Fe3O4 is Spinel-derived structured and crystallizes in the orthorhombic Pmma space group. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form corner-sharing FeO4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the second Fe site, Fe(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form corner-sharing FeO4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Fe(2)O4 tetrahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with four equivalent Fe(5)O6 octahedra. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent Fe(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, edges with two equivalent Fe(4)O6 octahedra, and edges with four equivalent Fe(5)O6 octahedra. In the fifth Fe site, Fe(5) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form FeO6 octahedra that share corners with three equivalent Fe(1)O4 tetrahedra, corners with three equivalent Fe(2)O4 tetrahedra, edges with two equivalent Fe(3)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, and edges with two equivalent Fe(5)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(3), and two equivalent Fe(5) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Fe(2), one Fe(4), and two equivalent Fe(5) atoms. In the third O site, O(3) is bonded to one Fe(2), one Fe(5), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing OFe4 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(5), and two equivalent Fe(4) atoms.
Fe3O4 is Spinel-derived structured and crystallizes in the orthorhombic Pmma space group. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form corner-sharing FeO4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. Both Fe(1)-O(1) bond lengths are 1.96 Å. Both Fe(1)-O(4) bond lengths are 1.92 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form corner-sharing FeO4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-60°. Both Fe(2)-O(2) bond lengths are 1.90 Å. Both Fe(2)-O(3) bond lengths are 1.97 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with two equivalent Fe(1)O4 tetrahedra, corners with four equivalent Fe(2)O4 tetrahedra, edges with two equivalent Fe(3)O6 octahedra, and edges with four equivalent Fe(5)O6 octahedra. Both Fe(3)-O(1) bond lengths are 2.04 Å. All Fe(3)-O(3) bond lengths are 2.06 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent Fe(2)O4 tetrahedra, corners with four equivalent Fe(1)O4 tetrahedra, edges with two equivalent Fe(4)O6 octahedra, and edges with four equivalent Fe(5)O6 octahedra. Both Fe(4)-O(2) bond lengths are 2.18 Å. All Fe(4)-O(4) bond lengths are 2.14 Å. In the fifth Fe site, Fe(5) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form FeO6 octahedra that share corners with three equivalent Fe(1)O4 tetrahedra, corners with three equivalent Fe(2)O4 tetrahedra, edges with two equivalent Fe(3)O6 octahedra, edges with two equivalent Fe(4)O6 octahedra, and edges with two equivalent Fe(5)O6 octahedra. The Fe(5)-O(3) bond length is 2.12 Å. The Fe(5)-O(4) bond length is 2.04 Å. Both Fe(5)-O(1) bond lengths are 2.15 Å. Both Fe(5)-O(2) bond lengths are 2.07 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(3), and two equivalent Fe(5) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Fe(2), one Fe(4), and two equivalent Fe(5) atoms. In the third O site, O(3) is bonded to one Fe(2), one Fe(5), and two equivalent Fe(3) atoms to form a mixture of distorted edge and corner-sharing OFe4 trigonal pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(5), and two equivalent Fe(4) atoms.