V4CrFe3O16 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-59°. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-59°. In the third V site, V(3) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. Cr(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. In the second Fe site, Fe(2) 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 FeO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Cr(1), and one Fe(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Fe(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(2) atom. In the sixth O site, O(6) is bonded to one V(3), one Cr(1), one Fe(1), and one Fe(2) atom to form distorted edge-sharing OVCrFe2 tetrahedra. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(1) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(3) and one Cr(1) atom.
V4CrFe3O16 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-59°. Both V(1)-O(2) bond lengths are 1.81 Å. Both V(1)-O(3) bond lengths are 1.70 Å. In the second V site, V(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra and corners with four equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-59°. Both V(2)-O(1) bond lengths are 1.81 Å. Both V(2)-O(4) bond lengths are 1.70 Å. In the third V site, V(3) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-63°. The V(3)-O(5) bond length is 1.73 Å. The V(3)-O(6) bond length is 1.87 Å. The V(3)-O(7) bond length is 1.70 Å. The V(3)-O(8) bond length is 1.70 Å. Cr(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. Both Cr(1)-O(2) bond lengths are 2.01 Å. Both Cr(1)-O(6) bond lengths are 2.11 Å. Both Cr(1)-O(8) bond lengths are 1.97 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.01 Å. Both Fe(1)-O(6) bond lengths are 2.17 Å. Both Fe(1)-O(7) bond lengths are 1.94 Å. In the second Fe site, Fe(2) 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 FeO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Fe(1)O6 octahedra. The Fe(2)-O(1) bond length is 2.08 Å. The Fe(2)-O(2) bond length is 2.08 Å. The Fe(2)-O(3) bond length is 1.98 Å. The Fe(2)-O(4) bond length is 1.98 Å. The Fe(2)-O(5) bond length is 1.94 Å. The Fe(2)-O(6) bond length is 2.14 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one Cr(1), and one Fe(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one Fe(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(2) atom. In the sixth O site, O(6) is bonded to one V(3), one Cr(1), one Fe(1), and one Fe(2) atom to form distorted edge-sharing OVCrFe2 tetrahedra. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(1) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(3) and one Cr(1) atom.