GaFeO3 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted FeO6 octahedra that share corners with four equivalent Fe(2)O6 octahedra, corners with four equivalent Ga(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with three equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. In the second Fe site, Fe(2) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form distorted FeO6 octahedra that share corners with two equivalent Ga(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one Ga(1)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form GaO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Ga(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, and corners with two equivalent Ga(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-67°. In the second Ga site, Ga(2) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form GaO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Ga(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Ga(2)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Ga(1) atoms. In the second O site, O(2) is bonded to one Fe(1), one Ga(1), and two equivalent Ga(2) atoms to form distorted OGa3Fe tetrahedra that share  a cornercorner with one O(3)Ga2Fe3 square pyramid, corners with two equivalent O(4)Ga2Fe2 tetrahedra, corners with two equivalent O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, and  an edgeedge with one O(4)Ga2Fe2 tetrahedra. In the third O site, O(3) is bonded to one Fe(1), two equivalent Fe(2), and two equivalent Ga(2) atoms to form distorted OGa2Fe3 square pyramids that share  a cornercorner with one O(4)Ga2Fe2 tetrahedra,  a cornercorner with one O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, edges with two equivalent O(4)Ga2Fe2 tetrahedra, and edges with two equivalent O(2)Ga3Fe tetrahedra. In the fourth O site, O(4) is bonded to one Fe(1), one Fe(2), one Ga(1), and one Ga(2) atom to form OGa2Fe2 tetrahedra that share  a cornercorner with one O(3)Ga2Fe3 square pyramid, corners with two equivalent O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, and  an edgeedge with one O(2)Ga3Fe tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Ga(2) atom.
GaFeO3 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted FeO6 octahedra that share corners with four equivalent Fe(2)O6 octahedra, corners with four equivalent Ga(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with three equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. The Fe(1)-O(1) bond length is 2.01 Å. The Fe(1)-O(2) bond length is 2.15 Å. The Fe(1)-O(3) bond length is 2.34 Å. The Fe(1)-O(4) bond length is 2.09 Å. The Fe(1)-O(5) bond length is 1.93 Å. The Fe(1)-O(6) bond length is 1.96 Å. In the second Fe site, Fe(2) is bonded to one O(4), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form distorted FeO6 octahedra that share corners with two equivalent Ga(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra,  a cornercorner with one Ga(1)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-59°. The Fe(2)-O(4) bond length is 2.11 Å. The Fe(2)-O(6) bond length is 1.95 Å. There is one shorter (2.12 Å) and one longer (2.41 Å) Fe(2)-O(3) bond length. There is one shorter (1.97 Å) and one longer (1.98 Å) Fe(2)-O(5) bond length. There are two inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form GaO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Ga(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, and corners with two equivalent Ga(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-67°. The Ga(1)-O(2) bond length is 1.89 Å. The Ga(1)-O(4) bond length is 1.87 Å. There is one shorter (1.85 Å) and one longer (1.87 Å) Ga(1)-O(1) bond length. In the second Ga site, Ga(2) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form GaO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Ga(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, edges with two equivalent Ga(2)O6 octahedra, and edges with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-49°. The Ga(2)-O(4) bond length is 2.06 Å. The Ga(2)-O(6) bond length is 1.91 Å. There is one shorter (2.03 Å) and one longer (2.06 Å) Ga(2)-O(2) bond length. There is one shorter (2.00 Å) and one longer (2.08 Å) Ga(2)-O(3) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Ga(1) atoms. In the second O site, O(2) is bonded to one Fe(1), one Ga(1), and two equivalent Ga(2) atoms to form distorted OGa3Fe tetrahedra that share  a cornercorner with one O(3)Ga2Fe3 square pyramid, corners with two equivalent O(4)Ga2Fe2 tetrahedra, corners with two equivalent O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, and  an edgeedge with one O(4)Ga2Fe2 tetrahedra. In the third O site, O(3) is bonded to one Fe(1), two equivalent Fe(2), and two equivalent Ga(2) atoms to form distorted OGa2Fe3 square pyramids that share  a cornercorner with one O(4)Ga2Fe2 tetrahedra,  a cornercorner with one O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, edges with two equivalent O(4)Ga2Fe2 tetrahedra, and edges with two equivalent O(2)Ga3Fe tetrahedra. In the fourth O site, O(4) is bonded to one Fe(1), one Fe(2), one Ga(1), and one Ga(2) atom to form OGa2Fe2 tetrahedra that share  a cornercorner with one O(3)Ga2Fe3 square pyramid, corners with two equivalent O(2)Ga3Fe tetrahedra, edges with two equivalent O(3)Ga2Fe3 square pyramids, and  an edgeedge with one O(2)Ga3Fe tetrahedra. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Ga(2) atom.