Li2V5Cr2O12 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(7) atom to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(5)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-14°. In the second V site, V(2) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-17°. In the third V site, V(3) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the fifth V site, V(5) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. In the second Cr site, Cr(2) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(7)Li2V2Cr square pyramid,  a cornercorner with one O(12)LiV3Cr square pyramid, corners with two equivalent O(11)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids,  an edgeedge with one O(11)Li2V2Cr square pyramid,  an edgeedge with one O(10)LiV3Cr square pyramid, and edges with two equivalent O(7)Li2V2Cr square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(11)Li2V2Cr square pyramid,  a cornercorner with one O(10)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(12)LiV3Cr square pyramids,  an edgeedge with one O(7)Li2V2Cr square pyramid,  an edgeedge with one O(12)LiV3Cr square pyramid, and edges with two equivalent O(10)LiV3Cr square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(4), and one Cr(1) atom. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Li(2), one V(2), one V(4), and one Cr(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one Cr(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one Cr(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(2), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(12)LiV3Cr square pyramid, corners with two equivalent O(10)LiV3Cr square pyramids,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with two equivalent O(1)Li2V2Cr square pyramids, and edges with two equivalent O(11)Li2V2Cr square pyramids. In the eighth O site, O(8) is bonded in a see-saw-like geometry to one Li(2), one V(2), one V(3), and one Cr(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(5), and one Cr(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one V(1), one V(3), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(11)Li2V2Cr square pyramid,  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(7)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid, edges with two equivalent O(12)LiV3Cr square pyramids, and edges with two equivalent O(2)LiV3Cr square pyramids. In the eleventh O site, O(11) is bonded to one Li(1), one Li(2), one V(2), one V(4), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(10)LiV3Cr square pyramid,  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(12)LiV3Cr square pyramid, and edges with two equivalent O(7)Li2V2Cr square pyramids. In the twelfth O site, O(12) is bonded to one Li(1), one V(1), one V(4), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(7)Li2V2Cr square pyramid, corners with two equivalent O(2)LiV3Cr square pyramids,  an edgeedge with one O(11)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, and edges with two equivalent O(10)LiV3Cr square pyramids.
Li2V5Cr2O12 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(7) atom to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-17°. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(10) bond length is 2.28 Å. The Li(1)-O(11) bond length is 2.20 Å. The Li(1)-O(12) bond length is 2.22 Å. The Li(1)-O(2) bond length is 2.13 Å. The Li(1)-O(7) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. The Li(2)-O(1) bond length is 2.31 Å. The Li(2)-O(11) bond length is 1.99 Å. The Li(2)-O(3) bond length is 2.27 Å. The Li(2)-O(4) bond length is 2.13 Å. The Li(2)-O(7) bond length is 2.21 Å. The Li(2)-O(8) bond length is 1.97 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(5)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-14°. The V(1)-O(10) bond length is 2.04 Å. The V(1)-O(12) bond length is 2.13 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(5) bond length is 2.06 Å. The V(1)-O(6) bond length is 1.99 Å. The V(1)-O(9) bond length is 2.09 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-17°. The V(2)-O(1) bond length is 1.97 Å. The V(2)-O(11) bond length is 2.11 Å. The V(2)-O(3) bond length is 1.98 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(7) bond length is 2.08 Å. The V(2)-O(8) bond length is 1.94 Å. In the third V site, V(3) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The V(3)-O(1) bond length is 2.05 Å. The V(3)-O(10) bond length is 2.10 Å. The V(3)-O(2) bond length is 2.23 Å. The V(3)-O(7) bond length is 1.96 Å. The V(3)-O(8) bond length is 2.10 Å. The V(3)-O(9) bond length is 2.14 Å. In the fourth V site, V(4) is bonded to one O(11), one O(12), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra, and  an edgeedge with one Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-14°. The V(4)-O(11) bond length is 2.04 Å. The V(4)-O(12) bond length is 2.17 Å. The V(4)-O(3) bond length is 1.93 Å. The V(4)-O(4) bond length is 2.09 Å. The V(4)-O(5) bond length is 2.11 Å. The V(4)-O(6) bond length is 2.17 Å. In the fifth V site, V(5) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. The V(5)-O(10) bond length is 2.11 Å. The V(5)-O(12) bond length is 2.00 Å. The V(5)-O(2) bond length is 2.14 Å. The V(5)-O(5) bond length is 2.04 Å. The V(5)-O(6) bond length is 2.07 Å. The V(5)-O(9) bond length is 1.98 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(11), one O(3), one O(4), one O(7), and one O(8) atom to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Cr(1)-O(1) bond length is 2.02 Å. The Cr(1)-O(11) bond length is 2.00 Å. The Cr(1)-O(3) bond length is 2.04 Å. The Cr(1)-O(4) bond length is 2.02 Å. The Cr(1)-O(7) bond length is 2.09 Å. The Cr(1)-O(8) bond length is 1.96 Å. In the second Cr site, Cr(2) is bonded to one O(10), one O(12), one O(2), one O(5), one O(6), and one O(9) atom to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. The Cr(2)-O(10) bond length is 2.11 Å. The Cr(2)-O(12) bond length is 2.01 Å. The Cr(2)-O(2) bond length is 1.98 Å. The Cr(2)-O(5) bond length is 2.06 Å. The Cr(2)-O(6) bond length is 2.00 Å. The Cr(2)-O(9) bond length is 2.01 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(2), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(7)Li2V2Cr square pyramid,  a cornercorner with one O(12)LiV3Cr square pyramid, corners with two equivalent O(11)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids,  an edgeedge with one O(11)Li2V2Cr square pyramid,  an edgeedge with one O(10)LiV3Cr square pyramid, and edges with two equivalent O(7)Li2V2Cr square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(3), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(11)Li2V2Cr square pyramid,  a cornercorner with one O(10)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(12)LiV3Cr square pyramids,  an edgeedge with one O(7)Li2V2Cr square pyramid,  an edgeedge with one O(12)LiV3Cr square pyramid, and edges with two equivalent O(10)LiV3Cr square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(2), one V(4), and one Cr(1) atom. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Li(2), one V(2), one V(4), and one Cr(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one Cr(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one Cr(2) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(2), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(12)LiV3Cr square pyramid, corners with two equivalent O(10)LiV3Cr square pyramids,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with two equivalent O(1)Li2V2Cr square pyramids, and edges with two equivalent O(11)Li2V2Cr square pyramids. In the eighth O site, O(8) is bonded in a see-saw-like geometry to one Li(2), one V(2), one V(3), and one Cr(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), one V(5), and one Cr(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one V(1), one V(3), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(11)Li2V2Cr square pyramid,  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(7)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid, edges with two equivalent O(12)LiV3Cr square pyramids, and edges with two equivalent O(2)LiV3Cr square pyramids. In the eleventh O site, O(11) is bonded to one Li(1), one Li(2), one V(2), one V(4), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(10)LiV3Cr square pyramid,  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(12)LiV3Cr square pyramid, and edges with two equivalent O(7)Li2V2Cr square pyramids. In the twelfth O site, O(12) is bonded to one Li(1), one V(1), one V(4), one V(5), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid,  a cornercorner with one O(7)Li2V2Cr square pyramid, corners with two equivalent O(2)LiV3Cr square pyramids,  an edgeedge with one O(11)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, and edges with two equivalent O(10)LiV3Cr square pyramids.