Ti9ZnS16 is beta indium sulfide-derived structured and crystallizes in the monoclinic Pc space group. There are nine inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(10), one S(12), one S(15), one S(2), and one S(5) atom to form a mixture of corner and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the second Ti site, Ti(2) is bonded to one S(1), one S(12), one S(2), one S(3), one S(5), and one S(6) atom to form edge-sharing TiS6 octahedra. In the third Ti site, Ti(3) is bonded to one S(2), one S(3), one S(4), one S(5), one S(6), and one S(9) atom to form TiS6 octahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Ti(7)S6 octahedra. In the fourth Ti site, Ti(4) is bonded to one S(1), one S(13), one S(15), one S(16), one S(3), and one S(4) atom to form TiS6 octahedra that share corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(5)S6 octahedra,  an edgeedge with one Ti(7)S6 octahedra,  an edgeedge with one Ti(8)S6 octahedra, and  an edgeedge with one Ti(9)S6 octahedra. In the fifth Ti site, Ti(5) is bonded to one S(11), one S(13), one S(14), one S(16), one S(7), and one S(8) atom to form TiS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(8)S6 octahedra, and edges with two equivalent Ti(9)S6 octahedra. In the sixth Ti site, Ti(6) is bonded to one S(10), one S(11), one S(12), one S(6), one S(7), and one S(9) atom to form TiS6 octahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(5)S6 octahedra,  an edgeedge with one Ti(7)S6 octahedra,  an edgeedge with one Ti(8)S6 octahedra, and  an edgeedge with one Ti(9)S6 octahedra. In the seventh Ti site, Ti(7) is bonded to one S(1), one S(12), one S(2), one S(4), one S(5), and one S(9) atom to form TiS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the eighth Ti site, Ti(8) is bonded to one S(10), one S(11), one S(13), one S(14), one S(15), and one S(8) atom to form TiS6 octahedra that share corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(5)S6 octahedra, and edges with two equivalent Ti(9)S6 octahedra. In the ninth Ti site, Ti(9) is bonded to one S(10), one S(14), one S(15), one S(16), one S(7), and one S(8) atom to form TiS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(5)S6 octahedra, and edges with two equivalent Ti(8)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. Zn(1) is bonded to one S(13), one S(14), one S(16), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Ti(3)S6 octahedra,  a cornercorner with one Ti(6)S6 octahedra,  a cornercorner with one Ti(7)S6 octahedra, corners with two equivalent Ti(4)S6 octahedra, corners with two equivalent Ti(8)S6 octahedra, corners with two equivalent Ti(9)S6 octahedra, and corners with three equivalent Ti(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), 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(3), and one Ti(7) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(3), and one Ti(4) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(4), and one Ti(7) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(3), and one Ti(7) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(3), and one Ti(6) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Ti(5), one Ti(6), and one Ti(9) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Ti(5), one Ti(8), and one Ti(9) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(3), one Ti(6), one Ti(7), and one Zn(1) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(6), one Ti(8), and one Ti(9) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(5), 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(1), one Ti(2), one Ti(6), and one Ti(7) atom. In the thirteenth S site, S(13) is bonded to one Ti(4), one Ti(5), one Ti(8), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn trigonal pyramids. In the fourteenth S site, S(14) is bonded to one Ti(5), one Ti(8), one Ti(9), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn tetrahedra. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(4), one Ti(8), and one Ti(9) atom. In the sixteenth S site, S(16) is bonded to one Ti(4), one Ti(5), one Ti(9), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn tetrahedra.
Ti9ZnS16 is beta indium sulfide-derived structured and crystallizes in the monoclinic Pc space group. There are nine inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(10), one S(12), one S(15), one S(2), and one S(5) atom to form a mixture of corner and edge-sharing TiS6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. The Ti(1)-S(1) bond length is 2.56 Å. The Ti(1)-S(10) bond length is 2.43 Å. The Ti(1)-S(12) bond length is 2.41 Å. The Ti(1)-S(15) bond length is 2.45 Å. The Ti(1)-S(2) bond length is 2.43 Å. The Ti(1)-S(5) bond length is 2.47 Å. In the second Ti site, Ti(2) is bonded to one S(1), one S(12), one S(2), one S(3), one S(5), and one S(6) atom to form edge-sharing TiS6 octahedra. The Ti(2)-S(1) bond length is 2.50 Å. The Ti(2)-S(12) bond length is 2.46 Å. The Ti(2)-S(2) bond length is 2.50 Å. The Ti(2)-S(3) bond length is 2.44 Å. The Ti(2)-S(5) bond length is 2.49 Å. The Ti(2)-S(6) bond length is 2.39 Å. In the third Ti site, Ti(3) is bonded to one S(2), one S(3), one S(4), one S(5), one S(6), and one S(9) atom to form TiS6 octahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Ti(7)S6 octahedra. The Ti(3)-S(2) bond length is 2.45 Å. The Ti(3)-S(3) bond length is 2.44 Å. The Ti(3)-S(4) bond length is 2.42 Å. The Ti(3)-S(5) bond length is 2.48 Å. The Ti(3)-S(6) bond length is 2.43 Å. The