LiV3O5F3 crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(8), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent V(4)O3F3 octahedra and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-60°. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(9), one F(4), and two equivalent F(6) atoms to form distorted LiO3F3 octahedra that share corners with two equivalent V(3)O5F octahedra and edges with two equivalent Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-61°. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(10), one O(6), two equivalent O(1), one F(1), and one F(5) atom. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(7), two equivalent O(5), and one F(2) atom. In the third V site, V(3) is bonded to one O(10), one O(2), one O(6), two equivalent O(3), and one F(4) atom to form VO5F octahedra that share corners with two equivalent Li(2)O3F3 octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 20-61°. In the fourth V site, V(4) is bonded to one O(1), one O(4), one O(8), one F(3), and two equivalent F(5) atoms to form distorted VO3F3 octahedra that share corners with two equivalent Li(1)O2F4 octahedra and corners with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 26-60°. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(5), one O(8), two equivalent O(7), and one F(6) atom. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(9), two equivalent O(10), and one F(3) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one V(4), one V(6), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(5) atoms. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(6) atom. In the tenth O site, O(10) is bonded to one V(1), one V(3), and two equivalent V(6) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one V(4) and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(4) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to two equivalent Li(2) and one V(5) atom.
LiV3O5F3 crystallizes in the monoclinic Pm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(8), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent V(4)O3F3 octahedra and edges with two equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-60°. The Li(1)-O(4) bond length is 2.01 Å. The Li(1)-O(8) bond length is 2.09 Å. Both Li(1)-F(1) bond lengths are 2.26 Å. Both Li(1)-F(2) bond lengths are 2.42 Å. In the second Li site, Li(2) is bonded to one O(2), two equivalent O(9), one F(4), and two equivalent F(6) atoms to form distorted LiO3F3 octahedra that share corners with two equivalent V(3)O5F octahedra and edges with two equivalent Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 29-61°. The Li(2)-O(2) bond length is 2.19 Å. Both Li(2)-O(9) bond lengths are 2.40 Å. The Li(2)-F(4) bond length is 1.96 Å. Both Li(2)-F(6) bond lengths are 2.33 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(10), one O(6), two equivalent O(1), one F(1), and one F(5) atom. The V(1)-O(10) bond length is 2.09 Å. The V(1)-O(6) bond length is 1.71 Å. Both V(1)-O(1) bond lengths are 2.00 Å. The V(1)-F(1) bond length is 1.88 Å. The V(1)-F(5) bond length is 2.36 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(7), two equivalent O(5), and one F(2) atom. The V(2)-O(2) bond length is 1.77 Å. The V(2)-O(7) bond length is 1.94 Å. Both V(2)-O(5) bond lengths are 1.95 Å. The V(2)-F(2) bond length is 1.86 Å. In the third V site, V(3) is bonded to one O(10), one O(2), one O(6), two equivalent O(3), and one F(4) atom to form VO5F octahedra that share corners with two equivalent Li(2)O3F3 octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 20-61°. The V(3)-O(10) bond length is 2.07 Å. The V(3)-O(2) bond length is 1.97 Å. The V(3)-O(6) bond length is 1.99 Å. Both V(3)-O(3) bond lengths are 1.93 Å. The V(3)-F(4) bond length is 1.87 Å. In the fourth V site, V(4) is bonded to one O(1), one O(4), one O(8), one F(3), and two equivalent F(5) atoms to form distorted VO3F3 octahedra that share corners with two equivalent Li(1)O2F4 octahedra and corners with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 26-60°. The V(4)-O(1) bond length is 2.20 Å. The V(4)-O(4) bond length is 1.65 Å. The V(4)-O(8) bond length is 1.97 Å. The V(4)-F(3) bond length is 2.01 Å. Both V(4)-F(5) bond lengths are 1.95 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one O(5), one O(8), two equivalent O(7), and one F(6) atom. The V(5)-O(5) bond length is 1.95 Å. The V(5)-O(8) bond length is 1.76 Å. Both V(5)-O(7) bond lengths are 1.95 Å. The V(5)-F(6) bond length is 1.87 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(9), two equivalent O(10), and one F(3) atom. The V(6)-O(1) bond length is 2.45 Å. The V(6)-O(3) bond length is 2.05 Å. The V(6)-O(9) bond length is 1.65 Å. Both V(6)-O(10) bond lengths are 2.00 Å. The V(6)-F(3) bond length is 1.98 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one V(4), one V(6), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one V(6) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Li(1) and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one V(5) and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(5) atoms. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(4), and one V(5) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to two equivalent Li(2) and one V(6) atom. In the tenth O site, O(10) is bonded to one V(1), one V(3), and two equivalent V(6) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 120 degrees geometry to one V(4) and one V(6) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Li(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one V(1) and two equivalent V(4) atoms. In the sixth F site, F(6) is bonded in a trigonal planar geometry to two equivalent Li(2) and one V(5) atom.