Li2V(CO3)2 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(2)O6 pentagonal pyramids and  an edgeedge with one V(1)O6 pentagonal pyramid. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(4), one O(5), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O6 pentagonal pyramids, corners with two equivalent Li(4)O4 tetrahedra, and  an edgeedge with one V(2)O6 pentagonal pyramid. In the fourth Li site, Li(4) is bonded to one O(10), one O(12), one O(3), and one O(7) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(2)O6 pentagonal pyramids, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 pentagonal pyramid. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(4), and one O(8) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. In the second V site, V(2) is bonded to one O(12), one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(2), one O(3), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(10), one O(8), and one O(9) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(7) 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(2), one V(1), and one C(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one C(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(2), 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(3), one Li(4), one V(1), and one C(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(2), and one C(4) atom.
Li2V(CO3)2 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(4), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(2)O6 pentagonal pyramids and  an edgeedge with one V(1)O6 pentagonal pyramid. The Li(1)-O(11) bond length is 1.99 Å. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(4) bond length is 2.15 Å. The Li(1)-O(5) bond length is 1.98 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(4), one O(5), and one O(9) atom. The Li(2)-O(1) bond length is 1.99 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-O(5) bond length is 2.19 Å. The Li(2)-O(9) bond length is 1.99 Å. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(1)O6 pentagonal pyramids, corners with two equivalent Li(4)O4 tetrahedra, and  an edgeedge with one V(2)O6 pentagonal pyramid. The Li(3)-O(10) bond length is 1.99 Å. The Li(3)-O(12) bond length is 2.18 Å. The Li(3)-O(6) bond length is 1.99 Å. The Li(3)-O(8) bond length is 1.98 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(12), one O(3), and one O(7) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(2)O6 pentagonal pyramids, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 pentagonal pyramid. The Li(4)-O(10) bond length is 2.16 Å. The Li(4)-O(12) bond length is 1.99 Å. The Li(4)-O(3) bond length is 1.99 Å. The Li(4)-O(7) bond length is 1.98 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(11), one O(3), one O(4), and one O(8) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 tetrahedra. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(10) bond length is 2.30 Å. The V(1)-O(11) bond length is 2.19 Å. The V(1)-O(3) bond length is 2.18 Å. The V(1)-O(4) bond length is 2.31 Å. The V(1)-O(8) bond length is 2.14 Å. In the second V site, V(2) is bonded to one O(12), one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The V(2)-O(12) bond length is 2.29 Å. The V(2)-O(2) bond length is 2.15 Å. The V(2)-O(5) bond length is 2.29 Å. The V(2)-O(6) bond length is 2.19 Å. The V(2)-O(7) bond length is 2.15 Å. The V(2)-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(2), one O(3), and one O(5) atom. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.29 Å. The C(1)-O(5) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(4) bond length is 1.31 Å. The C(2)-O(6) bond length is 1.29 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(10), one O(8), and one O(9) atom. The C(3)-O(10) bond length is 1.31 Å. The C(3)-O(8) bond length is 1.30 Å. The C(3)-O(9) bond length is 1.29 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(7) atom. The C(4)-O(11) bond length is 1.29 Å. The C(4)-O(12) bond length is 1.31 Å. The C(4)-O(7) bond length is 1.30 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(2), one V(1), and one C(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one C(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one C(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(4), one V(2), and one C(4) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one C(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(2), 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(3), one Li(4), one V(1), and one C(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Li(4), one V(2), and one C(4) atom.