TlCr5Te8 crystallizes in the triclinic P1 space group. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one Te(1), one Te(2), two equivalent Te(5), and two equivalent Te(7) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the second Cr site, Cr(2) is bonded to one Te(1), one Te(3), two equivalent Te(6), and two equivalent Te(7) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the third Cr site, Cr(3) is bonded to one Te(4), one Te(5), two equivalent Te(1), and two equivalent Te(8) atoms to form a mixture of corner and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. In the fourth Cr site, Cr(4) is bonded to one Te(6), one Te(8), two equivalent Te(2), and two equivalent Te(3) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the fifth Cr site, Cr(5) is bonded to one Te(7), one Te(8), two equivalent Te(2), and two equivalent Te(4) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. Tl(1) is bonded in a 5-coordinate geometry to one Te(8), two equivalent Te(3), and two equivalent Te(4) atoms. There are eight inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the second Te site, Te(2) is bonded to one Cr(1), two equivalent Cr(4), and two equivalent Cr(5) atoms to form distorted edge-sharing TeCr5 trigonal bipyramids. In the third Te site, Te(3) is bonded in a 3-coordinate geometry to one Cr(2), two equivalent Cr(4), and two equivalent Tl(1) atoms. In the fourth Te site, Te(4) is bonded in a 3-coordinate geometry to one Cr(3), two equivalent Cr(5), and two equivalent Tl(1) atoms. In the fifth Te site, Te(5) is bonded in a distorted T-shaped geometry to one Cr(3) and two equivalent Cr(1) atoms. In the sixth Te site, Te(6) is bonded in a distorted T-shaped geometry to one Cr(4) and two equivalent Cr(2) atoms. In the seventh Te site, Te(7) is bonded to one Cr(5), two equivalent Cr(1), and two equivalent Cr(2) atoms to form distorted edge-sharing TeCr5 trigonal bipyramids. In the eighth Te site, Te(8) is bonded in a rectangular see-saw-like geometry to one Cr(4), one Cr(5), two equivalent Cr(3), and one Tl(1) atom.
TlCr5Te8 crystallizes in the triclinic P1 space group. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one Te(1), one Te(2), two equivalent Te(5), and two equivalent Te(7) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The Cr(1)-Te(1) bond length is 2.72 Å. The Cr(1)-Te(2) bond length is 2.78 Å. Both Cr(1)-Te(5) bond lengths are 2.72 Å. There is one shorter (2.86 Å) and one longer (2.87 Å) Cr(1)-Te(7) bond length. In the second Cr site, Cr(2) is bonded to one Te(1), one Te(3), two equivalent Te(6), and two equivalent Te(7) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The Cr(2)-Te(1) bond length is 2.75 Å. The Cr(2)-Te(3) bond length is 2.71 Å. Both Cr(2)-Te(6) bond lengths are 2.72 Å. Both Cr(2)-Te(7) bond lengths are 2.83 Å. In the third Cr site, Cr(3) is bonded to one Te(4), one Te(5), two equivalent Te(1), and two equivalent Te(8) atoms to form a mixture of corner and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles are 49°. The Cr(3)-Te(4) bond length is 2.76 Å. The Cr(3)-Te(5) bond length is 2.75 Å. Both Cr(3)-Te(1) bond lengths are 2.72 Å. Both Cr(3)-Te(8) bond lengths are 2.72 Å. In the fourth Cr site, Cr(4) is bonded to one Te(6), one Te(8), two equivalent Te(2), and two equivalent Te(3) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The Cr(4)-Te(6) bond length is 2.70 Å. The Cr(4)-Te(8) bond length is 2.78 Å. Both Cr(4)-Te(2) bond lengths are 2.81 Å. Both Cr(4)-Te(3) bond lengths are 2.73 Å. In the fifth Cr site, Cr(5) is bonded to one Te(7), one Te(8), two equivalent Te(2), and two equivalent Te(4) atoms to form a mixture of face, corner, and edge-sharing CrTe6 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The Cr(5)-Te(7) bond length is 2.77 Å. The Cr(5)-Te(8) bond length is 2.74 Å. Both Cr(5)-Te(2) bond lengths are 2.87 Å. There is one shorter (2.72 Å) and one longer (2.73 Å) Cr(5)-Te(4) bond length. Tl(1) is bonded in a 5-coordinate geometry to one Te(8), two equivalent Te(3), and two equivalent Te(4) atoms. The Tl(1)-Te(8) bond length is 3.65 Å. There is one shorter (3.53 Å) and one longer (3.56 Å) Tl(1)-Te(3) bond length. There is one shorter (3.62 Å) and one longer (3.65 Å) Tl(1)-Te(4) bond length. There are eight inequivalent Te sites. In the first Te site, Te(1) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(2), and two equivalent Cr(3) atoms. In the second Te site, Te(2) is bonded to one Cr(1), two equivalent Cr(4), and two equivalent Cr(5) atoms to form distorted edge-sharing TeCr5 trigonal bipyramids. In the third Te site, Te(3) is bonded in a 3-coordinate geometry to one Cr(2), two equivalent Cr(4), and two equivalent Tl(1) atoms. In the fourth Te site, Te(4) is bonded in a 3-coordinate geometry to one Cr(3), two equivalent Cr(5), and two equivalent Tl(1) atoms. In the fifth Te site, Te(5) is bonded in a distorted T-shaped geometry to one Cr(3) and two equivalent Cr(1) atoms. In the sixth Te site, Te(6) is bonded in a distorted T-shaped geometry to one Cr(4) and two equivalent Cr(2) atoms. In the seventh Te site, Te(7) is bonded to one Cr(5), two equivalent Cr(1), and two equivalent Cr(2) atoms to form distorted edge-sharing TeCr5 trigonal bipyramids. In the eighth Te site, Te(8) is bonded in a rectangular see-saw-like geometry to one Cr(4), one Cr(5), two equivalent Cr(3), and one Tl(1) atom.