Li2V(CO3)2 crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(12), and one O(2) atom. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 69-83°. In the third Li site, Li(3) is bonded to one O(11), one O(2), one O(5), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(12), one O(4), one O(6), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra and corners with two equivalent Li(2)O4 trigonal pyramids. In the second V site, V(2) is bonded to one O(11), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. 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(2), and one O(9) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(3), 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 distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2VC trigonal pyramids. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(1), and one C(3) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(4), one V(2), and one C(2) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), and one C(2) atom to form distorted corner-sharing OLi2VC tetrahedra. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), one V(2), and one C(3) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one V(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2VC trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(1) and one C(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one C(4) atom.
Li2V(CO3)2 crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(1), one O(12), and one O(2) atom. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(12) bond length is 2.01 Å. The Li(1)-O(2) bond length is 2.12 Å. In the second Li site, Li(2) is bonded to one O(3), one O(5), one O(7), and one O(9) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 69-83°. The Li(2)-O(3) bond length is 1.93 Å. The Li(2)-O(5) bond length is 1.94 Å. The Li(2)-O(7) bond length is 1.95 Å. The Li(2)-O(9) bond length is 2.14 Å. In the third Li site, Li(3) is bonded to one O(11), one O(2), one O(5), and one O(9) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-58°. The Li(3)-O(11) bond length is 1.97 Å. The Li(3)-O(2) bond length is 2.11 Å. The Li(3)-O(5) bond length is 2.08 Å. The Li(3)-O(9) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(12), one O(4), one O(6), and one O(8) atom. The Li(4)-O(12) bond length is 2.13 Å. The Li(4)-O(4) bond length is 2.00 Å. The Li(4)-O(6) bond length is 1.99 Å. The Li(4)-O(8) bond length is 1.94 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(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra and corners with two equivalent Li(2)O4 trigonal pyramids. The V(1)-O(1) bond length is 2.20 Å. The V(1)-O(10) bond length is 2.11 Å. The V(1)-O(12) bond length is 2.21 Å. The V(1)-O(3) bond length is 2.15 Å. The V(1)-O(5) bond length is 2.28 Å. The V(1)-O(6) bond length is 2.21 Å. In the second V site, V(2) is bonded to one O(11), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  an edgeedge with one Li(3)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The V(2)-O(11) bond length is 2.15 Å. The V(2)-O(2) bond length is 2.22 Å. The V(2)-O(4) bond length is 2.16 Å. The V(2)-O(7) bond length is 2.14 Å. The V(2)-O(8) bond length is 2.20 Å. The V(2)-O(9) bond length is 2.21 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(2), and one O(9) atom. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(9) bond length is 1.30 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(6) atom. The C(2)-O(4) bond length is 1.29 Å. The C(2)-O(5) bond length is 1.33 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(3), one O(7), and one O(8) atom. The C(3)-O(3) bond length is 1.29 Å. The C(3)-O(7) bond length is 1.30 Å. The C(3)-O(8) bond length is 1.30 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 1.30 Å. The C(4)-O(12) bond length is 1.33 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2VC trigonal pyramids. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one V(1), and one C(3) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(4), one V(2), and one C(2) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), and one C(2) atom to form distorted corner-sharing OLi2VC tetrahedra. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(4), one V(2), and one C(3) atom. In the ninth O site, O(9) is bonded to one Li(2), one Li(3), one V(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing OLi2VC trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(1) and one C(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one C(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(1), and one C(4) atom.