K2Li14Zr3O14 crystallizes in the orthorhombic Immm space group. K(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(2) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Zr(1)O6 octahedra,  an edgeedge with one Zr(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. In the second Li site, Li(2) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-38°. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Zr(2)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-37°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Zr(2)O6 octahedra, and edges with eight equivalent Li(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted ZrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Zr(1)O6 octahedra, edges with two equivalent Li(3)O4 tetrahedra, and edges with four equivalent Li(1)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Zr(1), and one Zr(2) atom to form distorted OLi3Zr2 square pyramids that share corners with two equivalent O(1)Li3Zr2 square pyramids, edges with two equivalent O(4)Li6Zr hexagonal pyramids, and  an edgeedge with one O(1)Li3Zr2 square pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one Li(2), one Li(3), two equivalent Li(1), and one Zr(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one K(1), two equivalent Li(1), two equivalent Li(3), and one Zr(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), four equivalent Li(1), and one Zr(1) atom to form distorted OLi6Zr hexagonal pyramids that share  a cornercorner with one O(4)Li6Zr hexagonal pyramid,  an edgeedge with one O(4)Li6Zr hexagonal pyramid, and edges with four equivalent O(1)Li3Zr2 square pyramids.
K2Li14Zr3O14 crystallizes in the orthorhombic Immm space group. K(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(2) atoms. Both K(1)-O(3) bond lengths are 3.10 Å. All K(1)-O(2) bond lengths are 3.01 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Zr(1)O6 octahedra,  an edgeedge with one Zr(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(3) bond length is 1.97 Å. The Li(1)-O(4) bond length is 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 19-38°. Both Li(2)-O(2) bond lengths are 1.96 Å. Both Li(2)-O(4) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra, corners with two equivalent Zr(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra,  an edgeedge with one Zr(2)O6 octahedra,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-37°. The Li(3)-O(1) bond length is 1.91 Å. The Li(3)-O(2) bond length is 2.14 Å. Both Li(3)-O(3) bond lengths are 1.95 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Zr(2)O6 octahedra, and edges with eight equivalent Li(1)O4 tetrahedra. Both Zr(1)-O(4) bond lengths are 2.12 Å. All Zr(1)-O(1) bond lengths are 2.15 Å. In the second Zr site, Zr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted ZrO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Zr(1)O6 octahedra, edges with two equivalent Li(3)O4 tetrahedra, and edges with four equivalent Li(1)O4 tetrahedra. Both Zr(2)-O(1) bond lengths are 2.31 Å. Both Zr(2)-O(2) bond lengths are 2.07 Å. Both Zr(2)-O(3) bond lengths are 2.11 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), one Zr(1), and one Zr(2) atom to form distorted OLi3Zr2 square pyramids that share corners with two equivalent O(1)Li3Zr2 square pyramids, edges with two equivalent O(4)Li6Zr hexagonal pyramids, and  an edgeedge with one O(1)Li3Zr2 square pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one Li(2), one Li(3), two equivalent Li(1), and one Zr(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one K(1), two equivalent Li(1), two equivalent Li(3), and one Zr(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(2), four equivalent Li(1), and one Zr(1) atom to form distorted OLi6Zr hexagonal pyramids that share  a cornercorner with one O(4)Li6Zr hexagonal pyramid,  an edgeedge with one O(4)Li6Zr hexagonal pyramid, and edges with four equivalent O(1)Li3Zr2 square pyramids.