LiBa2TmCu3O7 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(6) atoms. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 6-coordinate geometry to two equivalent O(7) and four equivalent O(6) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to two equivalent O(3), two equivalent O(5), two equivalent O(7), and four equivalent O(2) atoms. Tm(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted corner-sharing CuO5 square pyramids. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(4) atoms. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(2), one O(6), and two equivalent O(7) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Tm(1), and two equivalent Cu(2) atoms to form distorted OLiTm2Cu2 trigonal bipyramids that share corners with four equivalent O(5)Ba2Tm2Cu2 octahedra and corners with four equivalent O(1)LiTm2Cu2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 70°. In the second O site, O(2) is bonded to four equivalent Ba(2), one Cu(1), and one Cu(3) atom to form distorted OBa4Cu2 octahedra that share corners with four equivalent O(5)Ba2Tm2Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra, corners with four equivalent O(7)Ba4Cu2 octahedra, edges with four equivalent O(2)Ba4Cu2 octahedra, faces with two equivalent O(5)Ba2Tm2Cu2 octahedra, and faces with two equivalent O(7)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 17-71°. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ba(2), two equivalent Tm(1), and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a see-saw-like geometry to two equivalent Tm(1) and two equivalent Cu(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Ba(2), two equivalent Tm(1), and two equivalent Cu(1) atoms to form distorted OBa2Tm2Cu2 octahedra that share corners with two equivalent O(5)Ba2Tm2Cu2 octahedra, corners with two equivalent O(7)Ba4Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra, corners with four equivalent O(1)LiTm2Cu2 trigonal bipyramids,  an edgeedge with one O(7)Ba4Cu2 octahedra, edges with two equivalent O(5)Ba2Tm2Cu2 octahedra, and faces with two equivalent O(2)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. In the sixth O site, O(6) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Ba(1), and one Cu(3) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Cu(3) atoms to form distorted OBa4Cu2 octahedra that share corners with two equivalent O(5)Ba2Tm2Cu2 octahedra, corners with two equivalent O(7)Ba4Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra,  an edgeedge with one O(5)Ba2Tm2Cu2 octahedra, edges with two equivalent O(7)Ba4Cu2 octahedra, and faces with two equivalent O(2)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°.
LiBa2TmCu3O7 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a 3-coordinate geometry to one O(1) and two equivalent O(6) atoms. The Li(1)-O(1) bond length is 1.82 Å. Both Li(1)-O(6) bond lengths are 2.45 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 6-coordinate geometry to two equivalent O(7) and four equivalent O(6) atoms. Both Ba(1)-O(7) bond lengths are 2.58 Å. All Ba(1)-O(6) bond lengths are 2.79 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to two equivalent O(3), two equivalent O(5), two equivalent O(7), and four equivalent O(2) atoms. Both Ba(2)-O(3) bond lengths are 3.08 Å. Both Ba(2)-O(5) bond lengths are 2.91 Å. Both Ba(2)-O(7) bond lengths are 2.93 Å. All Ba(2)-O(2) bond lengths are 2.79 Å. Tm(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms. Both Tm(1)-O(1) bond lengths are 2.43 Å. Both Tm(1)-O(3) bond lengths are 2.44 Å. Both Tm(1)-O(4) bond lengths are 2.32 Å. Both Tm(1)-O(5) bond lengths are 2.39 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted corner-sharing CuO5 square pyramids. The Cu(1)-O(2) bond length is 2.43 Å. Both Cu(1)-O(3) bond lengths are 1.91 Å. Both Cu(1)-O(5) bond lengths are 2.03 Å. In the second Cu site, Cu(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(4) atoms. Both Cu(2)-O(1) bond lengths are 1.88 Å. Both Cu(2)-O(4) bond lengths are 2.02 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to one O(2), one O(6), and two equivalent O(7) atoms. The Cu(3)-O(2) bond length is 1.87 Å. The Cu(3)-O(6) bond length is 2.14 Å. Both Cu(3)-O(7) bond lengths are 2.02 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Tm(1), and two equivalent Cu(2) atoms to form distorted OLiTm2Cu2 trigonal bipyramids that share corners with four equivalent O(5)Ba2Tm2Cu2 octahedra and corners with four equivalent O(1)LiTm2Cu2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 70°. In the second O site, O(2) is bonded to four equivalent Ba(2), one Cu(1), and one Cu(3) atom to form distorted OBa4Cu2 octahedra that share corners with four equivalent O(5)Ba2Tm2Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra, corners with four equivalent O(7)Ba4Cu2 octahedra, edges with four equivalent O(2)Ba4Cu2 octahedra, faces with two equivalent O(5)Ba2Tm2Cu2 octahedra, and faces with two equivalent O(7)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 17-71°. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ba(2), two equivalent Tm(1), and two equivalent Cu(1) atoms. In the fourth O site, O(4) is bonded in a see-saw-like geometry to two equivalent Tm(1) and two equivalent Cu(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Ba(2), two equivalent Tm(1), and two equivalent Cu(1) atoms to form distorted OBa2Tm2Cu2 octahedra that share corners with two equivalent O(5)Ba2Tm2Cu2 octahedra, corners with two equivalent O(7)Ba4Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra, corners with four equivalent O(1)LiTm2Cu2 trigonal bipyramids,  an edgeedge with one O(7)Ba4Cu2 octahedra, edges with two equivalent O(5)Ba2Tm2Cu2 octahedra, and faces with two equivalent O(2)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. In the sixth O site, O(6) is bonded in a 7-coordinate geometry to two equivalent Li(1), four equivalent Ba(1), and one Cu(3) atom. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Cu(3) atoms to form distorted OBa4Cu2 octahedra that share corners with two equivalent O(5)Ba2Tm2Cu2 octahedra, corners with two equivalent O(7)Ba4Cu2 octahedra, corners with four equivalent O(2)Ba4Cu2 octahedra,  an edgeedge with one O(5)Ba2Tm2Cu2 octahedra, edges with two equivalent O(7)Ba4Cu2 octahedra, and faces with two equivalent O(2)Ba4Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-71°.