Tl3PbCl5 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one Cl(2), one Cl(4), and one Cl(5) atom. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), one Cl(5), and two equivalent Cl(1) atoms. In the third Tl site, Tl(3) is bonded in a distorted L-shaped geometry to one Cl(2), two equivalent Cl(1), and two equivalent Cl(4) atoms. Pb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms to form distorted edge-sharing PbCl7 pentagonal bipyramids. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to two equivalent Tl(2), two equivalent Tl(3), and one Pb(1) atom. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Tl(1), one Tl(2), one Tl(3), and one Pb(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Tl(2) and one Pb(1) atom. In the fourth Cl site, Cl(4) is bonded in a 6-coordinate geometry to one Tl(1), one Tl(2), two equivalent Tl(3), and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded in a 3-coordinate geometry to one Tl(1), one Tl(2), and two equivalent Pb(1) atoms.
Tl3PbCl5 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one Cl(2), one Cl(4), and one Cl(5) atom. The Tl(1)-Cl(2) bond length is 3.21 Å. The Tl(1)-Cl(4) bond length is 3.18 Å. The Tl(1)-Cl(5) bond length is 3.15 Å. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), one Cl(5), and two equivalent Cl(1) atoms. The Tl(2)-Cl(2) bond length is 3.21 Å. The Tl(2)-Cl(3) bond length is 3.26 Å. The Tl(2)-Cl(4) bond length is 3.26 Å. The Tl(2)-Cl(5) bond length is 3.29 Å. There is one shorter (3.16 Å) and one longer (3.18 Å) Tl(2)-Cl(1) bond length. In the third Tl site, Tl(3) is bonded in a distorted L-shaped geometry to one Cl(2), two equivalent Cl(1), and two equivalent Cl(4) atoms. The Tl(3)-Cl(2) bond length is 3.08 Å. There is one shorter (3.09 Å) and one longer (3.25 Å) Tl(3)-Cl(1) bond length. There is one shorter (3.23 Å) and one longer (3.26 Å) Tl(3)-Cl(4) bond length. Pb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms to form distorted edge-sharing PbCl7 pentagonal bipyramids. The Pb(1)-Cl(1) bond length is 3.02 Å. The Pb(1)-Cl(2) bond length is 2.96 Å. The Pb(1)-Cl(3) bond length is 2.79 Å. There is one shorter (2.88 Å) and one longer (3.19 Å) Pb(1)-Cl(4) bond length. There is one shorter (3.00 Å) and one longer (3.16 Å) Pb(1)-Cl(5) bond length. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to two equivalent Tl(2), two equivalent Tl(3), and one Pb(1) atom. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Tl(1), one Tl(2), one Tl(3), and one Pb(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Tl(2) and one Pb(1) atom. In the fourth Cl site, Cl(4) is bonded in a 6-coordinate geometry to one Tl(1), one Tl(2), two equivalent Tl(3), and two equivalent Pb(1) atoms. In the fifth Cl site, Cl(5) is bonded in a 3-coordinate geometry to one Tl(1), one Tl(2), and two equivalent Pb(1) atoms.