V4Fe2HO12 crystallizes in the monoclinic P2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(4)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the second V site, V(2) is bonded to one O(10), one O(12), one O(4), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. In the third V site, V(3) is bonded to one O(1), one O(11), one O(3), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(2), one O(4), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(11), one O(2), one O(3), one O(5), and one O(9) atom to form FeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(6) atom to form FeO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-58°. H(1) is bonded in a single-bond geometry to one O(5) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(3), 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(4), one Fe(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 V(3), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Fe(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(4), one Fe(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one V(3) and one Fe(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Fe(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Fe(2) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one V(1), one V(3), and one Fe(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Fe(2) atom.
V4Fe2HO12 crystallizes in the monoclinic P2_1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(3), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(4)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The V(1)-O(11) bond length is 1.78 Å. The V(1)-O(3) bond length is 1.75 Å. The V(1)-O(8) bond length is 1.72 Å. The V(1)-O(9) bond length is 1.78 Å. In the second V site, V(2) is bonded to one O(10), one O(12), one O(4), and one O(7) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with three equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-64°. The V(2)-O(10) bond length is 1.78 Å. The V(2)-O(12) bond length is 1.77 Å. The V(2)-O(4) bond length is 1.76 Å. The V(2)-O(7) bond length is 1.70 Å. In the third V site, V(3) is bonded to one O(1), one O(11), one O(3), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The V(3)-O(1) bond length is 1.90 Å. The V(3)-O(11) bond length is 2.10 Å. The V(3)-O(3) bond length is 2.30 Å. The V(3)-O(6) bond length is 1.68 Å. The V(3)-O(7) bond length is 1.99 Å. The V(3)-O(9) bond length is 2.13 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(2), one O(4), one O(5), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-49°. The V(4)-O(10) bond length is 2.05 Å. The V(4)-O(12) bond length is 2.05 Å. The V(4)-O(2) bond length is 1.75 Å. The V(4)-O(4) bond length is 2.06 Å. The V(4)-O(5) bond length is 1.97 Å. The V(4)-O(8) bond length is 2.01 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(11), one O(2), one O(3), one O(5), and one O(9) atom to form FeO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-58°. The Fe(1)-O(1) bond length is 1.92 Å. The Fe(1)-O(11) bond length is 2.10 Å. The Fe(1)-O(2) bond length is 2.08 Å. The Fe(1)-O(3) bond length is 2.06 Å. The Fe(1)-O(5) bond length is 2.01 Å. The Fe(1)-O(9) bond length is 2.09 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(6) atom to form FeO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent V(2)O4 tetrahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-58°. The Fe(2)-O(1) bond length is 2.12 Å. The Fe(2)-O(10) bond length is 2.14 Å. The Fe(2)-O(12) bond length is 2.36 Å. The Fe(2)-O(2) bond length is 2.20 Å. The Fe(2)-O(4) bond length is 2.12 Å. The Fe(2)-O(6) bond length is 2.01 Å. H(1) is bonded in a single-bond geometry to one O(5) atom. The H(1)-O(5) bond length is 0.98 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(3), 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(4), one Fe(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 V(3), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Fe(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(4), one Fe(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one V(3) and one Fe(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(4) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one V(1), one V(3), and one Fe(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(2), one V(4), and one Fe(2) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one V(1), one V(3), and one Fe(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one Fe(2) atom.