Ti7S12 crystallizes in the triclinic P-1 space group. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(11), one S(2), one S(5), one S(9), and two equivalent S(10) atoms to form a mixture of edge, face, and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second Ti site, Ti(2) is bonded to one S(10), one S(12), one S(2), one S(3), one S(8), and one S(9) atom to form a mixture of edge, face, and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 6-48°. In the third Ti site, Ti(3) is bonded to one S(1), one S(6), two equivalent S(12), and two equivalent S(3) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 6°. In the fourth Ti site, Ti(4) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 46°. In the fifth Ti site, Ti(5) is bonded to one S(1), one S(3), one S(6), one S(8), and two equivalent S(7) atoms to form edge-sharing TiS6 octahedra. In the sixth Ti site, Ti(6) is bonded to one S(10), one S(11), one S(4), one S(5), and two equivalent S(9) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the seventh Ti site, Ti(7) is bonded to one S(1), one S(12), one S(6), one S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the eighth Ti site, Ti(8) is bonded to two equivalent S(11), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(5), and one Ti(7) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), and one Ti(8) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(5), and two equivalent Ti(3) atoms. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(4), one Ti(6), and one Ti(8) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(4), and one Ti(6) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(5), and one Ti(7) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Ti(7) and two equivalent Ti(5) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(5), and two equivalent Ti(7) atoms. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(6) atoms. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(6), and two equivalent Ti(1) atoms. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(6), and one Ti(8) atom. In the twelfth S site, S(12) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(7), and two equivalent Ti(3) atoms.
Ti7S12 crystallizes in the triclinic P-1 space group. There are eight inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(11), one S(2), one S(5), one S(9), and two equivalent S(10) atoms to form a mixture of edge, face, and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 47°. The Ti(1)-S(11) bond length is 2.40 Å. The Ti(1)-S(2) bond length is 2.45 Å. The Ti(1)-S(5) bond length is 2.40 Å. The Ti(1)-S(9) bond length is 2.46 Å. There is one shorter (2.46 Å) and one longer (2.47 Å) Ti(1)-S(10) bond length. In the second Ti site, Ti(2) is bonded to one S(10), one S(12), one S(2), one S(3), one S(8), and one S(9) atom to form a mixture of edge, face, and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 6-48°. The Ti(2)-S(10) bond length is 2.52 Å. The Ti(2)-S(12) bond length is 2.37 Å. The Ti(2)-S(2) bond length is 2.55 Å. The Ti(2)-S(3) bond length is 2.38 Å. The Ti(2)-S(8) bond length is 2.35 Å. The Ti(2)-S(9) bond length is 2.56 Å. In the third Ti site, Ti(3) is bonded to one S(1), one S(6), two equivalent S(12), and two equivalent S(3) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 6°. The Ti(3)-S(1) bond length is 2.43 Å. The Ti(3)-S(6) bond length is 2.39 Å. There is one shorter (2.43 Å) and one longer (2.46 Å) Ti(3)-S(12) bond length. There is one shorter (2.46 Å) and one longer (2.47 Å) Ti(3)-S(3) bond length. In the fourth Ti site, Ti(4) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Ti(4)-S(2) bond lengths are 2.46 Å. Both Ti(4)-S(4) bond lengths are 2.42 Å. Both Ti(4)-S(5) bond lengths are 2.42 Å. In the fifth Ti site, Ti(5) is bonded to one S(1), one S(3), one S(6), one S(8), and two equivalent S(7) atoms to form edge-sharing TiS6 octahedra. The Ti(5)-S(1) bond length is 2.41 Å. The Ti(5)-S(3) bond length is 2.49 Å. The Ti(5)-S(6) bond length is 2.39 Å. The Ti(5)-S(8) bond length is 2.51 Å. Both Ti(5)-S(7) bond lengths are 2.41 Å. In the sixth Ti site, Ti(6) is bonded to one S(10), one S(11), one S(4), one S(5), and two equivalent S(9) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. The Ti(6)-S(10) bond length is 2.51 Å. The Ti(6)-S(11) bond length is 2.38 Å. The Ti(6)-S(4) bond length is 2.37 Å. The Ti(6)-S(5) bond length is 2.39 Å. Both Ti(6)-S(9) bond lengths are 2.50 Å. In the seventh Ti site, Ti(7) is bonded to one S(1), one S(12), one S(6), one S(7), and two equivalent S(8) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 8°. The Ti(7)-S(1) bond length is 2.41 Å. The Ti(7)-S(12) bond length is 2.49 Å. The Ti(7)-S(6) bond length is 2.46 Å. The Ti(7)-S(7) bond length is 2.43 Å. There is one shorter (2.42 Å) and one longer (2.46 Å) Ti(7)-S(8) bond length. In the eighth Ti site, Ti(8) is bonded to two equivalent S(11), two equivalent S(2), and two equivalent S(4) atoms to form a mixture of edge and corner-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Ti(8)-S(11) bond lengths are 2.43 Å. Both Ti(8)-S(2) bond lengths are 2.46 Å. Both Ti(8)-S(4) bond lengths are 2.42 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(5), and one Ti(7) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), and one Ti(8) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(5), and two equivalent Ti(3) atoms. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(4), one Ti(6), and one Ti(8) atom. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(4), and one Ti(6) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(5), and one Ti(7) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Ti(7) and two equivalent Ti(5) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(5), and two equivalent Ti(7) atoms. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), and two equivalent Ti(6) atoms. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(6), and two equivalent Ti(1) atoms. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(6), and one Ti(8) atom. In the twelfth S site, S(12) is bonded in a rectangular see-saw-like geometry to one Ti(2), one Ti(7), and two equivalent Ti(3) atoms.