La3FeO6 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent La sites. In the first La site, La(1) is bonded to one O(4), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LaO7 pentagonal bipyramids that share  a cornercorner with one La(2)O7 hexagonal pyramid, corners with four equivalent La(1)O7 pentagonal bipyramids, corners with three equivalent Fe(1)O4 tetrahedra, edges with three equivalent La(2)O7 hexagonal pyramids, edges with two equivalent La(1)O7 pentagonal bipyramids,  an edgeedge with one Fe(1)O4 tetrahedra, and  a faceface with one La(1)O7 pentagonal bipyramid. In the second La site, La(2) is bonded to one O(4), two equivalent O(2), and four equivalent O(1) atoms to form distorted LaO7 hexagonal pyramids that share corners with two equivalent La(1)O7 pentagonal bipyramids,  a cornercorner with one Fe(1)O4 tetrahedra, edges with two equivalent La(2)O7 hexagonal pyramids, edges with six equivalent La(1)O7 pentagonal bipyramids, and  an edgeedge with one Fe(1)O4 tetrahedra. Fe(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form FeO4 tetrahedra that share  a cornercorner with one La(2)O7 hexagonal pyramid, corners with six equivalent La(1)O7 pentagonal bipyramids,  an edgeedge with one La(2)O7 hexagonal pyramid, and edges with two equivalent La(1)O7 pentagonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with two equivalent O(1)La4 tetrahedra, corners with four equivalent O(4)La3Fe tetrahedra, corners with six equivalent O(2)La3Fe trigonal pyramids, edges with three equivalent O(1)La4 tetrahedra, and  an edgeedge with one O(2)La3Fe trigonal pyramid. In the second O site, O(2) is bonded to one La(2), two equivalent La(1), and one Fe(1) atom to form distorted OLa3Fe trigonal pyramids that share corners with two equivalent O(4)La3Fe tetrahedra, corners with six equivalent O(1)La4 tetrahedra, corners with two equivalent O(2)La3Fe trigonal pyramids,  an edgeedge with one O(4)La3Fe tetrahedra,  an edgeedge with one O(1)La4 tetrahedra, and  an edgeedge with one O(2)La3Fe trigonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to four equivalent La(1) and one Fe(1) atom. In the fourth O site, O(4) is bonded to one La(2), two equivalent La(1), and one Fe(1) atom to form distorted OLa3Fe tetrahedra that share corners with eight equivalent O(1)La4 tetrahedra, corners with four equivalent O(2)La3Fe trigonal pyramids, and edges with two equivalent O(2)La3Fe trigonal pyramids.
La3FeO6 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent La sites. In the first La site, La(1) is bonded to one O(4), two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LaO7 pentagonal bipyramids that share  a cornercorner with one La(2)O7 hexagonal pyramid, corners with four equivalent La(1)O7 pentagonal bipyramids, corners with three equivalent Fe(1)O4 tetrahedra, edges with three equivalent La(2)O7 hexagonal pyramids, edges with two equivalent La(1)O7 pentagonal bipyramids,  an edgeedge with one Fe(1)O4 tetrahedra, and  a faceface with one La(1)O7 pentagonal bipyramid. The La(1)-O(4) bond length is 2.51 Å. There is one shorter (2.34 Å) and one longer (2.37 Å) La(1)-O(1) bond length. There is one shorter (2.43 Å) and one longer (2.51 Å) La(1)-O(2) bond length. There is one shorter (2.72 Å) and one longer (2.73 Å) La(1)-O(3) bond length. In the second La site, La(2) is bonded to one O(4), two equivalent O(2), and four equivalent O(1) atoms to form distorted LaO7 hexagonal pyramids that share corners with two equivalent La(1)O7 pentagonal bipyramids,  a cornercorner with one Fe(1)O4 tetrahedra, edges with two equivalent La(2)O7 hexagonal pyramids, edges with six equivalent La(1)O7 pentagonal bipyramids, and  an edgeedge with one Fe(1)O4 tetrahedra. The La(2)-O(4) bond length is 2.54 Å. Both La(2)-O(2) bond lengths are 2.60 Å. All La(2)-O(1) bond lengths are 2.42 Å. Fe(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form FeO4 tetrahedra that share  a cornercorner with one La(2)O7 hexagonal pyramid, corners with six equivalent La(1)O7 pentagonal bipyramids,  an edgeedge with one La(2)O7 hexagonal pyramid, and edges with two equivalent La(1)O7 pentagonal bipyramids. The Fe(1)-O(3) bond length is 1.89 Å. The Fe(1)-O(4) bond length is 1.89 Å. Both Fe(1)-O(2) bond lengths are 1.89 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(1) and two equivalent La(2) atoms to form OLa4 tetrahedra that share corners with two equivalent O(1)La4 tetrahedra, corners with four equivalent O(4)La3Fe tetrahedra, corners with six equivalent O(2)La3Fe trigonal pyramids, edges with three equivalent O(1)La4 tetrahedra, and  an edgeedge with one O(2)La3Fe trigonal pyramid. In the second O site, O(2) is bonded to one La(2), two equivalent La(1), and one Fe(1) atom to form distorted OLa3Fe trigonal pyramids that share corners with two equivalent O(4)La3Fe tetrahedra, corners with six equivalent O(1)La4 tetrahedra, corners with two equivalent O(2)La3Fe trigonal pyramids,  an edgeedge with one O(4)La3Fe tetrahedra,  an edgeedge with one O(1)La4 tetrahedra, and  an edgeedge with one O(2)La3Fe trigonal pyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to four equivalent La(1) and one Fe(1) atom. In the fourth O site, O(4) is bonded to one La(2), two equivalent La(1), and one Fe(1) atom to form distorted OLa3Fe tetrahedra that share corners with eight equivalent O(1)La4 tetrahedra, corners with four equivalent O(2)La3Fe trigonal pyramids, and edges with two equivalent O(2)La3Fe trigonal pyramids.