Ba2Sm(CuO2)3 crystallizes in the tetragonal P4/mmm space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. Sm(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2) and four equivalent O(1) atoms to form distorted corner-sharing CuO5 square pyramids. In the second Cu site, Cu(2) is bonded in a linear geometry to two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(1), two equivalent Sm(1), and two equivalent Cu(1) atoms to form a mixture of distorted face, corner, and edge-sharing OBa2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-68°. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Ba(1), one Cu(1), and one Cu(2) atom.
Ba2Sm(CuO2)3 crystallizes in the tetragonal P4/mmm space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. All Ba(1)-O(1) bond lengths are 2.94 Å. All Ba(1)-O(2) bond lengths are 2.82 Å. Sm(1) is bonded in a body-centered cubic geometry to eight equivalent O(1) atoms. All Sm(1)-O(1) bond lengths are 2.47 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one O(2) and four equivalent O(1) atoms to form distorted corner-sharing CuO5 square pyramids. The Cu(1)-O(2) bond length is 2.60 Å. All Cu(1)-O(1) bond lengths are 1.96 Å. In the second Cu site, Cu(2) is bonded in a linear geometry to two equivalent O(2) atoms. Both Cu(2)-O(2) bond lengths are 1.81 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ba(1), two equivalent Sm(1), and two equivalent Cu(1) atoms to form a mixture of distorted face, corner, and edge-sharing OBa2Sm2Cu2 octahedra. The corner-sharing octahedral tilt angles range from 0-68°. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Ba(1), one Cu(1), and one Cu(2) atom.