CaFe2O5 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Fe(1) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing FeO5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and two equivalent Fe(1) atoms to form OCa2Fe2 tetrahedra that share corners with two equivalent O(1)Ca2Fe2 tetrahedra, corners with two equivalent O(2)CaFe3 trigonal pyramids, and edges with four equivalent O(2)CaFe3 trigonal pyramids. In the second O site, O(2) is bonded to one Ca(1) and three equivalent Fe(1) atoms to form distorted OCaFe3 trigonal pyramids that share  a cornercorner with one O(1)Ca2Fe2 tetrahedra, corners with three equivalent O(2)CaFe3 trigonal pyramids, edges with two equivalent O(1)Ca2Fe2 tetrahedra, and edges with two equivalent O(2)CaFe3 trigonal pyramids. In the third O site, O(3) is bonded in a linear geometry to one Ca(1) and one Fe(1) atom.
CaFe2O5 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Ca(1)-O(1) bond lengths are 2.26 Å. Both Ca(1)-O(2) bond lengths are 2.50 Å. Both Ca(1)-O(3) bond lengths are 2.26 Å. Fe(1) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing FeO5 trigonal bipyramids. The Fe(1)-O(1) bond length is 1.94 Å. The Fe(1)-O(3) bond length is 1.82 Å. There is one shorter (1.98 Å) and two longer (2.04 Å) Fe(1)-O(2) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1) and two equivalent Fe(1) atoms to form OCa2Fe2 tetrahedra that share corners with two equivalent O(1)Ca2Fe2 tetrahedra, corners with two equivalent O(2)CaFe3 trigonal pyramids, and edges with four equivalent O(2)CaFe3 trigonal pyramids. In the second O site, O(2) is bonded to one Ca(1) and three equivalent Fe(1) atoms to form distorted OCaFe3 trigonal pyramids that share  a cornercorner with one O(1)Ca2Fe2 tetrahedra, corners with three equivalent O(2)CaFe3 trigonal pyramids, edges with two equivalent O(1)Ca2Fe2 tetrahedra, and edges with two equivalent O(2)CaFe3 trigonal pyramids. In the third O site, O(3) is bonded in a linear geometry to one Ca(1) and one Fe(1) atom.