Ti5(CuS5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(3), one S(4), one S(5), and two equivalent S(2) atoms to form TiS6 octahedra that share corners with seven equivalent Cu(1)S6 octahedra,  an edgeedge with one Ti(1)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and edges with three equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. In the second Ti site, Ti(2) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with four equivalent Cu(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, and  a faceface with one Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the third Ti site, Ti(3) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with two equivalent Cu(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. Cu(1) is bonded to one S(1), one S(2), one S(3), one S(5), and two equivalent S(4) atoms to form CuS6 octahedra that share  a cornercorner with one Ti(3)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with seven equivalent Ti(1)S6 octahedra,  an edgeedge with one Cu(1)S6 octahedra,  a faceface with one Ti(2)S6 octahedra, and  a faceface with one Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. There are five inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cu(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(1), and one Cu(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cu(1) atom. In the fourth S site, S(4) is bonded to one Ti(1), one Ti(2), one Ti(3), and two equivalent Cu(1) atoms to form a mixture of distorted corner and edge-sharing STi3Cu2 square pyramids. 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 Cu(1) atom.
Ti5(CuS5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(3), one S(4), one S(5), and two equivalent S(2) atoms to form TiS6 octahedra that share corners with seven equivalent Cu(1)S6 octahedra,  an edgeedge with one Ti(1)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and edges with three equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. The Ti(1)-S(1) bond length is 2.44 Å. The Ti(1)-S(3) bond length is 2.44 Å. The Ti(1)-S(4) bond length is 2.45 Å. The Ti(1)-S(5) bond length is 2.43 Å. There is one shorter (2.43 Å) and one longer (2.44 Å) Ti(1)-S(2) bond length. In the second Ti site, Ti(2) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with four equivalent Cu(1)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with three equivalent Ti(1)S6 octahedra, and  a faceface with one Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The Ti(2)-S(4) bond length is 2.48 Å. The Ti(2)-S(5) bond length is 2.44 Å. There is one shorter (2.43 Å) and one longer (2.46 Å) Ti(2)-S(1) bond length. There is one shorter (2.43 Å) and one longer (2.45 Å) Ti(2)-S(3) bond length. In the third Ti site, Ti(3) is bonded to two equivalent S(2), two equivalent S(4), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with two equivalent Cu(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and faces with two equivalent Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles are 47°. Both Ti(3)-S(2) bond lengths are 2.44 Å. Both Ti(3)-S(4) bond lengths are 2.46 Å. Both Ti(3)-S(5) bond lengths are 2.46 Å. Cu(1) is bonded to one S(1), one S(2), one S(3), one S(5), and two equivalent S(4) atoms to form CuS6 octahedra that share  a cornercorner with one Ti(3)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with seven equivalent Ti(1)S6 octahedra,  an edgeedge with one Cu(1)S6 octahedra,  a faceface with one Ti(2)S6 octahedra, and  a faceface with one Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. The Cu(1)-S(1) bond length is 2.46 Å. The Cu(1)-S(2) bond length is 2.47 Å. The Cu(1)-S(3) bond length is 2.43 Å. The Cu(1)-S(5) bond length is 2.43 Å. There is one shorter (2.52 Å) and one longer (2.53 Å) Cu(1)-S(4) bond length. There are five inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cu(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(3), two equivalent Ti(1), and one Cu(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Cu(1) atom. In the fourth S site, S(4) is bonded to one Ti(1), one Ti(2), one Ti(3), and two equivalent Cu(1) atoms to form a mixture of distorted corner and edge-sharing STi3Cu2 square pyramids. 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 Cu(1) atom.