LiV6O13 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), two equivalent O(11), and two equivalent O(7) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(2)O6 octahedra and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 74°. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(7), one O(8), and three equivalent O(1) atoms. In the second V site, V(2) is bonded to one O(10), one O(7), one O(9), and three equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. In the third V site, V(3) is bonded to one O(5), one O(8), two equivalent O(12), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 22°. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(6), one O(9), two equivalent O(13), and two equivalent O(3) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(5), and two equivalent O(6) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(4), one O(6), and two equivalent O(5) atoms. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(4) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded to one V(3), one V(5), and two equivalent V(6) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the sixth O site, O(6) is bonded to one V(4), one V(6), and two equivalent V(5) atoms to form a mixture of distorted corner and edge-sharing OV4 tetrahedra. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(1) and one V(3) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(2) and one V(4) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(2) and one V(5) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(3) atoms. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one V(6) and two equivalent V(4) atoms.
LiV6O13 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), two equivalent O(11), and two equivalent O(7) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(2)O6 octahedra and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 74°. The Li(1)-O(1) bond length is 2.00 Å. Both Li(1)-O(11) bond lengths are 2.25 Å. Both Li(1)-O(7) bond lengths are 2.40 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(7), one O(8), and three equivalent O(1) atoms. The V(1)-O(7) bond length is 1.96 Å. The V(1)-O(8) bond length is 1.69 Å. There are two shorter (1.98 Å) and one longer (2.00 Å) V(1)-O(1) bond length. In the second V site, V(2) is bonded to one O(10), one O(7), one O(9), and three equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 29°. The V(2)-O(10) bond length is 1.99 Å. The V(2)-O(7) bond length is 1.79 Å. The V(2)-O(9) bond length is 2.13 Å. There are two shorter (1.94 Å) and one longer (2.00 Å) V(2)-O(2) bond length. In the third V site, V(3) is bonded to one O(5), one O(8), two equivalent O(12), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 22°. The V(3)-O(5) bond length is 2.05 Å. The V(3)-O(8) bond length is 1.95 Å. There is one shorter (1.83 Å) and one longer (2.02 Å) V(3)-O(12) bond length. Both V(3)-O(4) bond lengths are 1.92 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(6), one O(9), two equivalent O(13), and two equivalent O(3) atoms. The V(4)-O(6) bond length is 2.04 Å. The V(4)-O(9) bond length is 1.69 Å. There is one shorter (1.76 Å) and one longer (2.37 Å) V(4)-O(13) bond length. Both V(4)-O(3) bond lengths are 1.93 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(3), one O(5), and two equivalent O(6) atoms. The V(5)-O(10) bond length is 1.70 Å. The V(5)-O(12) bond length is 1.99 Å. The V(5)-O(3) bond length is 1.98 Å. The V(5)-O(5) bond length is 2.41 Å. Both V(5)-O(6) bond lengths are 1.98 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(11), one O(13), one O(4), one O(6), and two equivalent O(5) atoms. The V(6)-O(11) bond length is 1.68 Å. The V(6)-O(13) bond length is 1.95 Å. The V(6)-O(4) bond length is 2.02 Å. The V(6)-O(6) bond length is 2.41 Å. Both V(6)-O(5) bond lengths are 1.97 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(4) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded to one V(3), one V(5), and two equivalent V(6) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the sixth O site, O(6) is bonded to one V(4), one V(6), and two equivalent V(5) atoms to form a mixture of distorted corner and edge-sharing OV4 tetrahedra. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(1) and one V(3) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(2) and one V(4) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(2) and one V(5) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(3) atoms. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one V(6) and two equivalent V(4) atoms.