Ba3CaLa2Cu6O13 crystallizes in the monoclinic Cm space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), and four equivalent O(7) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(2), one O(9), two equivalent O(3), and four equivalent O(7) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(9), two equivalent O(6), and four equivalent O(8) atoms. Ca(1) is bonded in a body-centered cubic geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one O(4), one O(5), one O(9), two equivalent O(6), and two equivalent O(8) atoms. In the second La site, La(2) is bonded in a body-centered cubic geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(7), and two equivalent O(3) atoms to form distorted corner-sharing CuO5 square pyramids. In the second Cu site, Cu(2) is bonded to one O(4), one O(5), one O(8), and two equivalent O(6) atoms to form corner-sharing CuO5 square pyramids. In the third Cu site, Cu(3) is bonded in a distorted T-shaped geometry to one O(7), one O(8), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(7) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Cu(1), and one Cu(3) atom. In the second O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Ba(3), one La(1), one Cu(2), and one Cu(3) atom. In the third O site, O(9) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), one La(1), and two equivalent Cu(3) atoms. In the fourth O site, O(1) is bonded to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms to form distorted OBa2CaLaCu2 octahedra that share corners with two equivalent O(2)Ba2CaLaCu2 octahedra, corners with four equivalent O(6)BaCaLa2Cu2 octahedra,  an edgeedge with one O(4)BaCaLa2Cu2 octahedra, and edges with two equivalent O(2)Ba2CaLaCu2 octahedra. The corner-sharing octahedral tilt angles range from 6-66°. In the fifth O site, O(2) is bonded to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms to form distorted OBa2CaLaCu2 octahedra that share corners with two equivalent O(1)Ba2CaLaCu2 octahedra, corners with two equivalent O(4)BaCaLa2Cu2 octahedra, corners with four equivalent O(6)BaCaLa2Cu2 octahedra, and edges with two equivalent O(1)Ba2CaLaCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the sixth O site, O(3) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms. In the seventh O site, O(4) is bonded to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms to form distorted OBaCaLa2Cu2 octahedra that share corners with two equivalent O(2)Ba2CaLaCu2 octahedra,  an edgeedge with one O(1)Ba2CaLaCu2 octahedra, and faces with four equivalent O(6)BaCaLa2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the eighth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms. In the ninth O site, O(6) is bonded to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms to form distorted OBaCaLa2Cu2 octahedra that share corners with two equivalent O(1)Ba2CaLaCu2 octahedra, corners with two equivalent O(2)Ba2CaLaCu2 octahedra, corners with two equivalent O(6)BaCaLa2Cu2 octahedra, edges with two equivalent O(6)BaCaLa2Cu2 octahedra, and faces with two equivalent O(4)BaCaLa2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-66°.
Ba3CaLa2Cu6O13 crystallizes in the monoclinic Cm space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), two equivalent O(3), and four equivalent O(7) atoms. The Ba(1)-O(1) bond length is 2.85 Å. The Ba(1)-O(2) bond length is 2.87 Å. Both Ba(1)-O(3) bond lengths are 2.91 Å. There are two shorter (2.75 Å) and two longer (2.91 Å) Ba(1)-O(7) bond lengths. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(1), one O(2), one O(9), two equivalent O(3), and four equivalent O(7) atoms. The Ba(2)-O(1) bond length is 2.87 Å. The Ba(2)-O(2) bond length is 2.96 Å. The Ba(2)-O(9) bond length is 3.12 Å. Both Ba(2)-O(3) bond lengths are 2.98 Å. There are two shorter (2.79 Å) and two longer (2.85 Å) Ba(2)-O(7) bond lengths. