CaFe3O5 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the second Fe site, Fe(2) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles range from 8-49°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted OCa2Fe3 trigonal bipyramids that share corners with four equivalent O(2)CaFe5 octahedra, corners with four equivalent O(3)Ca2Fe2 tetrahedra, corners with three equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with five equivalent O(2)CaFe5 octahedra,  an edgeedge with one O(3)Ca2Fe2 tetrahedra, and edges with three equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-41°. In the second O site, O(2) is bonded to one Ca(1), two equivalent Fe(1), and three equivalent Fe(2) atoms to form distorted OCaFe5 octahedra that share corners with three equivalent O(2)CaFe5 octahedra,  a cornercorner with one O(3)Ca2Fe2 tetrahedra, corners with four equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with five equivalent O(2)CaFe5 octahedra, edges with two equivalent O(3)Ca2Fe2 tetrahedra, and edges with five equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-56°. In the third O site, O(3) is bonded to two equivalent Ca(1) and two equivalent Fe(2) atoms to form distorted OCa2Fe2 tetrahedra that share corners with two equivalent O(2)CaFe5 octahedra, corners with two equivalent O(3)Ca2Fe2 tetrahedra, corners with eight equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with four equivalent O(2)CaFe5 octahedra, and edges with two equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 2°.
CaFe3O5 crystallizes in the orthorhombic Cmcm space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(3), and four equivalent O(1) atoms. Both Ca(1)-O(2) bond lengths are 2.87 Å. Both Ca(1)-O(3) bond lengths are 2.30 Å. All Ca(1)-O(1) bond lengths are 2.44 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both Fe(1)-O(1) bond lengths are 2.03 Å. All Fe(1)-O(2) bond lengths are 2.27 Å. In the second Fe site, Fe(2) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles range from 8-49°. The Fe(2)-O(3) bond length is 1.97 Å. Both Fe(2)-O(1) bond lengths are 2.08 Å. There are two shorter (2.08 Å) and one longer (2.21 Å) Fe(2)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), one Fe(1), and two equivalent Fe(2) atoms to form distorted OCa2Fe3 trigonal bipyramids that share corners with four equivalent O(2)CaFe5 octahedra, corners with four equivalent O(3)Ca2Fe2 tetrahedra, corners with three equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with five equivalent O(2)CaFe5 octahedra,  an edgeedge with one O(3)Ca2Fe2 tetrahedra, and edges with three equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-41°. In the second O site, O(2) is bonded to one Ca(1), two equivalent Fe(1), and three equivalent Fe(2) atoms to form distorted OCaFe5 octahedra that share corners with three equivalent O(2)CaFe5 octahedra,  a cornercorner with one O(3)Ca2Fe2 tetrahedra, corners with four equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with five equivalent O(2)CaFe5 octahedra, edges with two equivalent O(3)Ca2Fe2 tetrahedra, and edges with five equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-56°. In the third O site, O(3) is bonded to two equivalent Ca(1) and two equivalent Fe(2) atoms to form distorted OCa2Fe2 tetrahedra that share corners with two equivalent O(2)CaFe5 octahedra, corners with two equivalent O(3)Ca2Fe2 tetrahedra, corners with eight equivalent O(1)Ca2Fe3 trigonal bipyramids, edges with four equivalent O(2)CaFe5 octahedra, and edges with two equivalent O(1)Ca2Fe3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 2°.