Tl4TiS4 crystallizes in the triclinic P1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a tetrahedral geometry to one S(1), one S(13), one S(5), and one S(9) atom. In the second Ti site, Ti(2) is bonded in a tetrahedral geometry to one S(10), one S(14), one S(2), and one S(6) atom. In the third Ti site, Ti(3) is bonded in a tetrahedral geometry to one S(11), one S(15), one S(3), and one S(7) atom. In the fourth Ti site, Ti(4) is bonded in a tetrahedral geometry to one S(12), one S(16), one S(4), and one S(8) atom. There are sixteen inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one S(11), one S(16), and one S(3) atom. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one S(12), one S(15), and one S(4) atom. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one S(1), one S(14), and one S(9) atom. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one S(10), one S(13), and one S(2) atom. In the fifth Tl site, Tl(5) is bonded in a 3-coordinate geometry to one S(1), one S(15), and one S(3) atom. In the sixth Tl site, Tl(6) is bonded in a distorted T-shaped geometry to one S(16), one S(2), and one S(4) atom. In the seventh Tl site, Tl(7) is bonded in a distorted T-shaped geometry to one S(1), one S(13), and one S(3) atom. In the eighth Tl site, Tl(8) is bonded in a distorted T-shaped geometry to one S(14), one S(2), and one S(4) atom. In the ninth Tl site, Tl(9) is bonded in a 3-coordinate geometry to one S(1), one S(11), and one S(7) atom. In the tenth Tl site, Tl(10) is bonded in a 3-coordinate geometry to one S(12), one S(2), and one S(8) atom. In the eleventh Tl site, Tl(11) is bonded in a 3-coordinate geometry to one S(3), one S(5), and one S(9) atom. In the twelfth Tl site, Tl(12) is bonded in a 3-coordinate geometry to one S(10), one S(4), and one S(6) atom. In the thirteenth Tl site, Tl(13) is bonded in a 3-coordinate geometry to one S(15), one S(16), and one S(7) atom. In the fourteenth Tl site, Tl(14) is bonded in a 3-coordinate geometry to one S(15), one S(16), and one S(8) atom. In the fifteenth Tl site, Tl(15) is bonded in a distorted trigonal non-coplanar geometry to one S(13), one S(14), and one S(5) atom. In the sixteenth Tl site, Tl(16) is bonded in a distorted T-shaped geometry to one S(13), one S(14), and one S(6) atom. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ti(1), one Tl(3), one Tl(5), one Tl(7), and one Tl(9) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ti(2), one Tl(10), one Tl(4), one Tl(6), and one Tl(8) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ti(3), one Tl(1), one Tl(11), one Tl(5), and one Tl(7) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ti(4), one Tl(12), one Tl(2), one Tl(6), and one Tl(8) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Ti(1), one Tl(11), and one Tl(15) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Ti(2), one Tl(12), and one Tl(16) atom. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Ti(3), one Tl(13), and one Tl(9) atom. In the eighth S site, S(8) is bonded in a 1-coordinate geometry to one Ti(4), one Tl(10), and one Tl(14) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one Ti(1), one Tl(11), and one Tl(3) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Ti(2), one Tl(12), and one Tl(4) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(3), one Tl(1), and one Tl(9) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Ti(4), one Tl(10), and one Tl(2) atom. In the thirteenth S site, S(13) is bonded in a 5-coordinate geometry to one Ti(1), one Tl(15), one Tl(16), one Tl(4), and one Tl(7) atom. In the fourteenth S site, S(14) is bonded in a 5-coordinate geometry to one Ti(2), one Tl(15), one Tl(16), one Tl(3), and one Tl(8) atom. In the fifteenth S site, S(15) is bonded in a 5-coordinate geometry to one Ti(3), one Tl(13), one Tl(14), one Tl(2), and one Tl(5) atom. In the sixteenth S site, S(16) is bonded in a 5-coordinate geometry to one Ti(4), one Tl(1), one Tl(13), one Tl(14), and one Tl(6) atom.
