Tl3PbBr5 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and 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 2-coordinate geometry to one Br(4), two equivalent Br(3), and two equivalent Br(5) atoms. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one Br(1), one Br(2), one Br(3), one Br(4), and two equivalent Br(5) atoms. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one Br(2), one Br(3), and one Br(4) atom. Pb(1) is bonded to one Br(1), one Br(4), one Br(5), two equivalent Br(2), and two equivalent Br(3) atoms to form distorted edge-sharing PbBr7 pentagonal bipyramids. There are five inequivalent Br sites. In the first Br site, Br(5) is bonded in a 5-coordinate geometry to two equivalent Tl(1), two equivalent Tl(2), and one Pb(1) atom. In the second Br site, Br(1) is bonded in a 1-coordinate geometry to one Tl(2) and one Pb(1) atom. In the third Br site, Br(2) is bonded in a distorted rectangular see-saw-like geometry to one Tl(2), one Tl(3), and two equivalent Pb(1) atoms. In the fourth Br site, Br(3) is bonded to one Tl(2), one Tl(3), two equivalent Tl(1), and two equivalent Pb(1) atoms to form distorted corner-sharing BrTl4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 40-45°. In the fifth Br site, Br(4) is bonded in a see-saw-like geometry to one Tl(1), one Tl(2), one Tl(3), and one Pb(1) atom.
Tl3PbBr5 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and 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 2-coordinate geometry to one Br(4), two equivalent Br(3), and two equivalent Br(5) atoms. The Tl(1)-Br(4) bond length is 3.23 Å. There is one shorter (3.36 Å) and one longer (3.42 Å) Tl(1)-Br(3) bond length. There is one shorter (3.23 Å) and one longer (3.42 Å) Tl(1)-Br(5) bond length. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to one Br(1), one Br(2), one Br(3), one Br(4), and two equivalent Br(5) atoms. The Tl(2)-Br(1) bond length is 3.38 Å. The Tl(2)-Br(2) bond length is 3.40 Å. The Tl(2)-Br(3) bond length is 3.36 Å. The Tl(2)-Br(4) bond length is 3.32 Å. There is one shorter (3.32 Å) and one longer (3.33 Å) Tl(2)-Br(5) bond length. In the third Tl site, Tl(3) is bonded in a 3-coordinate geometry to one Br(2), one Br(3), and one Br(4) atom. The Tl(3)-Br(2) bond length is 3.31 Å. The Tl(3)-Br(3) bond length is 3.31 Å. The Tl(3)-Br(4) bond length is 3.34 Å. Pb(1) is bonded to one Br(1), one Br(4), one Br(5), two equivalent Br(2), and two equivalent Br(3) atoms to form distorted edge-sharing PbBr7 pentagonal bipyramids. The Pb(1)-Br(1) bond length is 2.93 Å. The Pb(1)-Br(4) bond length is 3.12 Å. The Pb(1)-Br(5) bond length is 3.14 Å. There is one shorter (3.18 Å) and one longer (3.30 Å) Pb(1)-Br(2) bond length. There is one shorter (3.02 Å) and one longer (3.32 Å) Pb(1)-Br(3) bond length. There are five inequivalent Br sites. In the first Br site, Br(5) is bonded in a 5-coordinate geometry to two equivalent Tl(1), two equivalent Tl(2), and one Pb(1) atom. In the second Br site, Br(1) is bonded in a 1-coordinate geometry to one Tl(2) and one Pb(1) atom. In the third Br site, Br(2) is bonded in a distorted rectangular see-saw-like geometry to one Tl(2), one Tl(3), and two equivalent Pb(1) atoms. In the fourth Br site, Br(3) is bonded to one Tl(2), one Tl(3), two equivalent Tl(1), and two equivalent Pb(1) atoms to form distorted corner-sharing BrTl4Pb2 octahedra. The corner-sharing octahedral tilt angles range from 40-45°. In the fifth Br site, Br(4) is bonded in a see-saw-like geometry to one Tl(1), one Tl(2), one Tl(3), and one Pb(1) atom.