Zr(TlSe)4 is Orthorhombic Perovskite-like structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Se(1), one Se(10), one Se(6), one Se(8), and two equivalent Se(2) atoms to form edge-sharing ZrSe6 octahedra. In the second Zr site, Zr(2) is bonded to one Se(10), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(7) atom to form edge-sharing ZrSe6 octahedra. In the third Zr site, Zr(3) is bonded to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(9) atoms to form edge-sharing ZrSe6 octahedra. There are ten inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one Se(1), one Se(10), and one Se(5) atom. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one Se(2), one Se(6), and one Se(8) atom. In the third Tl site, Tl(3) is bonded in a distorted rectangular see-saw-like geometry to one Se(2), one Se(8), and two equivalent Se(1) atoms. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one Se(10), one Se(2), one Se(4), and one Se(9) atom. In the fifth Tl site, Tl(5) is bonded in a 4-coordinate geometry to one Se(1), one Se(5), one Se(6), and one Se(8) atom. In the sixth Tl site, Tl(6) is bonded in a 3-coordinate geometry to one Se(4), one Se(7), and one Se(9) atom. In the seventh Tl site, Tl(7) is bonded in a 5-coordinate geometry to one Se(2), one Se(7), one Se(8), and two equivalent Se(6) atoms. In the eighth Tl site, Tl(8) is bonded in a distorted rectangular see-saw-like geometry to one Se(10), one Se(5), one Se(7), and one Se(8) atom. In the ninth Tl site, Tl(9) is bonded in a 3-coordinate geometry to one Se(3), one Se(7), and one Se(9) atom. In the tenth Tl site, Tl(10) is bonded in a 5-coordinate geometry to one Se(10), one Se(5), one Se(9), and two equivalent Se(3) atoms. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to one Zr(1), one Tl(1), one Tl(5), and two equivalent Tl(3) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to two equivalent Zr(1), one Tl(2), one Tl(3), one Tl(4), and one Tl(7) atom. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Zr(2), one Zr(3), one Tl(9), and two equivalent Tl(10) atoms. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to one Zr(2), one Zr(3), one Tl(4), and one Tl(6) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Zr(2), one Tl(1), one Tl(10), one Tl(5), and one Tl(8) atom. In the sixth Se site, Se(6) is bonded in a 6-coordinate geometry to one Zr(1), one Zr(2), one Tl(2), one Tl(5), and two equivalent Tl(7) atoms. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Zr(2), one Tl(6), one Tl(7), one Tl(8), and one Tl(9) atom. In the eighth Se site, Se(8) is bonded in a 6-coordinate geometry to one Zr(1), one Tl(2), one Tl(3), one Tl(5), one Tl(7), and one Tl(8) atom. In the ninth Se site, Se(9) is bonded in a 5-coordinate geometry to one Zr(3), one Tl(10), one Tl(4), one Tl(6), and one Tl(9) atom. In the tenth Se site, Se(10) is bonded in a 6-coordinate geometry to one Zr(1), one Zr(2), one Tl(1), one Tl(10), one Tl(4), and one Tl(8) atom.
Zr(TlSe)4 is Orthorhombic Perovskite-like structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Se(1), one Se(10), one Se(6), one Se(8), and two equivalent Se(2) atoms to form edge-sharing ZrSe6 octahedra. The Zr(1)-Se(1) bond length is 2.67 Å. The Zr(1)-Se(10) bond length is 2.72 Å. The Zr(1)-Se(6) bond length is 2.79 Å. The Zr(1)-Se(8) bond length is 2.66 Å. There is one shorter (2.73 Å) and one longer (2.75 Å) Zr(1)-Se(2) bond length. In the second Zr site, Zr(2) is bonded to one Se(10), one Se(3), one Se(4), one Se(5), one Se(6), and one Se(7) atom to form edge-sharing ZrSe6 octahedra. The Zr(2)-Se(10) bond length is 2.76 Å. The Zr(2)-Se(3) bond length is 2.75 Å. The Zr(2)-Se(4) bond length is 2.81 Å. The Zr(2)-Se(5) bond length is 2.66 Å. The Zr(2)-Se(6) bond length is 2.73 Å. The Zr(2)-Se(7) bond length is 2.67 Å. In the third Zr site, Zr(3) is bonded to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(9) atoms to form edge-sharing ZrSe6 octahedra. Both Zr(3)-Se(3) bond lengths are 2.73 Å. Both Zr(3)-Se(4) bond lengths are 2.74 Å. Both Zr(3)-Se(9) bond lengths are 2.72 Å. There are ten inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to one Se(1), one Se(10), and one Se(5) atom. The Tl(1)-Se(1) bond length is 3.12 Å. The Tl(1)-Se(10) bond length is 3.21 Å. The Tl(1)-Se(5) bond length is 2.99 Å. