V14Fe5O32 crystallizes in the triclinic P1 space group. There are fourteen inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(14), one O(20), one O(27), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(15), one O(18), and one O(3) atom to form VO6 octahedra that share corners with two equivalent V(13)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with two equivalent V(9)O6 octahedra, corners with three equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the third V site, V(3) is bonded to one O(15), one O(19), one O(3), one O(31), one O(5), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(12)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. In the fourth V site, V(4) is bonded to one O(10), one O(16), one O(20), one O(32), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the fifth V site, V(5) is bonded to one O(13), one O(15), one O(26), one O(31), one O(5), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(12)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. In the sixth V site, V(6) is bonded to one O(10), one O(14), one O(16), one O(27), one O(32), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the seventh V site, V(7) is bonded to one O(1), one O(11), one O(21), one O(23), one O(25), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(13)O6 octahedra, and edges with two equivalent V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. In the eighth V site, V(8) is bonded to one O(12), one O(2), one O(22), one O(24), one O(28), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(11)O6 octahedra, and edges with two equivalent V(14)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the ninth V site, V(9) is bonded to one O(1), one O(18), one O(21), one O(25), one O(29), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(13)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. In the tenth V site, V(10) is bonded to one O(13), one O(15), one O(25), and one O(3) atom to form corner-sharing VO4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 45-66°. In the eleventh V site, V(11) is bonded to one O(17), one O(2), one O(22), one O(28), one O(30), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(14)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the twelfth V site, V(12) is bonded to one O(19), one O(22), one O(24), one O(26), one O(30), and one O(31) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with three equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(11)O6 octahedra,  an edgeedge with one V(14)O6 octahedra, and  an edgeedge with one V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. In the thirteenth V site, V(13) is bonded to one O(11), one O(18), one O(23), one O(25), one O(29), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. In the fourteenth V site, V(14) is bonded to one O(12), one O(17), one O(24), one O(28), one O(30), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(11)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(16), one O(17), one O(2), and one O(4) atom to form FeO6 octahedra that share corners with two equivalent V(11)O6 octahedra, corners with two equivalent V(14)O6 octahedra, corners with two equivalent V(8)O6 octahedra, corners with three equivalent Fe(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. In the second Fe site, Fe(2) is bonded to one O(22), one O(24), one O(30), and one O(5) atom to form FeO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(11)O6 octahedra, corners with two equivalent V(14)O6 octahedra, corners with two equivalent V(8)O6 octahedra, and corners with three equivalent V(12)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-63°. In the third Fe site, Fe(3) is bonded to one O(21), one O(23), one O(29), and one O(6) atom to form FeO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(13)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with two equivalent V(9)O6 octahedra, and corners with three equivalent Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. In the fourth Fe site, Fe(4) is bonded to one O(14), one O(16), one O(28), and one O(4) atom to form FeO4 tetrahedra that share  a cornercorner with one V(11)O6 octahedra,  a cornercorner with one V(14)O6 octahedra,  a cornercorner with one V(8)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-66°. In the fifth Fe site, Fe(5) is bonded to one O(20), one O(21), one O(23), one O(27), one O(29), and one O(32) atom to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with three equivalent Fe(3)O4 tetrahedra,  an edgeedge with one V(13)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, and  an edgeedge with one