V3(FeO4)2 crystallizes in the hexagonal P6_3mc space group. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4) and three equivalent O(1) atoms to form FeO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. In the second Fe site, Fe(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Fe(1)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1), one Fe(1), and one Fe(2) atom to form distorted OV2Fe2 tetrahedra that share corners with two equivalent O(1)V2Fe2 tetrahedra,  a cornercorner with one O(4)V3Fe trigonal pyramid, edges with two equivalent O(1)V2Fe2 tetrahedra, and  an edgeedge with one O(4)V3Fe trigonal pyramid. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent V(1) and one Fe(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OV3Fe trigonal pyramids.
V3(FeO4)2 crystallizes in the hexagonal P6_3mc space group. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(4) bond length is 2.07 Å. Both V(1)-O(1) bond lengths are 2.09 Å. Both V(1)-O(2) bond lengths are 1.97 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4) and three equivalent O(1) atoms to form FeO4 tetrahedra that share corners with three equivalent Fe(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. The Fe(1)-O(4) bond length is 1.93 Å. All Fe(1)-O(1) bond lengths are 1.92 Å. In the second Fe site, Fe(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Fe(1)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. All Fe(2)-O(1) bond lengths are 2.17 Å. All Fe(2)-O(2) bond lengths are 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent V(1), one Fe(1), and one Fe(2) atom to form distorted OV2Fe2 tetrahedra that share corners with two equivalent O(1)V2Fe2 tetrahedra,  a cornercorner with one O(4)V3Fe trigonal pyramid, edges with two equivalent O(1)V2Fe2 tetrahedra, and  an edgeedge with one O(4)V3Fe trigonal pyramid. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent V(1) and one Fe(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OV3Fe trigonal pyramids.