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one Se(2), one Se(6), and one Se(8) atom. The Tl(2)-Se(2) bond length is 3.05 Å. The Tl(2)-Se(6) bond length is 3.13 Å. The Tl(2)-Se(8) bond length is 3.13 Å. In the third Tl site, Tl(3) is bonded in a distorted rectangular see-saw-like geometry to one Se(2), one Se(8), and two equivalent Se(1) atoms. The Tl(3)-Se(2) bond length is 3.28 Å. The Tl(3)-Se(8) bond length is 3.22 Å. There is one shorter (2.97 Å) and one longer (3.05 Å) Tl(3)-Se(1) bond length. In the fourth Tl site, Tl(4) is bonded in a 3-coordinate geometry to one Se(10), one Se(2), one Se(4), and one Se(9) atom. The Tl(4)-Se(10) bond length is 3.04 Å. The Tl(4)-Se(2) bond length is 3.34 Å. The Tl(4)-Se(4) bond length is 3.12 Å. The Tl(4)-Se(9) bond length is 3.09 Å. In the fifth Tl site, Tl(5) is bonded in a 4-coordinate geometry to one Se(1), one Se(5), one Se(6), and one Se(8) atom. The Tl(5)-Se(1) bond length is 3.09 Å. The Tl(5)-Se(5) bond length is 3.02 Å. The Tl(5)-Se(6) bond length is 3.02 Å. The Tl(5)-Se(8) bond length is 3.39 Å. In the sixth Tl site, Tl(6) is bonded in a 3-coordinate geometry to one Se(4), one Se(7), and one Se(9) atom. The Tl(6)-Se(4) bond length is 2.99 Å. The Tl(6)-Se(7) bond length is 3.11 Å. The Tl(6)-Se(9) bond length is 3.01 Å. In the seventh Tl site, Tl(7) is bonded in a 5-coordinate geometry to one Se(2), one Se(7), one Se(8), and two equivalent Se(6) atoms. The Tl(7)-Se(2) bond length is 3.22 Å. The Tl(7)-Se(7) bond length is 3.19 Å. The Tl(7)-Se(8) bond length is 2.99 Å. There is one shorter (3.33 Å) and one longer (3.39 Å) Tl(7)-Se(6) bond length. In the eighth Tl site, Tl(8) is bonded in a distorted rectangular see-saw-like geometry to one Se(10), one Se(5), one Se(7), and one Se(8) atom. The Tl(8)-Se(10) bond length is 3.30 Å. The Tl(8)-Se(5) bond length is 3.23 Å. The Tl(8)-Se(7) bond length is 2.96 Å. The Tl(8)-Se(8) bond length is 3.06 Å. In the ninth Tl site, Tl(9) is bonded in a 3-coordinate geometry to one Se(3), one Se(7), and one Se(9) atom. The Tl(9)-Se(3) bond length is 3.17 Å. The Tl(9)-Se(7) bond length is 3.01 Å. The Tl(9)-Se(9) bond length is 2.98 Å. In the tenth Tl site, Tl(10) is bonded in a 5-coordinate geometry to one Se(10), one Se(5), one Se(9), and two equivalent Se(3) atoms. The Tl(10)-Se(10) bond length is 3.33 Å. The Tl(10)-Se(5) bond length is 3.18 Å. The Tl(10)-Se(9) bond length is 3.14 Å. There is one shorter (3.02 Å) and one longer (3.42 Å) Tl(10)-Se(3) bond length. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to one Zr(1), one Tl(1), one Tl(5), and two equivalent Tl(3) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to two equivalent Zr(1), one Tl(2), one Tl(3), one Tl(4), and one Tl(7) atom. In the third Se site, Se(3) is bonded in a distorted rectangular see-saw-like geometry to one Zr(2), one Zr(3), one Tl(9), and two equivalent Tl(10) atoms. In the fourth Se site, Se(4) is bonded in a 4-coordinate geometry to one Zr(2), one Zr(3), one Tl(4), and one Tl(6) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Zr(2), one Tl(1), one Tl(10), one Tl(5), and one Tl(8) atom. In the sixth Se site, Se(6) is bonded in a 6-coordinate geometry to one Zr(1), one Zr(2), one Tl(2), one Tl(5), and two equivalent Tl(7) atoms. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Zr(2), one Tl(6), one Tl(7), one Tl(8), and one Tl(9) atom. In the eighth Se site, Se(8) is bonded in a 6-coordinate geometry to one Zr(1), one Tl(2), one Tl(3), one Tl(5), one Tl(7), and one Tl(8) atom. In the ninth Se site, Se(9) is bonded in a 5-coordinate geometry to one Zr(3), one Tl(10), one Tl(4), one Tl(6), and one Tl(9) atom. In the tenth Se site, Se(10) is bonded in a 6-coordinate geometry to one Zr(1), one Zr(2), one Tl(1), one Tl(10), one Tl(4), and one Tl(8) atom.