Li4ZrO4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Zr(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Zr(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. Zr(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form ZrO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra and corners with eight equivalent Li(2)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Zr(1) atom to form distorted corner-sharing OLi4Zr trigonal bipyramids. 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 Zr(1) atom.
Li4ZrO4 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Zr(1)O4 tetrahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 1.97 Å. Both Li(1)-O(2) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Zr(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. There is one shorter (2.01 Å) and one longer (2.19 Å) Li(2)-O(1) bond length. Both Li(2)-O(2) bond lengths are 1.99 Å. Zr(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form ZrO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra and corners with eight equivalent Li(2)O4 tetrahedra. Both Zr(1)-O(1) bond lengths are 2.01 Å. Both Zr(1)-O(2) bond lengths are 2.00 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Zr(1) atom to form distorted corner-sharing OLi4Zr trigonal bipyramids. 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 Zr(1) atom.