Tl4GeSe4 crystallizes in the monoclinic C2/c space group. There are five inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to two equivalent Se(1) and two equivalent Se(2) atoms. In the second Tl site, Tl(2) is bonded in a 1-coordinate geometry to one Se(1) atom. In the third Tl site, Tl(3) is bonded in a 5-coordinate geometry to one Se(1), one Se(2), one Se(3), and two equivalent Se(4) atoms. In the fourth Tl site, Tl(4) is bonded in a square co-planar geometry to two equivalent Se(1) and two equivalent Se(2) atoms. In the fifth Tl site, Tl(5) is bonded in a 4-coordinate geometry to two equivalent Se(3) and two equivalent Se(4) atoms. Ge(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(3), and one Se(4) atom. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 6-coordinate geometry to one Tl(2), one Tl(3), one Tl(4), two equivalent Tl(1), and one Ge(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to one Tl(3), one Tl(4), two equivalent Tl(1), and one Ge(1) atom. In the third Se site, Se(3) is bonded in a 2-coordinate geometry to one Tl(3), one Tl(5), and one Ge(1) atom. In the fourth Se site, Se(4) is bonded in a 2-coordinate geometry to one Tl(5), two equivalent Tl(3), and one Ge(1) atom.
Tl4GeSe4 crystallizes in the monoclinic C2/c space group. There are five inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to two equivalent Se(1) and two equivalent Se(2) atoms. There is one shorter (3.13 Å) and one longer (3.37 Å) Tl(1)-Se(1) bond length. There is one shorter (3.18 Å) and one longer (3.21 Å) Tl(1)-Se(2) bond length. In the second Tl site, Tl(2) is bonded in a 1-coordinate geometry to one Se(1) atom. The Tl(2)-Se(1) bond length is 3.08 Å. In the third Tl site, Tl(3) is bonded in a 5-coordinate geometry to one Se(1), one Se(2), one Se(3), and two equivalent Se(4) atoms. The Tl(3)-Se(1) bond length is 3.36 Å. The Tl(3)-Se(2) bond length is 3.22 Å. The Tl(3)-Se(3) bond length is 3.18 Å. There is one shorter (3.36 Å) and one longer (3.44 Å) Tl(3)-Se(4) bond length. In the fourth Tl site, Tl(4) is bonded in a square co-planar geometry to two equivalent Se(1) and two equivalent Se(2) atoms. Both Tl(4)-Se(1) bond lengths are 3.31 Å. Both Tl(4)-Se(2) bond lengths are 3.23 Å. In the fifth Tl site, Tl(5) is bonded in a 4-coordinate geometry to two equivalent Se(3) and two equivalent Se(4) atoms. Both Tl(5)-Se(3) bond lengths are 3.34 Å. Both Tl(5)-Se(4) bond lengths are 3.08 Å. Ge(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(3), and one Se(4) atom. The Ge(1)-Se(1) bond length is 2.40 Å. The Ge(1)-Se(2) bond length is 2.42 Å. The Ge(1)-Se(3) bond length is 2.39 Å. The Ge(1)-Se(4) bond length is 2.39 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a 6-coordinate geometry to one Tl(2), one Tl(3), one Tl(4), two equivalent Tl(1), and one Ge(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to one Tl(3), one Tl(4), two equivalent Tl(1), and one Ge(1) atom. In the third Se site, Se(3) is bonded in a 2-coordinate geometry to one Tl(3), one Tl(5), and one Ge(1) atom. In the fourth Se site, Se(4) is bonded in a 2-coordinate geometry to one Tl(5), two equivalent Tl(3), and one Ge(1) atom.