Ba4Ca4Cu6Tl3O19 crystallizes in the tetragonal I4/mmm 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(7), four equivalent O(1), and four equivalent O(6) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(5), four equivalent O(2), and four equivalent O(4) atoms. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a body-centered cubic geometry to four equivalent O(3) and four equivalent O(4) atoms. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to four equivalent O(4) atoms. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to four equivalent O(3) atoms. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to one O(2) and five equivalent O(5) atoms to form a mixture of distorted edge and corner-sharing TlO6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the second Tl site, Tl(2) is bonded to two equivalent O(6) and four equivalent O(7) atoms to form a mixture of distorted edge and corner-sharing TlO6 octahedra. The corner-sharing octahedra are not tilted. There are seven inequivalent O sites. In the first O site, O(1) 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(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(7)Ba2Tl4 octahedra, corners with six equivalent O(3)Ca4Cu2 octahedra,  an edgeedge with one O(3)Ca4Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Ba(2) and one Tl(1) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(3)Ca4Cu2 octahedra, corners with six equivalent O(1)Ba2Ca2Cu2 octahedra, corners with six equivalent O(4)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(4)Ba2Ca2Cu2 octahedra, edges with two equivalent O(3)Ca4Cu2 octahedra, and faces with four equivalent O(3)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fourth O site, O(4) 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(4)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)BaTl5 octahedra, corners with six equivalent O(3)Ca4Cu2 octahedra,  an edgeedge with one O(3)Ca4Cu2 octahedra, edges with two equivalent O(4)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(4)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded to one Ba(2) and five equivalent Tl(1) atoms to form distorted OBaTl5 octahedra that share corners with four equivalent O(4)Ba2Ca2Cu2 octahedra, corners with four equivalent O(5)BaTl5 octahedra, and edges with eight equivalent O(5)BaTl5 octahedra. The corner-sharing octahedral tilt angles range from 9-44°. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(2) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1) and four equivalent Tl(2) atoms to form OBa2Tl4 octahedra that share corners with four equivalent O(7)Ba2Tl4 octahedra, corners with eight equivalent O(1)Ba2Ca2Cu2 octahedra, and edges with four equivalent O(7)Ba2Tl4 octahedra. The corner-sharing octahedral tilt angles range from 0-41°.
Ba4Ca4Cu6Tl3O19 crystallizes in the tetragonal I4/mmm 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(7), four equivalent O(1), and four equivalent O(6) atoms. The Ba(1)-O(7) bond length is 2.71 Å. All Ba(1)-O(1) bond lengths are 2.96 Å. All Ba(1)-O(6) bond lengths are 2.80 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(5), four equivalent O(2), and four equivalent O(4) atoms. The Ba(2)-O(5) bond length is 3.08 Å. All Ba(2)-O(2) bond lengths are 2.86 Å. All Ba(2)-O(4) bond lengths are 2.76 Å. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a body-centered cubic geometry to four equivalent O(3) and four equivalent O(4) atoms. All Ca(1)-O(3) bond lengths are 2.50 Å. All Ca(1)-O(4) bond lengths are 2.50 Å. In the second Ca site, Ca(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Ca(2)-O(1) bond lengths are 2.42 Å. All Ca(2)-O(3) bond lengths are 2.59 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to four equivalent O(4) atoms. All Cu(1)-O(4) bond lengths are 1.93 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. All Cu(2)-O(1) bond lengths are 1.94 Å. In the third Cu site, Cu(3) is bonded in a rectangular see-saw-like geometry to four equivalent O(3) atoms. All Cu(3)-O(3) bond lengths are 1.93 Å. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to one O(2) and five equivalent O(5) atoms to form a mixture of distorted edge and corner-sharing TlO6 octahedra. The corner-sharing octahedral tilt angles are 9°. The Tl(1)-O(2) bond length is 2.03 Å. There is one shorter (2.08 Å) and four longer (2.74 Å) Tl(1)-O(5) bond lengths. In the second Tl site, Tl(2) is bonded to two equivalent O(6) and four equivalent O(7) atoms to form a mixture of distorted edge and corner-sharing TlO6 octahedra. The corner-sharing octahedra are not tilted. Both Tl(2)-O(6) bond lengths are 2.10 Å. All Tl(2)-O(7) bond lengths are 2.73 Å. There are seven inequivalent O sites. In the first O site, O(1) 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(1)Ba2Ca2Cu2 octahedra, corners with two equivalent O(7)Ba2Tl4 octahedra, corners with six equivalent O(3)Ca4Cu2 octahedra,  an edgeedge with one O(3)Ca4Cu2 octahedra, edges with two equivalent O(1)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(1)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-66°. In the second O site, O(2) is bonded in a 5-coordinate geometry to four equivalent Ba(2) and one Tl(1) atom. In the third O site, O(3) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Cu(3) atoms to form OCa4Cu2 octahedra that share corners with two equivalent O(3)Ca4Cu2 octahedra, corners with six equivalent O(1)Ba2Ca2Cu2 octahedra, corners with six equivalent O(4)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(1)Ba2Ca2Cu2 octahedra,  an edgeedge with one O(4)Ba2Ca2Cu2 octahedra, edges with two equivalent O(3)Ca4Cu2 octahedra, and faces with four equivalent O(3)Ca4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fourth O site, O(4) 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(4)Ba2Ca2Cu2 octahedra, corners with two equivalent O(5)BaTl5 octahedra, corners with six equivalent O(3)Ca4Cu2 octahedra,  an edgeedge with one O(3)Ca4Cu2 octahedra, edges with two equivalent O(4)Ba2Ca2Cu2 octahedra, and faces with four equivalent O(4)Ba2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded to one Ba(2) and five equivalent Tl(1) atoms to form distorted OBaTl5 octahedra that share corners with four equivalent O(4)Ba2Ca2Cu2 octahedra, corners with four equivalent O(5)BaTl5 octahedra, and edges with eight equivalent O(5)BaTl5 octahedra. The corner-sharing octahedral tilt angles range from 9-44°. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to four equivalent Ba(1) and one Tl(2) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1) and four equivalent Tl(2) atoms to form OBa2Tl4 octahedra that share corners with four equivalent O(7)Ba2Tl4 octahedra, corners with eight equivalent O(1)Ba2Ca2Cu2 octahedra, and edges with four equivalent O(7)Ba2Tl4 octahedra. The corner-sharing octahedral tilt angles range from 0-41°.