V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. There are thirty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(7), and one V(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(11), one V(8), and one Fe(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(10), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one V(1), one V(4), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(14)V2Fe2 tetrahedra,  an edgeedge with one O(16)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(3), one V(5), and one Fe(2) atom. In the sixth O site, O(6) is bonded to one V(1), one V(4), one V(6), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OV3Fe trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(11), one V(14), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(13), one V(7), and one V(9) atom. In the ninth O site, O(9) is bonded in a water-like geometry to one V(3) and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(6) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(13), one V(2), and one V(7) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(14), one V(8), and one Fe(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(10), one V(2), and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(1), one V(6), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(16)V2Fe2 tetrahedra,  an edgeedge with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the fifteenth O site, O(15) is bonded in a distorted tetrahedral geometry to one V(10), one V(2), one V(3), and one V(5) atom. In the sixteenth O site, O(16) is bonded to one V(4), one V(6), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(14)V2Fe2 tetrahedra,  an edgeedge with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one V(11), one V(14), and one Fe(1) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one V(13), one V(2), and one V(9) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one V(12) and one V(3) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Fe(5) atom. In the twenty-first O site, O(21) is bonded to one V(7), one V(9), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(23)V2Fe2 tetrahedra,  a cornercorner with one O(29)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(23)V2Fe2 tetrahedra, and  an edgeedge with one O(29)V2Fe2 tetrahedra. In the twenty-second O site, O(22) is bonded to one V(11), one V(12), one V(8), and one Fe(2) atom to form distorted edge-sharing OV3Fe tetrahedra. In the twenty-third O site, O(23) is bonded to one V(13), one V(7), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(21)V2Fe2 tetrahedra,  a cornercorner with one O(29)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(21)V2Fe2 tetrahedra, and  an edgeedge with one O(29)V2Fe2 tetrahedra. In the twenty-fourth O site, O(24) is bonded in a rectangular see-saw-like geometry to one V(12), one V(14), one V(8), and one Fe(2) atom. In the twenty-fifth O site, O(25) is bonded in a rectangular see-saw-like geometry to one V(10), one V(13), one V(7), and one V(9) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one V(12) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted trigonal planar geometry to one V(1), one V(6), and one Fe(5) atom. In the twenty-eighth O site, O(28) is bonded to one V(11), one V(14), one V(8), and one Fe(4) atom to form OV3Fe tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(22)V3Fe tetrahedra. In the twenty-ninth O site, O(29) is bonded to one V(13), one V(9), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(21)V2Fe2 tetrahedra,  a cornercorner with one O(23)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(21)V2Fe2 tetrahedra, and  an edgeedge with one O(23)V2Fe2 tetrahedra. In the thirtieth O site, O(30) is bonded in a distorted rectangular see-saw-like geometry to one V(11), one V(12), one V(14), and one Fe(2) atom. In the thirty-first O site, O(31) is bonded in a distorted T-shaped geometry to one V(12), one V(3), and one V(5) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal planar geometry to one V(4), one V(6), and one Fe(5) atom.