Tl4TiS4 crystallizes in the triclinic P1 space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a tetrahedral geometry to one S(1), one S(13), one S(5), and one S(9) atom. The Ti(1)-S(1) bond length is 2.37 Å. The Ti(1)-S(13) bond length is 2.32 Å. The Ti(1)-S(5) bond length is 2.18 Å. The Ti(1)-S(9) bond length is 2.24 Å. In the second Ti site, Ti(2) is bonded in a tetrahedral geometry to one S(10), one S(14), one S(2), and one S(6) atom. The Ti(2)-S(10) bond length is 2.20 Å. The Ti(2)-S(14) bond length is 2.32 Å. The Ti(2)-S(2) bond length is 2.27 Å. The Ti(2)-S(6) bond length is 2.25 Å. In the third Ti site, Ti(3) is bonded in a tetrahedral geometry to one S(11), one S(15), one S(3), and one S(7) atom. The Ti(3)-S(11) bond length is 2.29 Å. The Ti(3)-S(15) bond length is 2.33 Å. The Ti(3)-S(3) bond length is 2.24 Å. The Ti(3)-S(7) bond length is 2.31 Å. In the fourth Ti site, Ti(4) is bonded in a tetrahedral geometry to one S(12), one S(16), one S(4), and one S(8) atom. The Ti(4)-S(12) bond length is 2.22 Å. The Ti(4)-S(16) bond length is 2.30 Å. The Ti(4)-S(4) bond length is 2.37 Å. The Ti(4)-S(8) bond length is 2.26 Å. There are sixteen inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one S(11), one S(16), and one S(3) atom. The Tl(1)-S(11) bond length is 2.96 Å. The Tl(1)-S(16) bond length is 3.20 Å. The Tl(1)-S(3) bond length is 3.05 Å. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one S(12), one S(15), and one S(4) atom. The Tl(2)-S(12) bond length is 3.00 Å. The Tl(2)-S(15) bond length is 3.20 Å. The Tl(2)-S(4) bond length is 3.00 Å. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one S(1), one S(14), and one S(9) atom. The Tl(3)-S(1) bond length is 3.00 Å. The Tl(3)-S(14) bond length is 3.20 Å. The Tl(3)-S(9) bond length is 2.98 Å. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one S(10), one S(13), and one S(2) atom. The Tl(4)-S(10) bond length is 3.05 Å. The Tl(4)-S(13) bond length is 3.22 Å. The Tl(4)-S(2) bond length is 3.08 Å. In the fifth Tl site, Tl(5) is bonded in a 3-coordinate geometry to one S(1), one S(15), and one S(3) atom. The Tl(5)-S(1) bond length is 3.15 Å. The Tl(5)-S(15) bond length is 3.09 Å. The Tl(5)-S(3) bond length is 2.98 Å. In the sixth Tl site, Tl(6) is bonded in a distorted T-shaped geometry to one S(16), one S(2), and one S(4) atom. The Tl(6)-S(16) bond length is 3.10 Å. The Tl(6)-S(2) bond length is 3.04 Å. The Tl(6)-S(4) bond length is 2.99 Å. In the seventh Tl site, Tl(7) is bonded in a distorted T-shaped geometry to one S(1), one S(13), and one S(3) atom. The Tl(7)-S(1) bond length is 3.01 Å. The Tl(7)-S(13) bond length is 3.10 Å. The Tl(7)-S(3) bond length is 3.12 Å. In the eighth Tl site, Tl(8) is bonded in a distorted T-shaped geometry to one S(14), one S(2), and one S(4) atom. The Tl(8)-S(14) bond length is 3.11 Å. The Tl(8)-S(2) bond length is 3.01 Å. The Tl(8)-S(4) bond length is 3.10 Å. In the ninth Tl site, Tl(9) is bonded in a 3-coordinate geometry to one S(1), one S(11), and