Li3V2(CO3)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(2), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O5 square pyramids. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(11), and one O(3) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form VO5 square pyramids that share corners with two equivalent Li(2)O4 tetrahedra and  an edgeedge with one V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form edge-sharing VO6 octahedra. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(9) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(6), one O(7), and one O(8) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(12) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one C(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one C(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one C(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one C(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one C(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(2), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(2) and one C(4) atom.
Li3V2(CO3)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(2), one O(6), and one O(7) atom. The Li(1)-O(10) bond length is 2.03 Å. The Li(1)-O(11) bond length is 2.51 Å. The Li(1)-O(2) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.10 Å. The Li(1)-O(7) bond length is 2.29 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O5 square pyramids. The Li(2)-O(3) bond length is 1.95 Å. The Li(2)-O(5) bond length is 1.99 Å. The Li(2)-O(6) bond length is 1.90 Å. The Li(2)-O(8) bond length is 1.93 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(11), and one O(3) atom. The Li(3)-O(1) bond length is 2.34 Å. The Li(3)-O(10) bond length is 1.93 Å. The Li(3)-O(11) bond length is 1.99 Å. The Li(3)-O(3) bond length is 2.02 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form VO5 square pyramids that share corners with two equivalent Li(2)O4 tetrahedra and  an edgeedge with one V(2)O6 octahedra. The V(1)-O(2) bond length is 2.23 Å. The V(1)-O(4) bond length is 2.14 Å. The V(1)-O(5) bond length is 2.12 Å. The V(1)-O(7) bond length is 2.07 Å. The V(1)-O(8) bond length is 2.06 Å. In the second V site, V(2) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(9) atom to form edge-sharing VO6 octahedra. The V(2)-O(1) bond length is 2.06 Å. The V(2)-O(11) bond length is 2.08 Å. The V(2)-O(12) bond length is 2.02 Å. The V(2)-O(2) bond length is 2.14 Å. The V(2)-O(4) bond length is 2.06 Å. The V(2)-O(9) bond length is 1.98 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. The C(1)-O(1) bond length is 1.31 Å. The C(1)-O(3) bond length is 1.26 Å. The C(1)-O(4) bond length is 1.33 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(5), and one O(9) atom. The C(2)-O(2) bond length is 1.33 Å. The C(2)-O(5) bond length is 1.28 Å. The C(2)-O(9) bond length is 1.27 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(6), one O(7), and one O(8) atom. The C(3)-O(6) bond length is 1.28 Å. The C(3)-O(7) bond length is 1.32 Å. The C(3)-O(8) bond length is 1.29 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(12) atom. The C(4)-O(10) bond length is 1.27 Å. The C(4)-O(11) bond length is 1.33 Å. The C(4)-O(12) bond length is 1.30 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one C(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(3), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one C(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one C(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(2) and one C(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one C(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(2), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one V(2) and one C(4) atom.