Tl2Ba2Ca2Cu3O10 crystallizes in the triclinic P1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(9), two equivalent O(6), two equivalent O(8), and four equivalent O(7) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and four equivalent O(2) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(10), two equivalent O(3), and two equivalent O(5) atoms. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to two equivalent O(10), two equivalent O(5), two equivalent O(6), and two equivalent O(8) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(6) and two equivalent O(8) atoms. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(10) and two equivalent O(5) atoms. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a see-saw-like geometry to one O(4), one O(7), and two equivalent O(9) atoms. In the second Tl site, Tl(2) is bonded in a see-saw-like geometry to one O(2), one O(9), and two equivalent O(4) atoms. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent Ca(1), and two equivalent Cu(1) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(10)Ca4Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-65°. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Ba(2) and one Tl(2) atom. In the third O site, O(3) is bonded to two equivalent Ba(2), two equivalent Ca(1), and two equivalent Cu(1) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(10)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-71°. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(2), one Tl(1), and two equivalent Tl(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form distorted OCa4Cu2 octahedra that share corners with two equivalent O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(6)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(8)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(6)Ba2Ca2Cu2 octahedra, edges with two equivalent O(5)Ca4Cu2 octahedra, and faces with four equivalent O(10)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-70°. In the sixth O site, O(6) is bonded to two equivalent Ba(1), two equivalent Ca(2), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(6)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(10)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(6)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(8)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-65°. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(1) atom. In the eighth O site, O(8) is bonded to two equivalent Ba(1), two equivalent Ca(2), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(8)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(10)Ca4Cu2 octahedra, edges with two equivalent O(8)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(6)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 4-70°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ba(1), one Tl(2), and two equivalent Tl(1) atoms. In the tenth O site, O(10) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form distorted OCa4Cu2 octahedra that share corners with two equivalent O(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(8)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, corners with four equivalent O(6)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(8)Ba2Ca2Cu2 octahedra, edges with two equivalent O(10)Ca4Cu2 octahedra, and faces with four equivalent O(5)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-71°.
Tl2Ba2Ca2Cu3O10 crystallizes in the triclinic P1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(9), two equivalent O(6), two equivalent O(8), and four equivalent O(7) atoms. The Ba(1)-O(9) bond length is 3.16 Å. There is one shorter (2.74 Å) and one longer (2.76 Å) Ba(1)-O(6) bond length. There is one shorter (2.85 Å) and one longer (2.90 Å) Ba(1)-O(8) bond length. There are a spread of Ba(1)-O(7) bond distances ranging from 2.84-2.90 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and four equivalent O(2) atoms. The Ba(2)-O(4) bond length is 3.16 Å. There is one shorter (2.74 Å) and one longer (2.78 Å) Ba(2)-O(1) bond length. There is one shorter (2.85 Å) and one longer (2.87 Å) Ba(2)-O(3) bond length. There are a spread of Ba(2)-O(2) bond distances ranging from 2.83-2.91 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(10), two equivalent O(3), and two equivalent O(5) atoms. There is one shorter (2.52 Å) and one longer (2.56 Å) Ca(1)-O(1) bond length. There is one shorter (2.48 Å) and one longer (2.49 Å) Ca(1)-O(10) bond length. There is one shorter (2.42 Å) and one longer (2.47 Å) Ca(1)-O(3) bond length. There is one shorter (2.51 Å) and one longer (2.78 Å) Ca(1)-O(5) bond length. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to two equivalent O(10), two equivalent O(5), two equivalent O(6), and two equivalent O(8) atoms. There is one shorter (2.57 Å) and one longer (2.72 Å) Ca(2)-O(10) bond length. There is one shorter (2.45 Å) and one longer (2.49 Å) Ca(2)-O(5) bond length. There is one shorter (2.52 Å) and one longer (2.57 Å) Ca(2)-O(6) bond length. There is one shorter (2.42 Å) and one longer (2.47 Å) Ca(2)-O(8) bond length. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. There is one shorter (1.94 Å) and one longer (1.95 Å) Cu(1)-O(1) bond length. Both Cu(1)-O(3) bond lengths are 1.95 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(6) and two equivalent O(8) atoms. Both Cu(2)-O(6) bond lengths are 1.95 Å. Both Cu(2)-O(8) bond lengths are 1.94 Å. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(10) and two equivalent O(5) atoms. There is one shorter (1.94 Å) and one longer (1.95 Å) Cu(3)-O(10) bond length. There is one shorter (1.95 Å) and one longer (1.96 Å) Cu(3)-O(5) bond length. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a see-saw-like geometry to one O(4), one O(7), and two equivalent O(9) atoms. The Tl(1)-O(4) bond length is 2.13 Å. The Tl(1)-O(7) bond length is 2.07 Å. There is one shorter (2.43 Å) and one longer (2.44 Å) Tl(1)-O(9) bond length. In the second Tl site, Tl(2) is bonded in a see-saw-like geometry to one O(2), one O(9), and two equivalent O(4) atoms. The Tl(2)-O(2) bond length is 2.07 Å. The Tl(2)-O(9) bond length is 2.14 Å. There is one shorter (2.43 Å) and one longer (2.44 Å) Tl(2)-O(4) bond length. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(2), two equivalent Ca(1), and two equivalent Cu(1) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(10)Ca4Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-65°. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Ba(2) and one Tl(2) atom. In the third O site, O(3) is bonded to two equivalent Ba(2), two equivalent Ca(1), and two equivalent Cu(1) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(10)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-71°. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Ba(2), one Tl(1), and two equivalent Tl(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form distorted OCa4Cu2 octahedra that share corners with two equivalent O(3)Ba2Ca2Cu2 octahedra, corners with two equivalent O(6)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(1)Ba2Ca2Cu2 octahedra, corners with four equivalent O(8)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(3)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(6)Ba2Ca2Cu2 octahedra, edges with two equivalent O(5)Ca4Cu2 octahedra, and faces with four equivalent O(10)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-70°. In the sixth O site, O(6) is bonded to two equivalent Ba(1), two equivalent Ca(2), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(6)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(10)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(6)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(8)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-65°. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(1) atom. In the eighth O site, O(8) is bonded to two equivalent Ba(1), two equivalent Ca(2), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(8)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(10)Ca4Cu2 octahedra, edges with two equivalent O(8)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(6)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 4-70°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Ba(1), one Tl(2), and two equivalent Tl(1) atoms. In the tenth O site, O(10) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form distorted OCa4Cu2 octahedra that share corners with two equivalent O(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(8)Ba2Ca2Cu2 octahedra, corners with two equivalent O(10)Ca4Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, corners with four equivalent O(6)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(8)Ba2Ca2Cu2 octahedra, edges with two equivalent O(10)Ca4Cu2 octahedra, and faces with four equivalent O(5)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-71°.