Tl5Cu14Se10 crystallizes in the monoclinic C2/m space group. There are seven inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to two equivalent Cu(4), one Se(4), and two equivalent Se(3) atoms. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one Se(2) and two equivalent Se(1) atoms. In the third Cu site, Cu(3) is bonded in a distorted trigonal non-coplanar geometry to one Se(3) and two equivalent Se(2) atoms. In the fourth Cu site, Cu(4) is bonded in a 9-coordinate geometry to one Cu(7), two equivalent Cu(1), two equivalent Cu(6), one Se(3), one Se(5), and two equivalent Se(4) atoms. In the fifth Cu site, Cu(5) is bonded in a 2-coordinate geometry to one Se(1) and three equivalent Se(2) atoms. In the sixth Cu site, Cu(6) is bonded to two equivalent Cu(4), one Se(4), and three equivalent Se(5) atoms to form distorted edge-sharing CuCu2Se4 tetrahedra. In the seventh Cu site, Cu(7) is bonded in a 3-coordinate geometry to one Cu(4), one Se(1), and two equivalent Se(4) atoms. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(5) atoms. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to two equivalent Se(2) and four equivalent Se(1) atoms. In the third Tl site, Tl(3) is bonded in a 4-coordinate geometry to four equivalent Se(3) atoms. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded in a 4-coordinate geometry to one Cu(5), one Cu(7), two equivalent Cu(2), and four equivalent Tl(2) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to one Cu(2), two equivalent Cu(3), three equivalent Cu(5), and two equivalent Tl(2) atoms. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one Cu(3), one Cu(4), two equivalent Cu(1), two equivalent Tl(1), and two equivalent Tl(3) atoms. In the fourth Se site, Se(4) is bonded in a 6-coordinate geometry to one Cu(1), one Cu(6), two equivalent Cu(4), two equivalent Cu(7), and two equivalent Tl(1) atoms. In the fifth Se site, Se(5) is bonded in a 6-coordinate geometry to one Cu(4), three equivalent Cu(6), and two equivalent Tl(1) atoms.
Tl5Cu14Se10 crystallizes in the monoclinic C2/m space group. There are seven inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to two equivalent Cu(4), one Se(4), and two equivalent Se(3) atoms. Both Cu(1)-Cu(4) bond lengths are 2.70 Å. The Cu(1)-Se(4) bond length is 2.49 Å. Both Cu(1)-Se(3) bond lengths are 2.47 Å. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one Se(2) and two equivalent Se(1) atoms. The Cu(2)-Se(2) bond length is 2.51 Å. Both Cu(2)-Se(1) bond lengths are 2.47 Å. In the third Cu site, Cu(3) is bonded in a distorted trigonal non-coplanar geometry to one Se(3) and two equivalent Se(2) atoms. The Cu(3)-Se(3) bond length is 2.38 Å. Both Cu(3)-Se(2) bond lengths are 2.51 Å. In the fourth Cu site, Cu(4) is bonded in a 9-coordinate geometry to one Cu(7), two equivalent Cu(1), two equivalent Cu(6), one Se(3), one Se(5), and two equivalent Se(4) atoms. The Cu(4)-Cu(7) bond length is 2.53 Å. Both Cu(4)-Cu(6) bond lengths are 2.71 Å. The Cu(4)-Se(3) bond length is 2.52 Å. The Cu(4)-Se(5) bond length is 2.40 Å. Both Cu(4)-Se(4) bond lengths are 2.69 Å. In the fifth Cu site, Cu(5) is bonded in a 2-coordinate geometry to one Se(1) and three equivalent Se(2) atoms. The Cu(5)-Se(1) bond length is 2.52 Å. There is one shorter (2.40 Å) and two longer (2.76 Å) Cu(5)-Se(2) bond lengths. In the sixth Cu site, Cu(6) is bonded to two equivalent Cu(4), one Se(4), and three equivalent Se(5) atoms to form distorted edge-sharing CuCu2Se4 tetrahedra. The Cu(6)-Se(4) bond length is 2.58 Å. There is one shorter (2.48 Å) and two longer (2.50 Å) Cu(6)-Se(5) bond lengths. In the seventh Cu site, Cu(7) is bonded in a 3-coordinate geometry to one Cu(4), one Se(1), and two equivalent Se(4) atoms. The Cu(7)-Se(1) bond length is 2.40 Å. Both Cu(7)-Se(4) bond lengths are 2.54 Å. There are three inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 6-coordinate geometry to two equivalent Se(3), two equivalent Se(4), and two equivalent Se(5) atoms. Both Tl(1)-Se(3) bond lengths are 3.36 Å. Both Tl(1)-Se(4) bond lengths are 3.40 Å. Both Tl(1)-Se(5) bond lengths are 3.27 Å. In the second Tl site, Tl(2) is bonded in a 6-coordinate geometry to two equivalent Se(2) and four equivalent Se(1) atoms. Both Tl(2)-Se(2) bond lengths are 3.42 Å. There are two shorter (3.34 Å) and two longer (3.39 Å) Tl(2)-Se(1) bond lengths. In the third Tl site, Tl(3) is bonded in a 4-coordinate geometry to four equivalent Se(3) atoms. All Tl(3)-Se(3) bond lengths are 3.37 Å. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded in a 4-coordinate geometry to one Cu(5), one Cu(7), two equivalent Cu(2), and four equivalent Tl(2) atoms. In the second Se site, Se(2) is bonded in a 6-coordinate geometry to one Cu(2), two equivalent Cu(3), three equivalent Cu(5), and two equivalent Tl(2) atoms. In the third Se site, Se(3) is bonded in a 4-coordinate geometry to one Cu(3), one Cu(4), two equivalent Cu(1), two equivalent Tl(1), and two equivalent Tl(3) atoms. In the fourth Se site, Se(4) is bonded in a 6-coordinate geometry to one Cu(1), one Cu(6), two equivalent Cu(4), two equivalent Cu(7), and two equivalent Tl(1) atoms. In the fifth Se site, Se(5) is bonded in a 6-coordinate geometry to one Cu(4), three equivalent Cu(6), and two equivalent Tl(1) atoms.