La2Cu2O5 crystallizes in the tetragonal P4_2/m space group. La(1) is bonded in a body-centered cubic geometry to two equivalent O(2) and six equivalent O(1) atoms. Cu(1) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent La(1) and two equivalent Cu(1) atoms to form distorted OLa3Cu2 trigonal bipyramids that share corners with four equivalent O(2)La4 tetrahedra, corners with eight equivalent O(1)La3Cu2 trigonal bipyramids,  an edgeedge with one O(2)La4 tetrahedra, edges with five equivalent O(1)La3Cu2 trigonal bipyramids, and  a faceface with one O(1)La3Cu2 trigonal bipyramid. In the second O site, O(2) is bonded to four equivalent La(1) atoms to form OLa4 tetrahedra that share corners with sixteen equivalent O(1)La3Cu2 trigonal bipyramids, edges with two equivalent O(2)La4 tetrahedra, and edges with four equivalent O(1)La3Cu2 trigonal bipyramids.
La2Cu2O5 crystallizes in the tetragonal P4_2/m space group. La(1) is bonded in a body-centered cubic geometry to two equivalent O(2) and six equivalent O(1) atoms. Both La(1)-O(2) bond lengths are 2.38 Å. There are a spread of La(1)-O(1) bond distances ranging from 2.47-2.71 Å. Cu(1) is bonded in a rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two shorter (1.99 Å) and two longer (2.01 Å) Cu(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent La(1) and two equivalent Cu(1) atoms to form distorted OLa3Cu2 trigonal bipyramids that share corners with four equivalent O(2)La4 tetrahedra, corners with eight equivalent O(1)La3Cu2 trigonal bipyramids,  an edgeedge with one O(2)La4 tetrahedra, edges with five equivalent O(1)La3Cu2 trigonal bipyramids, and  a faceface with one O(1)La3Cu2 trigonal bipyramid. In the second O site, O(2) is bonded to four equivalent La(1) atoms to form OLa4 tetrahedra that share corners with sixteen equivalent O(1)La3Cu2 trigonal bipyramids, edges with two equivalent O(2)La4 tetrahedra, and edges with four equivalent O(1)La3Cu2 trigonal bipyramids.