Li2V(CO3)2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), one O(7), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. In the third Li site, Li(3) is bonded to one O(11), one O(3), one O(6), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. In the fourth Li site, Li(4) is bonded to one O(12), one O(4), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. 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(4), one O(5), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(4)O4 trigonal pyramid. In the second V site, V(2) is bonded to one O(11), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Li(3)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(5), and one O(9) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(6) atom. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(3), and one O(7) atom. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(12), one O(4), and one O(8) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(2), 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(1), and one C(4) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one V(1), and one C(1) atom to form a mixture of edge and corner-sharing OLi2VC trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one V(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing OLi2VC trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one V(2), and one C(3) atom to form a mixture of edge and corner-sharing OLi2VC trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one V(1), and one C(4) atom to form a mixture of distorted edge and corner-sharing OLi2VC trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one C(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one C(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(4) atom.
Li2V(CO3)2 crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), one O(7), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(6) bond length is 2.12 Å. The Li(1)-O(7) bond length is 2.02 Å. The Li(1)-O(9) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. The Li(2)-O(10) bond length is 1.99 Å. The Li(2)-O(2) bond length is 1.97 Å. The Li(2)-O(5) bond length is 2.12 Å. The Li(2)-O(8) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(11), one O(3), one O(6), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. The Li(3)-O(11) bond length is 1.99 Å. The Li(3)-O(3) bond length is 1.96 Å. The Li(3)-O(6) bond length is 2.02 Å. The Li(3)-O(7) bond length is 2.12 Å. In the fourth Li site, Li(4) is bonded to one O(12), one O(4), one O(5), and one O(8) atom to form distorted LiO4 trigonal pyramids that share corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 43-82°. The Li(4)-O(12) bond length is 1.99 Å. The Li(4)-O(4) bond length is 1.97 Å. The Li(4)-O(5) bond length is 2.02 Å. The Li(4)-O(8) bond length is 2.12 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(4), one O(5), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(4)O4 trigonal pyramid. The V(1)-O(1) bond length is 2.24 Å. The V(1)-O(10) bond length is 2.12 Å. The V(1)-O(12) bond length is 2.12 Å. The V(1)-O(4) bond length is 2.24 Å. The V(1)-O(5) bond length is 2.18 Å. The V(1)-O(8) bond length is 2.19 Å. In the second V site, V(2) is bonded to one O(11), one O(2), one O(3), one O(6), one O(7), and one O(9) atom to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O4 trigonal pyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, corners with two equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Li(3)O4 trigonal pyramid. The V(2)-O(11) bond length is 2.13 Å. The V(2)-O(2) bond length is 2.24 Å. The V(2)-O(3) bond length is 2.24 Å. The V(2)-O(6) bond length is 2.19 Å. The V(2)-O(7) bond length is 2.18 Å. The V(2)-O(9) bond length is 2.13 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(5), and one O(9) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.32 Å. The C(1)-O(9) bond length is 1.28 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(2), and one O(6) atom. The C(2)-O(10) bond length is 1.28 Å. The C(2)-O(2) bond length is 1.30 Å. The C(2)-O(6) bond length is 1.32 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one O(11), one O(3), and one O(7) atom. The C(3)-O(11) bond length is 1.28 Å. The C(3)-O(3) bond length is 1.30 Å. The C(3)-O(7) bond length is 1.32 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one O(12), one O(4), and one O(8) atom. The C(4)-O(12) bond length is 1.28 Å. The C(4)-O(4) bond length is 1.30 Å. The C(4)-O(8) bond length is 1.32 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one C(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one C(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(2), 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(1), and one C(4) atom. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one V(1), and one C(1) atom to form a mixture of edge and corner-sharing OLi2VC trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one V(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing OLi2VC trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one V(2), and one C(3) atom to form a mixture of edge and corner-sharing OLi2VC trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one V(1), and one C(4) atom to form a mixture of distorted edge and corner-sharing OLi2VC trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one C(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one C(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one C(4) atom.