V14Fe5O32 crystallizes in the triclinic P1 space group. There are fourteen inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(14), one O(20), one O(27), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The V(1)-O(10) bond length is 2.01 Å. The V(1)-O(14) bond length is 2.03 Å. The V(1)-O(20) bond length is 2.02 Å. The V(1)-O(27) bond length is 2.01 Å. The V(1)-O(4) bond length is 2.03 Å. The V(1)-O(6) bond length is 2.09 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(13), one O(15), one O(18), and one O(3) atom to form VO6 octahedra that share corners with two equivalent V(13)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with two equivalent V(9)O6 octahedra, corners with three equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(3)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(11) bond length is 2.07 Å. The V(2)-O(13) bond length is 2.08 Å. The V(2)-O(15) bond length is 2.12 Å. The V(2)-O(18) bond length is 2.01 Å. The V(2)-O(3) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(15), one O(19), one O(3), one O(31), one O(5), and one O(9) atom to form distorted VO6 octahedra that share corners with two equivalent V(12)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-51°. The V(3)-O(15) bond length is 2.17 Å. The V(3)-O(19) bond length is 1.72 Å. The V(3)-O(3) bond length is 2.29 Å. The V(3)-O(31) bond length is 1.96 Å. The V(3)-O(5) bond length is 2.01 Å. The V(3)-O(9) bond length is 1.99 Å. In the fourth V site, V(4) is bonded to one O(10), one O(16), one O(20), one O(32), one O(4), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. The V(4)-O(10) bond length is 1.93 Å. The V(4)-O(16) bond length is 2.06 Å. The V(4)-O(20) bond length is 1.83 Å. The V(4)-O(32) bond length is 1.92 Å. The V(4)-O(4) bond length is 2.01 Å. The V(4)-O(6) bond length is 2.12 Å. In the fifth V site, V(5) is bonded to one O(13), one O(15), one O(26), one O(31), one O(5), and one O(9) atom to form VO6 octahedra that share corners with two equivalent V(12)O6 octahedra,  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent V(10)O4 trigonal pyramids,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-44°. The V(5)-O(13) bond length is 2.06 Å. The V(5)-O(15) bond length is 2.11 Å. The V(5)-O(26) bond length is 1.99 Å. The V(5)-O(31) bond length is 2.02 Å. The V(5)-O(5) bond length is 2.03 Å. The V(5)-O(9) bond length is 1.73 Å. In the sixth V site, V(6) is bonded to one O(10), one O(14), one O(16), one O(27), one O(32), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Fe(5)O6 octahedra,  a cornercorner with one Fe(3)O4 tetrahedra, corners with two equivalent Fe(4)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. The V(6)-O(10) bond length is 1.93 Å. The V(6)-O(14) bond length is 2.01 Å. The V(6)-O(16) bond length is 2.07 Å. The V(6)-O(27) bond length is 1.82 Å. The V(6)-O(32) bond length is 1.93 Å. The V(6)-O(6) bond length is 2.12 Å. In the seventh V site, V(7) is bonded to one O(1), one O(11), one O(21), one O(23), one O(25), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(13)O6 octahedra, and edges with two equivalent V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-48°. The V(7)-O(1) bond length is 1.95 Å. The V(7)-O(11) bond length is 1.84 Å. The V(7)-O(21) bond length is 2.07 Å. The V(7)-O(23) bond length is 2.03 Å. The V(7)-O(25) bond length is 2.10 Å. The V(7)-O(8) bond length is 1.92 Å. In the eighth V site, V(8) is bonded to one O(12), one O(2), one O(22), one O(24), one O(28), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(11)O6 octahedra, and edges with two equivalent V(14)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(8)-O(12) bond length is 1.92 Å. The V(8)-O(2) bond length is 1.95 Å. The V(8)-O(22) bond length is 2.11 Å. The V(8)-O(24) bond length is 2.13 Å. The V(8)-O(28) bond length is 2.04 Å. The V(8)-O(7) bond length is 2.04 Å. In the ninth V site, V(9) is bonded to one O(1), one O(18), one O(21), one O(25), one O(29), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(13)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. The V(9)-O(1) bond length is 1.99 Å. The V(9)-O(18) bond length is 1.89 Å. The V(9)-O(21) bond length is 2.08 Å. The V(9)-O(25) bond length is 2.08 Å. The V(9)-O(29) bond length is 2.03 Å. The V(9)-O(8) bond length is 1.93 Å. In the tenth V site, V(10) is bonded to one O(13), one O(15), one O(25), and one O(3) atom to form corner-sharing VO4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 45-66°. The V(10)-O(13) bond length is 1.79 Å. The V(10)-O(15) bond length is 1.97 Å. The V(10)-O(25) bond length is 1.94 Å. The V(10)-O(3) bond length is 1.76 Å. In the eleventh V site, V(11) is bonded to one O(17), one O(2), one O(22), one O(28), one O(30), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(14)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(11)-O(17) bond length is 1.92 Å. The V(11)-O(2) bond length is 1.95 Å. The V(11)-O(22) bond length is 2.10 Å. The V(11)-O(28) bond length is 2.05 Å. The V(11)-O(30) bond length is 2.15 Å. The V(11)-O(7) bond length is 2.04 Å. In the twelfth V site, V(12) is bonded to one O(19), one O(22), one O(24), one O(26), one O(30), and one O(31) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(5)O6 