Ti2S crystallizes in the orthorhombic Pnnm space group. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(3) atoms. In the second Ti site, Ti(2) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. In the third Ti site, Ti(3) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted edge-sharing TiS5 trigonal bipyramids. In the fourth Ti site, Ti(4) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(3) atom. In the fifth Ti site, Ti(5) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(2) atoms. In the sixth Ti site, Ti(6) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Ti(4), one Ti(5), two equivalent Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms. In the second S site, S(2) is bonded in a 9-coordinate geometry to one Ti(1), one Ti(2), one Ti(4), two equivalent Ti(3), two equivalent Ti(5), and two equivalent Ti(6) atoms. In the third S site, S(3) is bonded to one Ti(2), one Ti(3), one Ti(4), two equivalent Ti(1), and two equivalent Ti(6) atoms to form distorted edge-sharing STi7 pentagonal bipyramids.
Ti2S crystallizes in the orthorhombic Pnnm space group. There are six inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(3) atoms. The Ti(1)-S(2) bond length is 2.80 Å. Both Ti(1)-S(1) bond lengths are 2.47 Å. Both Ti(1)-S(3) bond lengths are 2.50 Å. In the second Ti site, Ti(2) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Ti(2)-S(2) bond length is 2.75 Å. The Ti(2)-S(3) bond length is 2.44 Å. Both Ti(2)-S(1) bond lengths are 2.52 Å. In the third Ti site, Ti(3) is bonded to one S(3), two equivalent S(1), and two equivalent S(2) atoms to form distorted edge-sharing TiS5 trigonal bipyramids. The Ti(3)-S(3) bond length is 2.44 Å. Both Ti(3)-S(1) bond lengths are 2.48 Å. Both Ti(3)-S(2) bond lengths are 2.47 Å. In the fourth Ti site, Ti(4) is bonded in a distorted T-shaped geometry to one S(1), one S(2), and one S(3) atom. The Ti(4)-S(1) bond length is 2.60 Å. The Ti(4)-S(2) bond length is 2.56 Å. The Ti(4)-S(3) bond length is 2.51 Å. In the fifth Ti site, Ti(5) is bonded in a 3-coordinate geometry to one S(1) and two equivalent S(2) atoms. The Ti(5)-S(1) bond length is 2.50 Å. Both Ti(5)-S(2) bond lengths are 2.44 Å. In the sixth Ti site, Ti(6) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. Both Ti(6)-S(2) bond lengths are 2.53 Å. Both Ti(6)-S(3) bond lengths are 2.48 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 8-coordinate geometry to one Ti(4), one Ti(5), two equivalent Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms. In the second S site, S(2) is bonded in a 9-coordinate geometry to one Ti(1), one Ti(2), one Ti(4), two equivalent Ti(3), two equivalent Ti(5), and two equivalent Ti(6) atoms. In the third S site, S(3) is bonded to one Ti(2), one Ti(3), one Ti(4), two equivalent Ti(1), and two equivalent Ti(6) atoms to form distorted edge-sharing STi7 pentagonal bipyramids.