Zn3Fe4V6O24 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(12), one O(6), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Zn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 47-58°. In the second V site, V(2) is bonded to one O(10), one O(3), one O(4), and one O(7) 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 Zn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-63°. In the third V site, V(3) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Zn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-51°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(2), one O(6), one O(7), and two equivalent O(9) atoms to form FeO6 octahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(3), one O(4), one O(5), one O(8), and two equivalent O(1) 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(2)O6 octahedra, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a square co-planar geometry to two equivalent O(10) and two equivalent O(12) atoms. In the second Zn site, Zn(2) is bonded to one O(11), one O(4), one O(6), one O(7), and one O(8) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one 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 Fe(2)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one Fe(2), and one Zn(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 in a distorted trigonal planar geometry to one V(1), one Fe(1), and one Zn(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Fe(1), and one Zn(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one Fe(2), and one Zn(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Fe(1) atoms. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one V(2), one Fe(1), and one Zn(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one V(3) and one Zn(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(1) atom.
Zn3Fe4V6O24 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(12), one O(6), and one O(9) atom to form VO4 tetrahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Zn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 47-58°. The V(1)-O(1) bond length is 1.78 Å. The V(1)-O(12) bond length is 1.68 Å. The V(1)-O(6) bond length is 1.76 Å. The V(1)-O(9) bond length is 1.80 Å. In the second V site, V(2) is bonded to one O(10), one O(3), one O(4), and one O(7) 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 Zn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-63°. The V(2)-O(10) bond length is 1.79 Å. The V(2)-O(3) bond length is 1.69 Å. The V(2)-O(4) bond length is 1.77 Å. The V(2)-O(7) bond length is 1.76 Å. In the third V site, V(3) is bonded to one O(11), one O(2), one O(5), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Zn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 22-51°. The V(3)-O(11) bond length is 1.74 Å. The V(3)-O(2) bond length is 1.73 Å. The V(3)-O(5) bond length is 1.72 Å. The V(3)-O(8) bond length is 1.80 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(2), one O(6), one O(7), and two equivalent O(9) atoms to form FeO6 octahedra that share  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. The Fe(1)-O(10) bond length is 2.07 Å. The Fe(1)-O(2) bond length is 1.91 Å. The Fe(1)-O(6) bond length is 2.03 Å. The Fe(1)-O(7) bond length is 2.09 Å. There is one shorter (2.05 Å) and one longer (2.10 Å) Fe(1)-O(9) bond length. In the second Fe site, Fe(2) is bonded to one O(3), one O(4), one O(5), one O(8), and two equivalent O(1) 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(2)O6 octahedra, and  an edgeedge with one Zn(2)O5 trigonal bipyramid. The Fe(2)-O(3) bond length is 1.99 Å. The Fe(2)-O(4) bond length is 2.00 Å. The Fe(2)-O(5) bond length is 1.95 Å. The Fe(2)-O(8) bond length is 2.08 Å. There is one shorter (2.01 Å) and one longer (2.14 Å) Fe(2)-O(1) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a square co-planar geometry to two equivalent O(10) and two equivalent O(12) atoms. Both Zn(1)-O(10) bond lengths are 2.15 Å. Both Zn(1)-O(12) bond lengths are 1.99 Å. In the second Zn site, Zn(2) is bonded to one O(11), one O(4), one O(6), one O(7), and one O(8) atom to form ZnO5 trigonal bipyramids that share  a cornercorner with one 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 Fe(2)O6 octahedra. The Zn(2)-O(11) bond length is 1.97 Å. The Zn(2)-O(4) bond length is 2.15 Å. The Zn(2)-O(6) bond length is 2.10 Å. The Zn(2)-O(7) bond length is 2.05 Å. The Zn(2)-O(8) bond length is 2.04 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(3) and one Fe(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Fe(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one V(2), one Fe(2), and one Zn(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 in a distorted trigonal planar geometry to one V(1), one Fe(1), and one Zn(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Fe(1), and one Zn(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one Fe(2), and one Zn(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Fe(1) atoms. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one V(2), one Fe(1), and one Zn(1) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one V(3) and one Zn(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(1) atom.