Li4CO4 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. C(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom.
Li4CO4 crystallizes in the monoclinic Cm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 2.42 Å. The Li(1)-O(3) bond length is 2.06 Å. There is one shorter (2.06 Å) and one longer (2.19 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(3), and two equivalent O(2) atoms. The Li(2)-O(1) bond length is 1.85 Å. The Li(2)-O(3) bond length is 1.84 Å. There is one shorter (1.84 Å) and one longer (1.88 Å) Li(2)-O(2) bond length. C(1) is bonded in a tetrahedral geometry to one O(1), one O(3), and two equivalent O(2) atoms. The C(1)-O(1) bond length is 1.40 Å. The C(1)-O(3) bond length is 1.47 Å. Both C(1)-O(2) bond lengths are 1.43 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one C(1) atom.