V3Fe2CuO12 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-62°. In the second V site, V(2) is bonded to one O(12), one O(4), one O(6), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-48°. In the third V site, V(3) is bonded to one O(10), one O(11), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and  a cornercorner with one Cu(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-60°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), one O(6), one O(9), and two equivalent O(10) atoms 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 Fe(1)O6 octahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(12), one O(2), one O(5), one O(8), and two equivalent O(11) atoms to form distorted FeO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. Cu(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one Fe(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one Fe(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(1), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(2), and one Cu(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one Fe(1), and one Cu(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(3), one Fe(2), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent Fe(1) atoms. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(3) and two equivalent Fe(2) atoms. In the twelfth O site, O(12) is bonded in a linear geometry to one V(2) and one Fe(2) atom.
V3Fe2CuO12 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 20-62°. The V(1)-O(1) bond length is 1.69 Å. The V(1)-O(2) bond length is 1.70 Å. The V(1)-O(3) bond length is 1.85 Å. The V(1)-O(5) bond length is 1.82 Å. In the second V site, V(2) is bonded to one O(12), one O(4), one O(6), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent Cu(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-48°. The V(2)-O(12) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.74 Å. The V(2)-O(6) bond length is 1.76 Å. The V(2)-O(9) bond length is 1.73 Å. In the third V site, V(3) is bonded to one O(10), one O(11), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and  a cornercorner with one Cu(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 45-60°. The V(3)-O(10) bond length is 1.78 Å. The V(3)-O(11) bond length is 1.81 Å. The V(3)-O(7) bond length is 1.62 Å. The V(3)-O(8) bond length is 1.82 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), one O(6), one O(9), and two equivalent O(10) atoms 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 Fe(1)O6 octahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Fe(1)-O(1) bond length is 2.01 Å. The Fe(1)-O(3) bond length is 2.10 Å. The Fe(1)-O(6) bond length is 1.99 Å. The Fe(1)-O(9) bond length is 1.94 Å. There is one shorter (1.99 Å) and one longer (2.15 Å) Fe(1)-O(10) bond length. In the second Fe site, Fe(2) is bonded to one O(12), one O(2), one O(5), one O(8), and two equivalent O(11) atoms to form distorted FeO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Cu(1)O5 trigonal bipyramid. The Fe(2)-O(12) bond length is 1.92 Å. The Fe(2)-O(2) bond length is 2.00 Å. The Fe(2)-O(5) bond length is 2.15 Å. The Fe(2)-O(8) bond length is 1.99 Å. There is one shorter (1.97 Å) and one longer (2.19 Å) Fe(2)-O(11) bond length. Cu(1) is bonded to one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted CuO5 trigonal bipyramids that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The Cu(1)-O(3) bond length is 1.90 Å. The Cu(1)-O(4) bond length is 1.82 Å. The Cu(1)-O(5) bond length is 1.90 Å. The Cu(1)-O(6) bond length is 2.37 Å. The Cu(1)-O(8) bond length is 1.90 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one Fe(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one Fe(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(1), and one Cu(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one Cu(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one Fe(2), and one Cu(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(2), one Fe(1), and one Cu(1) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one V(3) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one V(3), one Fe(2), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent Fe(1) atoms. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(3) and two equivalent Fe(2) atoms. In the twelfth O site, O(12) is bonded in a linear geometry to one V(2) and one Fe(2) atom.