octahedra, corners with three equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(11)O6 octahedra,  an edgeedge with one V(14)O6 octahedra, and  an edgeedge with one V(8)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-51°. The V(12)-O(19) bond length is 1.98 Å. The V(12)-O(22) bond length is 2.09 Å. The V(12)-O(24) bond length is 2.15 Å. The V(12)-O(26) bond length is 1.71 Å. The V(12)-O(30) bond length is 2.05 Å. The V(12)-O(31) bond length is 1.99 Å. In the thirteenth V site, V(13) is bonded to one O(11), one O(18), one O(23), one O(25), one O(29), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Fe(3)O4 tetrahedra,  a cornercorner with one V(10)O4 trigonal pyramid,  an edgeedge with one Fe(5)O6 octahedra, edges with two equivalent V(7)O6 octahedra, and edges with two equivalent V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. The V(13)-O(11) bond length is 2.03 Å. The V(13)-O(18) bond length is 2.01 Å. The V(13)-O(23) bond length is 2.06 Å. The V(13)-O(25) bond length is 2.09 Å. The V(13)-O(29) bond length is 2.07 Å. The V(13)-O(8) bond length is 2.02 Å. In the fourteenth V site, V(14) is bonded to one O(12), one O(17), one O(24), one O(28), one O(30), and one O(7) atom to form VO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra,  a cornercorner with one Fe(4)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra,  an edgeedge with one V(12)O6 octahedra, edges with two equivalent V(11)O6 octahedra, and edges with two equivalent V(8)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. The V(14)-O(12) bond length is 1.98 Å. The V(14)-O(17) bond length is 1.98 Å. The V(14)-O(24) bond length is 2.12 Å. The V(14)-O(28) bond length is 1.95 Å. The V(14)-O(30) bond length is 2.11 Å. The V(14)-O(7) bond length is 1.81 Å. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(14), one O(16), one O(17), one O(2), and one O(4) atom to form FeO6 octahedra that share corners with two equivalent V(11)O6 octahedra, corners with two equivalent V(14)O6 octahedra, corners with two equivalent V(8)O6 octahedra, corners with three equivalent Fe(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-51°. The Fe(1)-O(12) bond length is 2.02 Å. The Fe(1)-O(14) bond length is 2.10 Å. The Fe(1)-O(16) bond length is 2.06 Å. The Fe(1)-O(17) bond length is 2.00 Å. The Fe(1)-O(2) bond length is 2.00 Å. The Fe(1)-O(4) bond length is 2.09 Å. In the second Fe site, Fe(2) is bonded to one O(22), one O(24), one O(30), and one O(5) atom to form FeO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, corners with two equivalent V(11)O6 octahedra, corners with two equivalent V(14)O6 octahedra, corners with two equivalent V(8)O6 octahedra, and corners with three equivalent V(12)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-63°. The Fe(2)-O(22) bond length is 1.95 Å. The Fe(2)-O(24) bond length is 1.94 Å. The Fe(2)-O(30) bond length is 1.96 Å. The Fe(2)-O(5) bond length is 1.89 Å. In the third Fe site, Fe(3) is bonded to one O(21), one O(23), one O(29), and one O(6) atom to form FeO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(13)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with two equivalent V(9)O6 octahedra, and corners with three equivalent Fe(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-63°. The Fe(3)-O(21) bond length is 1.92 Å. The Fe(3)-O(23) bond length is 1.94 Å. The Fe(3)-O(29) bond length is 1.94 Å. The Fe(3)-O(6) bond length is 1.91 Å. In the fourth Fe site, Fe(4) is bonded to one O(14), one O(16), one O(28), and one O(4) atom to form FeO4 tetrahedra that share  a cornercorner with one V(11)O6 octahedra,  a cornercorner with one V(14)O6 octahedra,  a cornercorner with one V(8)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, and corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-66°. The Fe(4)-O(14) bond length is 2.02 Å. The Fe(4)-O(16) bond length is 1.98 Å. The Fe(4)-O(28) bond length is 2.07 Å. The Fe(4)-O(4) bond length is 2.01 Å. In the fifth Fe site, Fe(5) is bonded to one O(20), one O(21), one O(23), one O(27), one O(29), and one O(32) atom to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with three equivalent Fe(3)O4 tetrahedra,  an edgeedge with one V(13)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, and  an edgeedge with one V(9)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Fe(5)-O(20) bond length is 2.05 Å. The Fe(5)-O(21) bond length is 2.21 Å. The Fe(5)-O(23) bond length is 2.24 Å. The Fe(5)-O(27) bond length is 2.08 Å. The Fe(5)-O(29) bond length is 2.26 Å. The Fe(5)-O(32) bond length is 2.05 Å. There are thirty-two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(7), and