(6) bond length is 2.21 Å. The Cu(1)-S(9) bond length is 2.32 Å. Both Cu(1)-S(7) bond lengths are 2.35 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(2), one S(5), and two equivalent S(4) atoms. The Cu(2)-S(2) bond length is 2.31 Å. The Cu(2)-S(5) bond length is 2.21 Å. Both Cu(2)-S(4) bond lengths are 2.35 Å. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one S(12), one S(15), and two equivalent S(13) atoms. The Cu(3)-S(12) bond length is 2.21 Å. The Cu(3)-S(15) bond length is 2.32 Å. Both Cu(3)-S(13) bond lengths are 2.35 Å. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to one S(11), one S(8), and two equivalent S(10) atoms. The Cu(4)-S(11) bond length is 2.21 Å. The Cu(4)-S(8) bond length is 2.32 Å. Both Cu(4)-S(10) bond lengths are 2.35 Å. In the fifth Cu site, Cu(5) is bonded in a distorted rectangular see-saw-like geometry to one S(14), one S(17), and two equivalent S(16) atoms. The Cu(5)-S(14) bond length is 2.31 Å. The Cu(5)-S(17) bond length is 2.20 Å. Both Cu(5)-S(16) bond lengths are 2.35 Å. In the sixth Cu site, Cu(6) is bonded in a 4-coordinate geometry to one S(16), one S(19), and two equivalent S(18) atoms. The Cu(6)-S(16) bond length is 2.33 Å. The Cu(6)-S(19) bond length is 2.20 Å. Both Cu(6)-S(18) bond lengths are 2.34 Å. In the seventh Cu site, Cu(7) is bonded in a 4-coordinate geometry to one S(18), one S(20), and two equivalent S(1) atoms. The Cu(7)-S(18) bond length is 2.34 Å. The Cu(7)-S(20) bond length is 2.21 Å. Both Cu(7)-S(1) bond lengths are 2.32 Å. There are twenty inequivalent S sites. In the first S site, S(1) is bonded to one Ti(2), two equivalent Ti(1), and two equivalent Cu(7) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(2), and one Cu(2) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(2) atoms. In the fourth S site, S(4) is bonded to one Ti(4), two equivalent Ti(3), and two equivalent Cu(2) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(3), and one Cu(2) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ti(6), two equivalent Ti(4), and one Cu(1) atom. In the seventh S site, S(7) is bonded to one Ti(3), two equivalent Ti(4), and two equivalent Cu(1) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Ti(5), two equivalent Ti(6), and one Cu(4) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(4), two equivalent Ti(6), and one Cu(1) atom. In the tenth S site, S(10) is bonded to one Ti(7), two equivalent Ti(5), and two equivalent Cu(4) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Ti(6), two equivalent Ti(5), and one Cu(4) atom. In the twelfth S site, S(12) is bonded in a rectangular see-saw-like geometry to one Ti(8), two equivalent Ti(7), and one Cu(3) atom. In the thirteenth S site, S(13) is bonded to one Ti(5), two equivalent Ti(7), and two equivalent Cu(3) atoms to form distorted edge-sharing STi3Cu2 square pyramids. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Ti(9), two equivalent Ti(8), and one Cu(5) atom. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Ti(7), two equivalent Ti(8), and one Cu(3) atom. In the sixteenth S site, S(16) is bonded in a 6-coordinate geometry to one Ti(10), two equivalent Ti(9), one Cu(6), and two equivalent Cu(5) atoms. In the seventeenth S site, S(17) is bonded in a rectangular see-saw-like geometry to one Ti(8), two equivalent Ti(9), and one Cu(5) atom. In the eighteenth S site, S(18) is bonded in a 6-coordinate geometry to one Ti(1), two equivalent Ti(10), one Cu(7), and two equivalent Cu(6) atoms. In the nineteenth S site, S(19) is bonded in a rectangular see-saw-like geometry to one Ti(9), two equivalent Ti(10), and one Cu(6) atom. In the twentieth S site, S(20) is bonded in a rectangular see-saw-like geometry to one Ti(10), two equivalent Ti(1), and one Cu(7) atom.