Li4CO4 crystallizes in the orthorhombic Pmn2_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(2), two equivalent O(1), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(1) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), and four equivalent O(1) atoms. C(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(3), two equivalent Li(1), and one C(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), four equivalent Li(1), and one C(1) atom to form distorted corner-sharing OLi6C pentagonal bipyramids.
Li4CO4 crystallizes in the orthorhombic Pmn2_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(2), two equivalent O(1), and two equivalent O(3) atoms. The Li(1)-O(2) bond length is 1.93 Å. There is one shorter (2.04 Å) and one longer (2.22 Å) Li(1)-O(1) bond length. There is one shorter (1.96 Å) and one longer (2.12 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3) and four equivalent O(1) atoms. The Li(2)-O(3) bond length is 2.00 Å. There are two shorter (2.06 Å) and two longer (2.32 Å) Li(2)-O(1) bond lengths. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), and four equivalent O(1) atoms. The Li(3)-O(2) bond length is 2.10 Å. The Li(3)-O(3) bond length is 2.20 Å. There are two shorter (2.09 Å) and two longer (2.33 Å) Li(3)-O(1) bond lengths. C(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. The C(1)-O(2) bond length is 1.38 Å. The C(1)-O(3) bond length is 1.46 Å. Both C(1)-O(1) bond lengths are 1.43 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 7-coordinate geometry to two equivalent Li(1), two equivalent Li(2), two equivalent Li(3), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(3), two equivalent Li(1), and one C(1) atom. In the third O site, O(3) is bonded to one Li(2), one Li(3), four equivalent Li(1), and one C(1) atom to form distorted corner-sharing OLi6C pentagonal bipyramids.