Ti(3)-S(9) bond length is 2.49 Å. In the fourth Ti site, Ti(4) is bonded to one S(1), one S(13), one S(15), one S(16), one S(3), and one S(4) atom to form TiS6 octahedra that share corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(5)S6 octahedra,  an edgeedge with one Ti(7)S6 octahedra,  an edgeedge with one Ti(8)S6 octahedra, and  an edgeedge with one Ti(9)S6 octahedra. The Ti(4)-S(1) bond length is 2.41 Å. The Ti(4)-S(13) bond length is 2.51 Å. The Ti(4)-S(15) bond length is 2.52 Å. The Ti(4)-S(16) bond length is 2.50 Å. The Ti(4)-S(3) bond length is 2.37 Å. The Ti(4)-S(4) bond length is 2.40 Å. In the fifth Ti site, Ti(5) is bonded to one S(11), one S(13), one S(14), one S(16), one S(7), and one S(8) atom to form TiS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(8)S6 octahedra, and edges with two equivalent Ti(9)S6 octahedra. The Ti(5)-S(11) bond length is 2.38 Å. The Ti(5)-S(13) bond length is 2.53 Å. The Ti(5)-S(14) bond length is 2.53 Å. The Ti(5)-S(16) bond length is 2.53 Å. The Ti(5)-S(7) bond length is 2.35 Å. The Ti(5)-S(8) bond length is 2.38 Å. In the sixth Ti site, Ti(6) is bonded to one S(10), one S(11), one S(12), one S(6), one S(7), and one S(9) atom to form TiS6 octahedra that share  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Ti(5)S6 octahedra,  an edgeedge with one Ti(7)S6 octahedra,  an edgeedge with one Ti(8)S6 octahedra, and  an edgeedge with one Ti(9)S6 octahedra. The Ti(6)-S(10) bond length is 2.47 Å. The Ti(6)-S(11) bond length is 2.44 Å. The Ti(6)-S(12) bond length is 2.50 Å. The Ti(6)-S(6) bond length is 2.43 Å. The Ti(6)-S(7) bond length is 2.47 Å. The Ti(6)-S(9) bond length is 2.49 Å. In the seventh Ti site, Ti(7) is bonded to one S(1), one S(12), one S(2), one S(4), one S(5), and one S(9) atom to form TiS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra,  a cornercorner with one Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. The Ti(7)-S(1) bond length is 2.48 Å. The Ti(7)-S(12) bond length is 2.44 Å. The Ti(7)-S(2) bond length is 2.41 Å. The Ti(7)-S(4) bond length is 2.41 Å. The Ti(7)-S(5) bond length is 2.50 Å. The Ti(7)-S(9) bond length is 2.46 Å. In the eighth Ti site, Ti(8) is bonded to one S(10), one S(11), one S(13), one S(14), one S(15), and one S(8) atom to form TiS6 octahedra that share corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(1)S6 octahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(5)S6 octahedra, and edges with two equivalent Ti(9)S6 octahedra. The Ti(8)-S(10) bond length is 2.44 Å. The Ti(8)-S(11) bond length is 2.39 Å. The Ti(8)-S(13) bond length is 2.47 Å. The Ti(8)-S(14) bond length is 2.50 Å. The Ti(8)-S(15) bond length is 2.49 Å. The Ti(8)-S(8) bond length is 2.44 Å. In the ninth Ti site, Ti(9) is bonded to one S(10), one S(14), one S(15), one S(16), one S(7), and one S(8) atom to form TiS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra,  an edgeedge with one Ti(4)S6 octahedra,  an edgeedge with one Ti(6)S6 octahedra, edges with two equivalent Ti(5)S6 octahedra, and edges with two equivalent Ti(8)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Ti(9)-S(10) bond length is 2.38 Å. The Ti(9)-S(14) bond length is 2.51 Å. The Ti(9)-S(15) bond length is 2.52 Å. The Ti(9)-S(16) bond length is 2.51 Å. The Ti(9)-S(7) bond length is 2.40 Å. The Ti(9)-S(8) bond length is 2.41 Å. Zn(1) is bonded to one S(13), one S(14), one S(16), and one S(9) atom to form ZnS4 tetrahedra that share  a cornercorner with one Ti(3)S6 octahedra,  a cornercorner with one Ti(6)S6 octahedra,  a cornercorner with one Ti(7)S6 octahedra, corners with two equivalent Ti(4)S6 octahedra, corners with two equivalent Ti(8)S6 octahedra, corners with two equivalent Ti(9)S6 octahedra, and corners with three equivalent Ti(5)S6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. The Zn(1)-S(13) bond length is 2.30 Å. The Zn(1)-S(14) bond length is 2.30 Å. The Zn(1)-S(16) bond length is 2.30 Å. The Zn(1)-S(9) bond length is 2.31 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(4), 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(3), and one Ti(7) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(3), and one Ti(4) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Ti(3), one Ti(4), and one Ti(7) atom. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(2), one Ti(3), and one Ti(7) atom. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Ti(2), one Ti(3), and one Ti(6) atom. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Ti(5), one Ti(6), and one Ti(9) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Ti(5), one Ti(8), and one Ti(9) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Ti(3), one Ti(6), one Ti(7), and one Zn(1) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(6), one Ti(8), and one Ti(9) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Ti(5), 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(1), one Ti(2), one Ti(6), and one Ti(7) atom. In the thirteenth S site, S(13) is bonded to one Ti(4), one Ti(5), one Ti(8), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn trigonal pyramids. In the fourteenth S site, S(14) is bonded to one Ti(5), one Ti(8), one Ti(9), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn tetrahedra. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(4), one Ti(8), and one Ti(9) atom. In the sixteenth S site, S(16) is bonded to one Ti(4), one Ti(5), one Ti(9), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing STi3Zn tetrahedra.