Li3V2(CO3)4 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(10) and two equivalent O(11) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(9) atoms. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(9), and two equivalent O(6) atoms. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-65°. There are three inequivalent V sites. In the first V site, V(1) is bonded in a distorted octahedral geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(7) atoms to form distorted VO6 octahedra that share faces with two equivalent Li(4)O5 square pyramids. In the third V site, V(3) is bonded to one O(10), one O(11), one O(12), one O(3), one O(4), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Li(4)O5 square pyramids. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(11), one O(5), and one O(7) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(6), and one O(8) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(9) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(4) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one C(4) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one C(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one C(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one C(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(4), one V(2), and one C(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Li(3), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one C(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(3), and one C(3) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one C(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one C(1) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one C(2) atom.
Li3V2(CO3)4 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(10) and two equivalent O(11) atoms. Both Li(1)-O(10) bond lengths are 2.37 Å. Both Li(1)-O(11) bond lengths are 1.89 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to two equivalent O(12) and two equivalent O(9) atoms. Both Li(2)-O(12) bond lengths are 1.89 Å. Both Li(2)-O(9) bond lengths are 2.37 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(9), and two equivalent O(6) atoms. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-O(3) bond length is 2.01 Å. The Li(3)-O(9) bond length is 2.13 Å. There is one shorter (2.02 Å) and one longer (2.38 Å) Li(3)-O(6) bond length. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-65°. The Li(4)-O(10) bond length is 2.14 Å. The Li(4)-O(2) bond length is 2.00 Å. The Li(4)-O(4) bond length is 2.01 Å. There is one shorter (2.02 Å) and one longer (2.37 Å) Li(4)-O(5) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded in a distorted octahedral geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms. Both V(1)-O(1) bond lengths are 2.01 Å. Both V(1)-O(6) bond lengths are 2.19 Å. Both V(1)-O(8) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(7) atoms to form distorted VO6 octahedra that share faces with two equivalent Li(4)O5 square pyramids. Both V(2)-O(2) bond lengths are 2.01 Å. Both V(2)-O(5) bond lengths are 2.19 Å. Both V(2)-O(7) bond lengths are 2.04 Å. In the third V site, V(3) is bonded to one O(10), one O(11), one O(12), one O(3), one O(4), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Li(4)O5 square pyramids. The V(3)-O(10) bond length is 2.19 Å. The V(3)-O(11) bond length is 2.15 Å. The V(3)-O(12) bond length is 2.16 Å. The V(3)-O(3) bond length is 2.12 Å. The V(3)-O(4) bond length is 2.13 Å. The V(3)-O(9) bond length is 2.19 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(11), one O(5), and one O(7) atom. The C(1)-O(11) bond length is 1.28 Å. The C(1)-O(5) bond length is 1.32 Å. The C(1)-O(7) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(12), one O(6), and one O(8) atom. The C(2)-O(12) bond length is 1.28 Å. The C(2)-O(6) bond length is 1.32 Å. The C(2)-O(8) bond length is 1.29 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(9) atom. The C(3)-O(2) bond length is 1.32 Å. The C(3)-O(3) bond length is 1.28 Å. The C(3)-O(9) bond length is 1.30 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(4) atom. The C(4)-O(1) bond length is 1.32 Å. The C(4)-O(10) bond length is 1.30 Å. The C(4)-O(4) bond length is 1.27 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one C(4) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(4), one V(2), and one C(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one C(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(3), and one C(4) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Li(4), one V(2), and one C(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Li(3), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one C(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(3), and one C(3) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), one V(3), and one C(4) atom. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one C(1) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one C(2) atom.