Li3V4FeO12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form LiO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(12), one O(2), one O(3), and one O(6) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(4), and one O(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-64°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-67°. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-62°. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-63°. Fe(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one Fe(1) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one Fe(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one V(3), and one Fe(1) atom to form distorted corner-sharing OLi2VFe trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(4) and one Fe(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Li(2), one V(4), and one Fe(1) atom to form distorted corner-sharing OLi2VFe trigonal pyramids.
Li3V4FeO12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(12), one O(2), one O(3), and one O(5) atom to form LiO6 octahedra that share  a cornercorner with one V(2)O4 tetrahedra,  a cornercorner with one V(4)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(10) bond length is 2.32 Å. The Li(1)-O(12) bond length is 2.36 Å. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(3) bond length is 2.24 Å. The Li(1)-O(5) bond length is 2.06 Å. In the second Li site, Li(2) is bonded in a distorted see-saw-like geometry to one O(12), one O(2), one O(3), and one O(6) atom. The Li(2)-O(12) bond length is 2.03 Å. The Li(2)-O(2) bond length is 2.07 Å. The Li(2)-O(3) bond length is 2.04 Å. The Li(2)-O(6) bond length is 2.25 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(4), and one O(8) atom. The Li(3)-O(1) bond length is 1.99 Å. The Li(3)-O(10) bond length is 2.02 Å. The Li(3)-O(4) bond length is 2.54 Å. The Li(3)-O(8) bond length is 2.08 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-64°. The V(1)-O(1) bond length is 1.73 Å. The V(1)-O(2) bond length is 1.70 Å. The V(1)-O(4) bond length is 1.78 Å. The V(1)-O(6) bond length is 1.79 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(6), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-67°. The V(2)-O(3) bond length is 1.77 Å. The V(2)-O(4) bond length is 1.90 Å. The V(2)-O(6) bond length is 1.91 Å. The V(2)-O(8) bond length is 1.75 Å. In the third V site, V(3) is bonded to one O(10), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-62°. The V(3)-O(10) bond length is 1.71 Å. The V(3)-O(5) bond length is 1.66 Å. The V(3)-O(7) bond length is 1.81 Å. The V(3)-O(9) bond length is 1.81 Å. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-63°. The V(4)-O(11) bond length is 1.67 Å. The V(4)-O(12) bond length is 1.71 Å. The V(4)-O(7) bond length is 1.80 Å. The V(4)-O(9) bond length is 1.81 Å. Fe(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(3), and one O(8) atom to form FeO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(3)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, corners with two equivalent V(4)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. The Fe(1)-O(1) bond length is 2.20 Å. The Fe(1)-O(10) bond length is 2.26 Å. The Fe(1)-O(11) bond length is 2.11 Å. The Fe(1)-O(12) bond length is 2.24 Å. The Fe(1)-O(3) bond length is 2.07 Å. The Fe(1)-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 rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one Fe(1) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one Fe(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one V(3), and one Fe(1) atom to form distorted corner-sharing OLi2VFe trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one V(4) and one Fe(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Li(2), one V(4), and one Fe(1) atom to form distorted corner-sharing OLi2VFe trigonal pyramids.