one V(9) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(11), one V(8), and one Fe(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(10), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one V(1), one V(4), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(14)V2Fe2 tetrahedra,  an edgeedge with one O(16)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one V(3), one V(5), and one Fe(2) atom. In the sixth O site, O(6) is bonded to one V(1), one V(4), one V(6), and one Fe(3) atom to form a mixture of distorted corner and edge-sharing OV3Fe trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(11), one V(14), and one V(8) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one V(13), one V(7), and one V(9) atom. In the ninth O site, O(9) is bonded in a water-like geometry to one V(3) and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one V(1), one V(4), and one V(6) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one V(13), one V(2), and one V(7) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one V(14), one V(8), and one Fe(1) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(10), one V(2), and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(1), one V(6), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(16)V2Fe2 tetrahedra,  an edgeedge with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the fifteenth O site, O(15) is bonded in a distorted tetrahedral geometry to one V(10), one V(2), one V(3), and one V(5) atom. In the sixteenth O site, O(16) is bonded to one V(4), one V(6), one Fe(1), and one Fe(4) atom to form OV2Fe2 tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra,  a cornercorner with one O(28)V3Fe tetrahedra,  an edgeedge with one O(14)V2Fe2 tetrahedra,  an edgeedge with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(6)V3Fe trigonal pyramid. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to one V(11), one V(14), and one Fe(1) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal planar geometry to one V(13), one V(2), and one V(9) atom. In the nineteenth O site, O(19) is bonded in a distorted bent 150 degrees geometry to one V(12) and one V(3) atom. In the twentieth O site, O(20) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one Fe(5) atom. In the twenty-first O site, O(21) is bonded to one V(7), one V(9), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(23)V2Fe2 tetrahedra,  a cornercorner with one O(29)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(23)V2Fe2 tetrahedra, and  an edgeedge with one O(29)V2Fe2 tetrahedra. In the twenty-second O site, O(22) is bonded to one V(11), one V(12), one V(8), and one Fe(2) atom to form distorted edge-sharing OV3Fe tetrahedra. In the twenty-third O site, O(23) is bonded to one V(13), one V(7), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(21)V2Fe2 tetrahedra,  a cornercorner with one O(29)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(21)V2Fe2 tetrahedra, and  an edgeedge with one O(29)V2Fe2 tetrahedra. In the twenty-fourth O site, O(24) is bonded in a rectangular see-saw-like geometry to one V(12), one V(14), one V(8), and one Fe(2) atom. In the twenty-fifth O site, O(25) is bonded in a rectangular see-saw-like geometry to one V(10), one V(13), one V(7), and one V(9) atom. In the twenty-sixth O site, O(26) is bonded in a bent 150 degrees geometry to one V(12) and one V(5) atom. In the twenty-seventh O site, O(27) is bonded in a distorted trigonal planar geometry to one V(1), one V(6), and one Fe(5) atom. In the twenty-eighth O site, O(28) is bonded to one V(11), one V(14), one V(8), and one Fe(4) atom to form OV3Fe tetrahedra that share  a cornercorner with one O(14)V2Fe2 tetrahedra,  a cornercorner with one O(16)V2Fe2 tetrahedra,  a cornercorner with one O(4)V2Fe2 tetrahedra, and  an edgeedge with one O(22)V3Fe tetrahedra. In the twenty-ninth O site, O(29) is bonded to one V(13), one V(9), one Fe(3), and one Fe(5) atom to form distorted OV2Fe2 tetrahedra that share  a cornercorner with one O(21)V2Fe2 tetrahedra,  a cornercorner with one O(23)V2Fe2 tetrahedra,  a cornercorner with one O(6)V3Fe trigonal pyramid,  an edgeedge with one O(21)V2Fe2 tetrahedra, and  an edgeedge with one O(23)V2Fe2 tetrahedra. In the thirtieth O site, O(30) is bonded in a distorted rectangular see-saw-like geometry to one V(11), one V(12), one V(14), and one Fe(2) atom. In the thirty-first O site, O(31) is bonded in a distorted T-shaped geometry to one V(12), one V(3), and one V(5) atom. In the thirty-second O site, O(32) is bonded in a distorted trigonal planar geometry to one V(4), one V(6), and one Fe(5) atom.