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one O(4), one O(5), one O(9), two equivalent O(6), and four equivalent O(8) atoms. The Ba(3)-O(4) bond length is 2.81 Å. The Ba(3)-O(5) bond length is 3.01 Å. The Ba(3)-O(9) bond length is 2.87 Å. Both Ba(3)-O(6) bond lengths are 2.90 Å. There are two shorter (2.80 Å) and two longer (2.86 Å) Ba(3)-O(8) bond lengths. Ca(1) is bonded in a body-centered cubic geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. The Ca(1)-O(1) bond length is 2.46 Å. The Ca(1)-O(2) bond length is 2.44 Å. The Ca(1)-O(4) bond length is 2.59 Å. The Ca(1)-O(5) bond length is 2.49 Å. Both Ca(1)-O(3) bond lengths are 2.45 Å. Both Ca(1)-O(6) bond lengths are 2.59 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 7-coordinate geometry to one O(4), one O(5), one O(9), two equivalent O(6), and two equivalent O(8) atoms. The La(1)-O(4) bond length is 2.60 Å. The La(1)-O(5) bond length is 2.62 Å. The La(1)-O(9) bond length is 2.64 Å. Both La(1)-O(6) bond lengths are 2.61 Å. Both La(1)-O(8) bond lengths are 2.40 Å. In the second La site, La(2) is bonded in a body-centered cubic geometry to one O(1), one O(2), one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms. The La(2)-O(1) bond length is 2.51 Å. The La(2)-O(2) bond length is 2.51 Å. The La(2)-O(4) bond length is 2.61 Å. The La(2)-O(5) bond length is 2.50 Å. Both La(2)-O(3) bond lengths are 2.50 Å. Both La(2)-O(6) bond lengths are 2.60 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(1), one O(2), one O(7), and two equivalent O(3) atoms to form distorted corner-sharing CuO5 square pyramids. The Cu(1)-O(1) bond length is 1.98 Å. The Cu(1)-O(2) bond length is 1.97 Å. The Cu(1)-O(7) bond length is 2.60 Å. Both Cu(1)-O(3) bond lengths are 1.95 Å. In the second Cu site, Cu(2) is bonded to one O(4), one O(5), one O(8), and two equivalent O(6) atoms to form corner-sharing CuO5 square pyramids. The Cu(2)-O(4) bond length is 1.98 Å. The Cu(2)-O(5) bond length is 1.97 Å. The Cu(2)-O(8) bond length is 2.40 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Cu(2)-O(6) bond length. In the third Cu site, Cu(3) is bonded in a distorted T-shaped geometry to one O(7), one O(8), and one O(9) atom. The Cu(3)-O(7) bond length is 1.82 Å. The Cu(3)-O(8) bond length is 1.84 Å. The Cu(3)-O(9) bond length is 1.94 Å. There are nine inequivalent O sites. In the first O site, O(7) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), one Cu(1), and one Cu(3) atom. In the second O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Ba(3), one La(1), one Cu(2), and one Cu(3) atom. In the third O site, O(9) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), one La(1), and two equivalent Cu(3) atoms. In the fourth O site, O(1) is bonded to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms to form distorted OBa2CaLaCu2 octahedra that share corners with two equivalent O(2)Ba2CaLaCu2 octahedra, corners with four equivalent O(6)BaCaLa2Cu2 octahedra,  an edgeedge with one O(4)BaCaLa2Cu2 octahedra, and edges with two equivalent O(2)Ba2CaLaCu2 octahedra. The corner-sharing octahedral tilt angles range from 6-66°. In the fifth O site, O(2) is bonded to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms to form distorted OBa2CaLaCu2 octahedra that share corners with two equivalent O(1)Ba2CaLaCu2 octahedra, corners with two equivalent O(4)BaCaLa2Cu2 octahedra, corners with four equivalent O(6)BaCaLa2Cu2 octahedra, and edges with two equivalent O(1)Ba2CaLaCu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the sixth O site, O(3) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ca(1), one La(2), and two equivalent Cu(1) atoms. In the seventh O site, O(4) is bonded to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms to form distorted OBaCaLa2Cu2 octahedra that share corners with two equivalent O(2)Ba2CaLaCu2 octahedra,  an edgeedge with one O(1)Ba2CaLaCu2 octahedra, and faces with four equivalent O(6)BaCaLa2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the eighth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms. In the ninth O site, O(6) is bonded to one Ba(3), one Ca(1), one La(1), one La(2), and two equivalent Cu(2) atoms to form distorted OBaCaLa2Cu2 octahedra that share corners with two equivalent O(1)Ba2CaLaCu2 octahedra, corners with two equivalent O(2)Ba2CaLaCu2 octahedra, corners with two equivalent O(6)BaCaLa2Cu2 octahedra, edges with two equivalent O(6)BaCaLa2Cu2 octahedra, and faces with two equivalent O(4)BaCaLa2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-66°.