CaBa2Sm2Cu2Ti3O14 crystallizes in the tetragonal P4/mmm space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent O(2) and four equivalent O(4) atoms. Ca(1) is bonded in a body-centered cubic geometry to eight equivalent O(4) atoms. Sm(1) is bonded to four equivalent O(1), four equivalent O(3), and four equivalent O(5) atoms to form distorted SmO12 cuboctahedra that share corners with eight equivalent Sm(1)O12 cuboctahedra, faces with five equivalent Sm(1)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, and faces with eight equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedra are not tilted. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, and faces with four equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-24°. Cu(1) is bonded in a rectangular see-saw-like geometry to four equivalent O(4) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Sm(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to four equivalent Ba(1) and one Ti(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to four equivalent Sm(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(1) atoms to form a mixture of distorted corner, edge, and face-sharing OBa2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded in a linear geometry to four equivalent Sm(1) and two equivalent Ti(1) atoms.
CaBa2Sm2Cu2Ti3O14 crystallizes in the tetragonal P4/mmm space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent O(2) and four equivalent O(4) atoms. All Ba(1)-O(2) bond lengths are 2.91 Å. All Ba(1)-O(4) bond lengths are 2.75 Å. Ca(1) is bonded in a body-centered cubic geometry to eight equivalent O(4) atoms. All Ca(1)-O(4) bond lengths are 2.51 Å. Sm(1) is bonded to four equivalent O(1), four equivalent O(3), and four equivalent O(5) atoms to form distorted SmO12 cuboctahedra that share corners with eight equivalent Sm(1)O12 cuboctahedra, faces with five equivalent Sm(1)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. All Sm(1)-O(1) bond lengths are 2.49 Å. All Sm(1)-O(3) bond lengths are 2.76 Å. All Sm(1)-O(5) bond lengths are 2.90 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, and faces with eight equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Ti(1)-O(3) bond lengths are 1.92 Å. All Ti(1)-O(5) bond lengths are 1.94 Å. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form distorted TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, and faces with four equivalent Sm(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-24°. The Ti(2)-O(2) bond length is 1.78 Å. The Ti(2)-O(3) bond length is 2.19 Å. All Ti(2)-O(1) bond lengths are 1.99 Å. 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 1.95 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Sm(1) and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a distorted single-bond geometry to four equivalent Ba(1) and one Ti(2) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to four equivalent Sm(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to two equivalent Ba(1), two equivalent Ca(1), and two equivalent Cu(1) atoms to form a mixture of distorted corner, edge, and face-sharing OBa2Ca2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-66°. In the fifth O site, O(5) is bonded in a linear geometry to four equivalent Sm(1) and two equivalent Ti(1) atoms.