V2Cr3S8Tl crystallizes in the monoclinic Cm space group. The structure consists of two 7440-28-0 atoms inside a V2Cr3S8 framework. In the V2Cr3S8 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one S(4), one S(7), two equivalent S(2), and two equivalent S(3) atoms to form VS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. In the second V site, V(2) is bonded to one S(1), one S(2), two equivalent S(7), and two equivalent S(8) atoms to form VS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(7), two equivalent S(3), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the second Cr site, Cr(2) is bonded to one S(6), one S(8), two equivalent S(4), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  a faceface with one Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. In the third Cr site, Cr(3) is bonded to one S(3), one S(8), two equivalent S(1), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  a faceface with one Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent Cr(3) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the third S site, S(3) is bonded to two equivalent V(1), one Cr(3), and two equivalent Cr(1) atoms to form distorted SV2Cr3 trigonal bipyramids that share edges with two equivalent S(3)V2Cr3 trigonal bipyramids, edges with two equivalent S(4)VCr4 trigonal bipyramids, and edges with two equivalent S(7)V3Cr trigonal pyramids. In the fourth S site, S(4) is bonded to one V(1), two equivalent Cr(2), and two equivalent Cr(3) atoms to form distorted SVCr4 trigonal bipyramids that share  a cornercorner with one S(7)V3Cr trigonal pyramid, edges with two equivalent S(3)V2Cr3 trigonal bipyramids, and edges with two equivalent S(4)VCr4 trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Cr(1) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Cr(2) and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded to one V(1), two equivalent V(2), and one Cr(1) atom to form SV3Cr trigonal pyramids that share  a cornercorner with one S(4)VCr4 trigonal bipyramid, corners with two equivalent S(7)V3Cr trigonal pyramids, and edges with two equivalent S(3)V2Cr3 trigonal bipyramids. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to two equivalent V(2), one Cr(2), and one Cr(3) atom.
V2Cr3S8Tl crystallizes in the monoclinic Cm space group. The structure consists of two 7440-28-0 atoms inside a V2Cr3S8 framework. In the V2Cr3S8 framework, there are two inequivalent V sites. In the first V site, V(1) is bonded to one S(4), one S(7), two equivalent S(2), and two equivalent S(3) atoms to form VS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  a faceface with one Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The V(1)-S(4) bond length is 2.50 Å. The V(1)-S(7) bond length is 2.33 Å. Both V(1)-S(2) bond lengths are 2.35 Å. Both V(1)-S(3) bond lengths are 2.58 Å. In the second V site, V(2) is bonded to one S(1), one S(2), two equivalent S(7), and two equivalent S(8) atoms to form VS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. The V(2)-S(1) bond length is 2.45 Å. The V(2)-S(2) bond length is 2.33 Å. Both V(2)-S(7) bond lengths are 2.40 Å. Both V(2)-S(8) bond lengths are 2.43 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(7), two equivalent S(3), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  a faceface with one V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Cr(1)-S(5) bond length is 2.36 Å. The Cr(1)-S(7) bond length is 2.46 Å. Both Cr(1)-S(3) bond lengths are 2.49 Å. Both Cr(1)-S(6) bond lengths are 2.36 Å. In the second Cr site, Cr(2) is bonded to one S(6), one S(8), two equivalent S(4), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with two equivalent V(1)S6 octahedra, corners with two equivalent V(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  a faceface with one Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. The Cr(2)-S(6) bond length is 2.38 Å. The Cr(2)-S(8) bond length is 2.45 Å. Both Cr(2)-S(4) bond lengths are 2.52 Å. Both Cr(2)-S(5) bond lengths are 2.35 Å. In the third Cr site, Cr(3) is bonded to one S(3), one S(8), two equivalent S(1), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  a faceface with one Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Cr(3)-S(3) bond length is 2.40 Å. The Cr(3)-S(8) bond length is 2.37 Å. Both Cr(3)-S(1) bond lengths are 2.34 Å. Both Cr(3)-S(4) bond lengths are 2.52 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent Cr(3) atoms. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the third S site, S(3) is bonded to two equivalent V(1), one Cr(3), and two equivalent Cr(1) atoms to form distorted SV2Cr3 trigonal bipyramids that share edges with two equivalent S(3)V2Cr3 trigonal bipyramids, edges with two equivalent S(4)VCr4 trigonal bipyramids, and edges with two equivalent S(7)V3Cr trigonal pyramids. In the fourth S site, S(4) is bonded to one V(1), two equivalent Cr(2), and two equivalent Cr(3) atoms to form distorted SVCr4 trigonal bipyramids that share  a cornercorner with one S(7)V3Cr trigonal pyramid, edges with two equivalent S(3)V2Cr3 trigonal bipyramids, and edges with two equivalent S(4)VCr4 trigonal bipyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Cr(1) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Cr(2) and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded to one V(1), two equivalent V(2), and one Cr(1) atom to form SV3Cr trigonal pyramids that share  a cornercorner with one S(4)VCr4 trigonal bipyramid, corners with two equivalent S(7)V3Cr trigonal pyramids, and edges with two equivalent S(3)V2Cr3 trigonal bipyramids. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to two equivalent V(2), one Cr(2), and one Cr(3) atom.