LiBa2SmCoCu2O7 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a distorted single-bond geometry to one O(1) and two equivalent O(3) 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(3) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to two equivalent O(2), two equivalent O(6), two equivalent O(7), and four equivalent O(4) atoms. Sm(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms. Co(1) is bonded in a square co-planar geometry to one O(3), one O(4), and two equivalent O(7) atoms. There are two 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(5) atoms. In the second Cu site, Cu(2) is bonded to one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted corner-sharing CuO5 square pyramids. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Sm(1), and two equivalent Cu(1) atoms to form distorted OLiSm2Cu2 trigonal bipyramids that share corners with two equivalent O(2)Ba2Sm2Cu2 octahedra, corners with four equivalent O(6)Ba2Sm2Cu2 octahedra, corners with four equivalent O(1)LiSm2Cu2 trigonal bipyramids, and  an edgeedge with one O(2)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-70°. In the second O site, O(2) is bonded to two equivalent Ba(2), two equivalent Sm(1), and two equivalent Cu(2) atoms to form distorted OBa2Sm2Cu2 octahedra that share corners with two equivalent O(2)Ba2Sm2Cu2 octahedra, corners with four equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(1)LiSm2Cu2 trigonal bipyramids, edges with two equivalent O(2)Ba2Sm2Cu2 octahedra,  an edgeedge with one O(1)LiSm2Cu2 trigonal bipyramid, and faces with four equivalent O(6)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-56°. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Li(1), four equivalent Ba(1), and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to four equivalent Ba(2), one Co(1), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a see-saw-like geometry to two equivalent Sm(1) and two equivalent Cu(1) atoms. In the sixth O site, O(6) is bonded to two equivalent Ba(2), two equivalent Sm(1), and two equivalent Cu(2) atoms to form distorted OBa2Sm2Cu2 octahedra that share corners with two equivalent O(6)Ba2Sm2Cu2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with four equivalent O(1)LiSm2Cu2 trigonal bipyramids,  an edgeedge with one O(7)Ba4Co2 octahedra, edges with two equivalent O(6)Ba2Sm2Cu2 octahedra, and faces with four equivalent O(2)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Co(1) atoms to form distorted OBa4Co2 octahedra that share corners with two equivalent O(6)Ba2Sm2Cu2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with four equivalent O(2)Ba2Sm2Cu2 octahedra,  an edgeedge with one O(6)Ba2Sm2Cu2 octahedra, and edges with two equivalent O(7)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-56°.
LiBa2SmCoCu2O7 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a distorted single-bond geometry to one O(1) and two equivalent O(3) atoms. The Li(1)-O(1) bond length is 1.74 Å. Both Li(1)-O(3) bond lengths are 2.59 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(3) atoms. Both Ba(1)-O(7) bond lengths are 2.56 Å. All Ba(1)-O(3) bond lengths are 2.79 Å. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to two equivalent O(2), two equivalent O(6), two equivalent O(7), and four equivalent O(4) atoms. Both Ba(2)-O(2) bond lengths are 2.94 Å. Both Ba(2)-O(6) bond lengths are 2.87 Å. Both Ba(2)-O(7) bond lengths are 2.97 Å. All Ba(2)-O(4) bond lengths are 2.83 Å. Sm(1) is bonded in a body-centered cubic geometry to two equivalent O(1), two equivalent O(2), two equivalent O(5), and two equivalent O(6) atoms. Both Sm(1)-O(1) bond lengths are 2.43 Å. Both Sm(1)-O(2) bond lengths are 2.52 Å. Both Sm(1)-O(5) bond lengths are 2.44 Å. Both Sm(1)-O(6) bond lengths are 2.44 Å. Co(1) is bonded in a square co-planar geometry to one O(3), one O(4), and two equivalent O(7) atoms. The Co(1)-O(3) bond length is 1.92 Å. The Co(1)-O(4) bond length is 1.75 Å. Both Co(1)-O(7) bond lengths are 2.02 Å. There are two 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(5) atoms. Both Cu(1)-O(1) bond lengths are 1.92 Å. Both Cu(1)-O(5) bond lengths are 2.02 Å. In the second Cu site, Cu(2) is bonded to one O(4), two equivalent O(2), and two equivalent O(6) atoms to form distorted corner-sharing CuO5 square pyramids. The Cu(2)-O(4) bond length is 2.57 Å. Both Cu(2)-O(2) bond lengths are 1.92 Å. Both Cu(2)-O(6) 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 Sm(1), and two equivalent Cu(1) atoms to form distorted OLiSm2Cu2 trigonal bipyramids that share corners with two equivalent O(2)Ba2Sm2Cu2 octahedra, corners with four equivalent O(6)Ba2Sm2Cu2 octahedra, corners with four equivalent O(1)LiSm2Cu2 trigonal bipyramids, and  an edgeedge with one O(2)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 3-70°. In the second O site, O(2) is bonded to two equivalent Ba(2), two equivalent Sm(1), and two equivalent Cu(2) atoms to form distorted OBa2Sm2Cu2 octahedra that share corners with two equivalent O(2)Ba2Sm2Cu2 octahedra, corners with four equivalent O(7)Ba4Co2 octahedra, corners with two equivalent O(1)LiSm2Cu2 trigonal bipyramids, edges with two equivalent O(2)Ba2Sm2Cu2 octahedra,  an edgeedge with one O(1)LiSm2Cu2 trigonal bipyramid, and faces with four equivalent O(6)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 5-56°. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Li(1), four equivalent Ba(1), and one Co(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to four equivalent Ba(2), one Co(1), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a see-saw-like geometry to two equivalent Sm(1) and two equivalent Cu(1) atoms. In the sixth O site, O(6) is bonded to two equivalent Ba(2), two equivalent Sm(1), and two equivalent Cu(2) atoms to form distorted OBa2Sm2Cu2 octahedra that share corners with two equivalent O(6)Ba2Sm2Cu2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with four equivalent O(1)LiSm2Cu2 trigonal bipyramids,  an edgeedge with one O(7)Ba4Co2 octahedra, edges with two equivalent O(6)Ba2Sm2Cu2 octahedra, and faces with four equivalent O(2)Ba2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. In the seventh O site, O(7) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Co(1) atoms to form distorted OBa4Co2 octahedra that share corners with two equivalent O(6)Ba2Sm2Cu2 octahedra, corners with two equivalent O(7)Ba4Co2 octahedra, corners with four equivalent O(2)Ba2Sm2Cu2 octahedra,  an edgeedge with one O(6)Ba2Sm2Cu2 octahedra, and edges with two equivalent O(7)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-56°.