one S(7) atom. The Tl(9)-S(1) bond length is 3.19 Å. The Tl(9)-S(11) bond length is 2.99 Å. The Tl(9)-S(7) bond length is 3.00 Å. In the tenth Tl site, Tl(10) is bonded in a 3-coordinate geometry to one S(12), one S(2), and one S(8) atom. The Tl(10)-S(12) bond length is 2.97 Å. The Tl(10)-S(2) bond length is 3.15 Å. The Tl(10)-S(8) bond length is 3.02 Å. In the eleventh Tl site, Tl(11) is bonded in a 3-coordinate geometry to one S(3), one S(5), and one S(9) atom. The Tl(11)-S(3) bond length is 3.17 Å. The Tl(11)-S(5) bond length is 3.01 Å. The Tl(11)-S(9) bond length is 3.02 Å. In the twelfth Tl site, Tl(12) is bonded in a 3-coordinate geometry to one S(10), one S(4), and one S(6) atom. The Tl(12)-S(10) bond length is 2.99 Å. The Tl(12)-S(4) bond length is 3.15 Å. The Tl(12)-S(6) bond length is 3.01 Å. In the thirteenth Tl site, Tl(13) is bonded in a 3-coordinate geometry to one S(15), one S(16), and one S(7) atom. The Tl(13)-S(15) bond length is 2.95 Å. The Tl(13)-S(16) bond length is 3.04 Å. The Tl(13)-S(7) bond length is 3.19 Å. In the fourteenth Tl site, Tl(14) is bonded in a 3-coordinate geometry to one S(15), one S(16), and one S(8) atom. The Tl(14)-S(15) bond length is 3.11 Å. The Tl(14)-S(16) bond length is 2.98 Å. The Tl(14)-S(8) bond length is 3.16 Å. In the fifteenth Tl site, Tl(15) is bonded in a distorted trigonal non-coplanar geometry to one S(13), one S(14), and one S(5) atom. The Tl(15)-S(13) bond length is 2.97 Å. The Tl(15)-S(14) bond length is 3.01 Å. The Tl(15)-S(5) bond length is 3.09 Å. In the sixteenth Tl site, Tl(16) is bonded in a distorted T-shaped geometry to one S(13), one S(14), and one S(6) atom. The Tl(16)-S(13) bond length is 3.04 Å. The Tl(16)-S(14) bond length is 3.05 Å. The Tl(16)-S(6) bond length is 3.09 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ti(1), one Tl(3), one Tl(5), one Tl(7), and one Tl(9) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Ti(2), one Tl(10), one Tl(4), one Tl(6), and one Tl(8) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Ti(3), one Tl(1), one Tl(11), one Tl(5), and one Tl(7) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ti(4), one Tl(12), one Tl(2), one Tl(6), and one Tl(8) atom. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Ti(1), one Tl(11), and one Tl(15) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Ti(2), one Tl(12), and one Tl(16) atom. In the seventh S site, S(7) is bonded in a 3-coordinate geometry to one Ti(3), one Tl(13), and one Tl(9) atom. In the eighth S site, S(8) is bonded in a 1-coordinate geometry to one Ti(4), one Tl(10), and one Tl(14) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one Ti(1), one Tl(11), and one Tl(3) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Ti(2), one Tl(12), and one Tl(4) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(3), one Tl(1), and one Tl(9) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Ti(4), one Tl(10), and one Tl(2) atom. In the thirteenth S site, S(13) is bonded in a 5-coordinate geometry to one Ti(1), one Tl(15), one Tl(16), one Tl(4), and one Tl(7) atom. In the fourteenth S site, S(14) is bonded in a 5-coordinate geometry to one Ti(2), one Tl(15), one Tl(16), one Tl(3), and one Tl(8) atom. In the fifteenth S site, S(15) is bonded in a 5-coordinate geometry to one Ti(3), one Tl(13), one Tl(14), one Tl(2), and one Tl(5) atom. In the sixteenth S site, S(16) is bonded in a 5-coordinate geometry to one Ti(4), one Tl(1), one Tl(13), one Tl(14), and one Tl(6) atom.