Ti8S3 crystallizes in the monoclinic C2/m space group. There are sixteen inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted L-shaped geometry to two equivalent S(5) atoms. In the second Ti site, Ti(2) is bonded in a linear geometry to one S(4) and one S(5) atom. In the third Ti site, Ti(3) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(6) atoms. In the fourth Ti site, Ti(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(4) atoms. In the fifth Ti site, Ti(5) is bonded in a 4-coordinate geometry to one S(3), two equivalent S(2), and two equivalent S(6) atoms. In the sixth Ti site, Ti(6) is bonded in an L-shaped geometry to one S(1) and one S(4) atom. In the seventh Ti site, Ti(7) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(6) atoms. In the eighth Ti site, Ti(8) is bonded in a distorted L-shaped geometry to one S(2) and one S(6) atom. In the ninth Ti site, Ti(9) is bonded in a 4-coordinate geometry to two equivalent S(4) and two equivalent S(5) atoms. In the tenth Ti site, Ti(10) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(5) atoms. In the eleventh Ti site, Ti(11) is bonded in a 3-coordinate geometry to one S(2) and two equivalent S(3) atoms. In the twelfth Ti site, Ti(12) is bonded in a 3-coordinate geometry to one S(6) and two equivalent S(3) atoms. In the thirteenth Ti site, Ti(13) is bonded in a distorted single-bond geometry to one S(5) atom. In the fourteenth Ti site, Ti(14) is bonded in a distorted single-bond geometry to one S(3) atom. In the fifteenth Ti site, Ti(15) is bonded in a distorted square co-planar geometry to two equivalent S(1) and two equivalent S(3) atoms. In the sixteenth Ti site, Ti(16) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(4) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ti(3), one Ti(6), one Ti(7), two equivalent Ti(15), and two equivalent Ti(4) atoms to form distorted edge-sharing STi7 pentagonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to one Ti(11), one Ti(8), two equivalent Ti(10), two equivalent Ti(16), and two equivalent Ti(5) atoms. In the third S site, S(3) is bonded in a 9-coordinate geometry to one Ti(14), one Ti(5), one Ti(7), two equivalent Ti(11), two equivalent Ti(12), and two equivalent Ti(15) atoms. In the fourth S site, S(4) is bonded in a 8-coordinate geometry to one Ti(2), one Ti(6), two equivalent Ti(16), two equivalent Ti(4), and two equivalent Ti(9) atoms. In the fifth S site, S(5) is bonded in a 8-coordinate geometry to one Ti(13), one Ti(2), two equivalent Ti(1), two equivalent Ti(10), and two equivalent Ti(9) atoms. In the sixth S site, S(6) is bonded in a 8-coordinate geometry to one Ti(12), one Ti(8), two equivalent Ti(3), two equivalent Ti(5), and two equivalent Ti(7) atoms.
Ti8S3 crystallizes in the monoclinic C2/m space group. There are sixteen inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a distorted L-shaped geometry to two equivalent S(5) atoms. Both Ti(1)-S(5) bond lengths are 2.49 Å. In the second Ti site, Ti(2) is bonded in a linear geometry to one S(4) and one S(5) atom. The Ti(2)-S(4) bond length is 2.56 Å. The Ti(2)-S(5) bond length is 2.52 Å. In the third Ti site, Ti(3) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(6) atoms. The Ti(3)-S(1) bond length is 2.43 Å. Both Ti(3)-S(6) bond lengths are 2.52 Å. In the fourth Ti site, Ti(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(1) and two equivalent S(4) atoms. Both Ti(4)-S(1) bond lengths are 2.55 Å. Both Ti(4)-S(4) bond lengths are 2.52 Å. In the fifth Ti site, Ti(5) is bonded in a 4-coordinate geometry to one S(3), two equivalent S(2), and two equivalent S(6) atoms. The Ti(5)-S(3) bond length is 2.99 Å. Both Ti(5)-S(2) bond lengths are 2.56 Å. Both Ti(5)-S(6) bond lengths are 2.52 Å. In the sixth Ti site, Ti(6) is bonded in an L-shaped geometry to one S(1) and one S(4) atom. The Ti(6)-S(1) bond length is 2.54 Å. The Ti(6)-S(4) bond length is 2.60 Å. In the seventh Ti site, Ti(7) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(3), and two equivalent S(6) atoms. The Ti(7)-S(1) bond length is 2.46 Å. The Ti(7)-S(3) bond length is 2.60 Å. Both Ti(7)-S(6) bond lengths are 2.54 Å. In the eighth Ti site, Ti(8) is bonded in a distorted L-shaped geometry to one S(2) and one S(6) atom. The Ti(8)-S(2) bond length is 2.62 Å. The Ti(8)-S(6) bond length is 2.57 Å. In the ninth Ti site, Ti(9) is bonded in a 4-coordinate geometry to two equivalent S(4) and two equivalent S(5) atoms. Both Ti(9)-S(4) bond lengths are 2.52 Å. Both Ti(9)-S(5) bond lengths are 2.50 Å. In the tenth Ti site, Ti(10) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(5) atoms. Both Ti(10)-S(2) bond lengths are 2.48 Å. Both Ti(10)-S(5) bond lengths are 2.51 Å. In the eleventh Ti site, Ti(11) is bonded in a 3-coordinate geometry to one S(2) and two equivalent S(3) atoms. The Ti(11)-S(2) bond length is 2.54 Å. Both Ti(11)-S(3) bond lengths are 2.44 Å. In the twelfth Ti site, Ti(12) is bonded in a 3-coordinate geometry to one S(6) and two equivalent S(3) atoms. The Ti(12)-S(6) bond length is 2.53 Å. Both Ti(12)-S(3) bond lengths are 2.47 Å. In the thirteenth Ti site, Ti(13) is bonded in a distorted single-bond geometry to one S(5) atom. The Ti(13)-S(5) bond length is 2.53 Å. In the fourteenth Ti site, Ti(14) is bonded in a distorted single-bond geometry to one S(3) atom. The Ti(14)-S(3) bond length is 2.52 Å. In the fifteenth Ti site, Ti(15) is bonded in a distorted square co-planar geometry to two equivalent S(1) and two equivalent S(3) atoms. Both Ti(15)-S(1) bond lengths are 2.48 Å. Both Ti(15)-S(3) bond lengths are 2.48 Å. In the sixteenth Ti site, Ti(16) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(4) atoms. Both Ti(16)-S(2) bond lengths are 2.51 Å. Both Ti(16)-S(4) bond lengths are 2.49 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ti(3), one Ti(6), one Ti(7), two equivalent Ti(15), and two equivalent Ti(4) atoms to form distorted edge-sharing STi7 pentagonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to one Ti(11), one Ti(8), two equivalent Ti(10), two equivalent Ti(16), and two equivalent Ti(5) atoms. In the third S site, S(3) is bonded in a 9-coordinate geometry to one Ti(14), one Ti(5), one Ti(7), two equivalent Ti(11), two equivalent Ti(12), and two equivalent Ti(15) atoms. In the fourth S site, S(4) is bonded in a 8-coordinate geometry to one Ti(2), one Ti(6), two equivalent Ti(16), two equivalent Ti(4), and two equivalent Ti(9) atoms. In the fifth S site, S(5) is bonded in a 8-coordinate geometry to one Ti(13), one Ti(2), two equivalent Ti(1), two equivalent Ti(10), and two equivalent Ti(9) atoms. In the sixth S site, S(6) is bonded in a 8-coordinate geometry to one Ti(12), one Ti(8), two equivalent Ti(3), two equivalent Ti(5), and two equivalent Ti(7) atoms.