GdBaCo2O5 crystallizes in the orthorhombic Pmmm space group. Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form distorted BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Ba(1)O12 cuboctahedra, and faces with eight equivalent Co(1)O5 trigonal bipyramids. Gd(1) is bonded in a body-centered cubic geometry to four equivalent O(2) and four equivalent O(3) atoms. Co(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO5 trigonal bipyramids that share corners with five equivalent Co(1)O5 trigonal bipyramids and faces with four equivalent Ba(1)O12 cuboctahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ba(1) and two equivalent Co(1) atoms to form a mixture of corner and edge-sharing OBa4Co2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Gd(1), and two equivalent Co(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent Gd(1), and two equivalent Co(1) atoms.
GdBaCo2O5 crystallizes in the orthorhombic Pmmm space group. Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form distorted BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Ba(1)O12 cuboctahedra, and faces with eight equivalent Co(1)O5 trigonal bipyramids. All Ba(1)-O(1) bond lengths are 2.78 Å. All Ba(1)-O(2) bond lengths are 3.04 Å. All Ba(1)-O(3) bond lengths are 3.14 Å. Gd(1) is bonded in a body-centered cubic geometry to four equivalent O(2) and four equivalent O(3) atoms. All Gd(1)-O(2) bond lengths are 2.42 Å. All Gd(1)-O(3) bond lengths are 2.46 Å. Co(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO5 trigonal bipyramids that share corners with five equivalent Co(1)O5 trigonal bipyramids and faces with four equivalent Ba(1)O12 cuboctahedra. The Co(1)-O(1) bond length is 1.96 Å. Both Co(1)-O(2) bond lengths are 2.05 Å. Both Co(1)-O(3) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Ba(1) and two equivalent Co(1) atoms to form a mixture of corner and edge-sharing OBa4Co2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent Ba(1), two equivalent Gd(1), and two equivalent Co(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent Gd(1), and two equivalent Co(1) atoms.