Tl2Ba2Ca2Cu3O10 crystallizes in the orthorhombic Imm2 space group. Ba(1) is bonded in a 9-coordinate geometry to one O(6), two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. Ca(1) is bonded in a body-centered cubic geometry to two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Tl(1) is bonded in a see-saw-like geometry to one O(1) and three equivalent O(6) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(2)Ba2Ca2Cu2 octahedra, corners with two equivalent O(4)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(4)Ca4Cu2 octahedra, edges with two equivalent O(2)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 1-66°. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(2) 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(4)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(2)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 1-66°. In the fourth O site, O(4) is bonded to four equivalent Ca(1) and two equivalent Cu(1) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(4)Ca4Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with eight equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(2)Ba2Ca2Cu2 octahedra, edges with two equivalent O(4)Ca4Cu2 octahedra, and faces with four equivalent O(5)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded to four equivalent Ca(1) and two equivalent Cu(1) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, corners with eight equivalent O(2)Ba2Ca2Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(5)Ca4Cu2 octahedra, and faces with four equivalent O(4)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ba(1) and three equivalent Tl(1) atoms.
Tl2Ba2Ca2Cu3O10 crystallizes in the orthorhombic Imm2 space group. Ba(1) is bonded in a 9-coordinate geometry to one O(6), two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. The Ba(1)-O(6) bond length is 3.09 Å. There is one shorter (2.78 Å) and one longer (2.80 Å) Ba(1)-O(2) bond length. Both Ba(1)-O(3) bond lengths are 2.78 Å. There are two shorter (2.84 Å) and two longer (2.88 Å) Ba(1)-O(1) bond lengths. Ca(1) is bonded in a body-centered cubic geometry to two equivalent O(2), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Both Ca(1)-O(2) bond lengths are 2.49 Å. Both Ca(1)-O(3) bond lengths are 2.49 Å. Both Ca(1)-O(4) bond lengths are 2.54 Å. Both Ca(1)-O(5) bond lengths are 2.54 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Cu(1)-O(4) bond lengths are 1.94 Å. Both Cu(1)-O(5) 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(2) and two equivalent O(3) atoms. Both Cu(2)-O(2) bond lengths are 1.94 Å. Both Cu(2)-O(3) bond lengths are 1.95 Å. Tl(1) is bonded in a see-saw-like geometry to one O(1) and three equivalent O(6) atoms. The Tl(1)-O(1) bond length is 2.06 Å. There is one shorter (2.13 Å) and two longer (2.46 Å) Tl(1)-O(6) bond lengths. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(2) atoms to form distorted OBa2Ca2Cu2 octahedra that share corners with two equivalent O(2)Ba2Ca2Cu2 octahedra, corners with two equivalent O(4)Ca4Cu2 octahedra, corners with four equivalent O(5)Ca4Cu2 octahedra,  an edgeedge with one O(4)Ca4Cu2 octahedra, edges with two equivalent O(2)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(3)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 1-66°. In the third O site, O(3) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(2) 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(4)Ca4Cu2 octahedra,  an edgeedge with one O(5)Ca4Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(2)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 1-66°. In the fourth O site, O(4) is bonded to four equivalent Ca(1) and two equivalent Cu(1) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(4)Ca4Cu2 octahedra, corners with four equivalent O(2)Ba2Ca2Cu2 octahedra, corners with eight equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(2)Ba2Ca2Cu2 octahedra, edges with two equivalent O(4)Ca4Cu2 octahedra, and faces with four equivalent O(5)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded to four equivalent Ca(1) and two equivalent Cu(1) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(5)Ca4Cu2 octahedra, corners with four equivalent O(3)Ba2Ca2Cu2 octahedra, corners with eight equivalent O(2)Ba2Ca2Cu2 octahedra, edges with two equivalent O(3)Ba2Ca2Cu2 octahedra, edges with two equivalent O(5)Ca4Cu2 octahedra, and faces with four equivalent O(4)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ba(1) and three equivalent Tl(1) atoms.