Ti4FeCoS8 crystallizes in the triclinic P-1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with two equivalent Co(1)S6 octahedra, corners with four equivalent Fe(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and  a faceface with one Co(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the second Ti site, Ti(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent Co(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Fe(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Co(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. Co(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form CoS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ti(2), two equivalent Ti(1), one Fe(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing STi3FeCo square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Fe(1) atom. In the third S site, S(3) is bonded to one Ti(1), two equivalent Ti(2), one Fe(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing STi3FeCo square pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Co(1) atom.
Ti4FeCoS8 crystallizes in the triclinic P-1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form TiS6 octahedra that share corners with two equivalent Co(1)S6 octahedra, corners with four equivalent Fe(1)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(2)S6 octahedra, and  a faceface with one Co(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Ti(1)-S(2) bond length is 2.42 Å. The Ti(1)-S(3) bond length is 2.50 Å. There is one shorter (2.45 Å) and one longer (2.49 Å) Ti(1)-S(1) bond length. There is one shorter (2.41 Å) and one longer (2.42 Å) Ti(1)-S(4) bond length. In the second Ti site, Ti(2) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(3) atoms to form TiS6 octahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent Co(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(1)S6 octahedra, and  a faceface with one Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Ti(2)-S(1) bond length is 2.46 Å. The Ti(2)-S(4) bond length is 2.40 Å. There is one shorter (2.42 Å) and one longer (2.43 Å) Ti(2)-S(2) bond length. There is one shorter (2.45 Å) and one longer (2.48 Å) Ti(2)-S(3) bond length. Fe(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(1)S6 octahedra, edges with two equivalent Co(1)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. Both Fe(1)-S(1) bond lengths are 2.32 Å. Both Fe(1)-S(2) bond lengths are 2.29 Å. Both Fe(1)-S(3) bond lengths are 2.31 Å. Co(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form CoS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(2)S6 octahedra, edges with two equivalent Fe(1)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Both Co(1)-S(1) bond lengths are 2.35 Å. Both Co(1)-S(3) bond lengths are 2.34 Å. Both Co(1)-S(4) bond lengths are 2.30 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ti(2), two equivalent Ti(1), one Fe(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing STi3FeCo square pyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ti(1), two equivalent Ti(2), and one Fe(1) atom. In the third S site, S(3) is bonded to one Ti(1), two equivalent Ti(2), one Fe(1), and one Co(1) atom to form a mixture of distorted corner and edge-sharing STi3FeCo square pyramids. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Co(1) atom.