Tl4Sn5S12 crystallizes in the triclinic P-1 space group. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 2-coordinate geometry to one S(3) and one S(4) atom. In the second Tl site, Tl(2) is bonded in a single-bond geometry to one S(10) atom. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(6) atom. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one S(10) and two equivalent S(11) atoms. There are five inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), one S(6), and two equivalent S(1) atoms. In the second Sn site, Sn(2) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form corner-sharing SnS4 tetrahedra. In the third Sn site, Sn(3) is bonded to one S(3), one S(5), one S(7), and one S(9) atom to form SnS4 tetrahedra that share  a cornercorner with one Sn(4)S6 octahedra,  a cornercorner with one Sn(5)S6 octahedra, and  a cornercorner with one Sn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 73°. In the fourth Sn site, Sn(4) is bonded to one S(10), one S(11), one S(12), one S(9), and two equivalent S(8) atoms to form SnS6 octahedra that share  a cornercorner with one Sn(3)S4 tetrahedra,  an edgeedge with one Sn(4)S6 octahedra, and edges with three equivalent Sn(5)S6 octahedra. In the fifth Sn site, Sn(5) is bonded to one S(10), one S(11), one S(7), one S(8), and two equivalent S(12) atoms to form SnS6 octahedra that share  a cornercorner with one Sn(3)S4 tetrahedra,  an edgeedge with one Sn(5)S6 octahedra, and edges with three equivalent Sn(4)S6 octahedra. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Tl(3) and two equivalent Sn(1) atoms. In the second S site, S(2) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Tl(1), one Sn(1), and one Sn(3) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Tl(1), one Tl(3), one Sn(1), and one Sn(2) atom. In the fifth S site, S(5) is bonded in a water-like geometry to one Sn(2) and one Sn(3) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Tl(3), one Sn(1), and one Sn(2) atom. In the seventh S site, S(7) is bonded in a water-like geometry to one Sn(3) and one Sn(5) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Sn(5) and two equivalent Sn(4) atoms. In the ninth S site, S(9) is bonded in a water-like geometry to one Sn(3) and one Sn(4) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Tl(2), one Tl(4), one Sn(4), and one Sn(5) atom. In the eleventh S site, S(11) is bonded in a distorted L-shaped geometry to two equivalent Tl(4), one Sn(4), and one Sn(5) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Sn(4) and two equivalent Sn(5) atoms.
Tl4Sn5S12 crystallizes in the triclinic P-1 space group. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 2-coordinate geometry to one S(3) and one S(4) atom. The Tl(1)-S(3) bond length is 3.15 Å. The Tl(1)-S(4) bond length is 3.11 Å. In the second Tl site, Tl(2) is bonded in a single-bond geometry to one S(10) atom. The Tl(2)-S(10) bond length is 3.02 Å. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(6) atom. The Tl(3)-S(1) bond length is 3.16 Å. The Tl(3)-S(4) bond length is 3.10 Å. The Tl(3)-S(6) bond length is 3.16 Å. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one S(10) and two equivalent S(11) atoms. The Tl(4)-S(10) bond length is 3.26 Å. There is one shorter (3.20 Å) and one longer (3.27 Å) Tl(4)-S(11) bond length. There are five inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), one S(6), and two equivalent S(1) atoms. The Sn(1)-S(2) bond length is 2.50 Å. The Sn(1)-S(3) bond length is 2.57 Å. The Sn(1)-S(4) bond length is 3.11 Å. The Sn(1)-S(6) bond length is 2.65 Å. There is one shorter (2.51 Å) and one longer (2.52 Å) Sn(1)-S(1) bond length. In the second Sn site, Sn(2) is bonded to one S(2), one S(4), one S(5), and one S(6) atom to form corner-sharing SnS4 tetrahedra. The Sn(2)-S(2) bond length is 2.42 Å. The Sn(2)-S(4) bond length is 2.39 Å. The Sn(2)-S(5) bond length is 2.47 Å. The Sn(2)-S(6) bond length is 2.44 Å. In the third Sn site, Sn(3) is bonded to one S(3), one S(5), one S(7), and one S(9) atom to form SnS4 tetrahedra that share  a cornercorner with one Sn(4)S6 octahedra,  a cornercorner with one Sn(5)S6 octahedra, and  a cornercorner with one Sn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles are 73°. The Sn(3)-S(3) bond length is 2.43 Å. The Sn(3)-S(5) bond length is 2.44 Å. The Sn(3)-S(7) bond length is 2.43 Å. The Sn(3)-S(9) bond length is 2.43 Å. In the fourth Sn site, Sn(4) is bonded to one S(10), one S(11), one S(12), one S(9), and two equivalent S(8) atoms to form SnS6 octahedra that share  a cornercorner with one Sn(3)S4 tetrahedra,  an edgeedge with one Sn(4)S6 octahedra, and edges with three equivalent Sn(5)S6 octahedra. The Sn(4)-S(10) bond length is 2.58 Å. The Sn(4)-S(11) bond length is 2.55 Å. The Sn(4)-S(12) bond length is 2.60 Å. The Sn(4)-S(9) bond length is 2.62 Å. There is one shorter (2.63 Å) and one longer (2.64 Å) Sn(4)-S(8) bond length. In the fifth Sn site, Sn(5) is bonded to one S(10), one S(11), one S(7), one S(8), and two equivalent S(12) atoms to form SnS6 octahedra that share  a cornercorner with one Sn(3)S4 tetrahedra,  an edgeedge with one Sn(5)S6 octahedra, and edges with three equivalent Sn(4)S6 octahedra. The Sn(5)-S(10) bond length is 2.58 Å. The Sn(5)-S(11) bond length is 2.57 Å. The Sn(5)-S(7) bond length is 2.60 Å. The Sn(5)-S(8) bond length is 2.62 Å. There is one shorter (2.61 Å) and one longer (2.64 Å) Sn(5)-S(12) bond length. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Tl(3) and two equivalent Sn(1) atoms. In the second S site, S(2) is bonded in a water-like geometry to one Sn(1) and one Sn(2) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Tl(1), one Sn(1), and one Sn(3) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Tl(1), one Tl(3), one Sn(1), and one Sn(2) atom. In the fifth S site, S(5) is bonded in a water-like geometry to one Sn(2) and one Sn(3) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Tl(3), one Sn(1), and one Sn(2) atom. In the seventh S site, S(7) is bonded in a water-like geometry to one Sn(3) and one Sn(5) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Sn(5) and two equivalent Sn(4) atoms. In the ninth S site, S(9) is bonded in a water-like geometry to one Sn(3) and one Sn(4) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Tl(2), one Tl(4), one Sn(4), and one Sn(5) atom. In the eleventh S site, S(11) is bonded in a distorted L-shaped geometry to two equivalent Tl(4), one Sn(4), and one Sn(5) atom. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to one Sn(4) and two equivalent Sn(5) atoms.