Li4Y3ZrO8 is Caswellsilverite-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Y(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Y(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form YO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Y(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the second Y site, Y(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form YO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Zr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Zr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Y(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Y(1), one Y(2), and one Zr(1) atom to form OLi3Y2Zr octahedra that share corners with six equivalent O(1)Li3Y2Zr octahedra, edges with four equivalent O(1)Li3Y2Zr octahedra, edges with four equivalent O(2)Li3Y2Zr octahedra, and edges with four equivalent O(3)Li3Y3 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Y(1), and one Zr(1) atom to form distorted OLi3Y2Zr octahedra that share corners with two equivalent O(2)Li3Y2Zr octahedra, corners with four equivalent O(3)Li3Y3 octahedra, edges with two equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(3)Li3Y3 octahedra, and edges with eight equivalent O(1)Li3Y2Zr octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Y(2), and two equivalent Y(1) atoms to form OLi3Y3 octahedra that share corners with two equivalent O(3)Li3Y3 octahedra, corners with four equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(3)Li3Y3 octahedra, and edges with eight equivalent O(1)Li3Y2Zr octahedra. The corner-sharing octahedral tilt angles range from 0-8°.
Li4Y3ZrO8 is Caswellsilverite-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted LiO6 octahedra that share corners with two equivalent Zr(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Li(1)-O(2) bond lengths are 2.61 Å. All Li(1)-O(1) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Y(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Li(2)-O(1) bond lengths are 2.48 Å. Both Li(2)-O(2) bond lengths are 2.28 Å. Both Li(2)-O(3) bond lengths are 2.23 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Y(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Li(3)-O(3) bond lengths are 2.52 Å. All Li(3)-O(1) bond lengths are 2.26 Å. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form YO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Y(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Y(2)O6 octahedra, edges with two equivalent Zr(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Y(1)-O(1) bond lengths are 2.36 Å. Both Y(1)-O(2) bond lengths are 2.24 Å. Both Y(1)-O(3) bond lengths are 2.26 Å. In the second Y site, Y(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form YO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Zr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Both Y(2)-O(3) bond lengths are 2.31 Å. All Y(2)-O(1) bond lengths are 2.31 Å. Zr(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Y(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Y(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Both Zr(1)-O(2) bond lengths are 2.23 Å. All Zr(1)-O(1) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Y(1), one Y(2), and one Zr(1) atom to form OLi3Y2Zr octahedra that share corners with six equivalent O(1)Li3Y2Zr octahedra, edges with four equivalent O(1)Li3Y2Zr octahedra, edges with four equivalent O(2)Li3Y2Zr octahedra, and edges with four equivalent O(3)Li3Y3 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Y(1), and one Zr(1) atom to form distorted OLi3Y2Zr octahedra that share corners with two equivalent O(2)Li3Y2Zr octahedra, corners with four equivalent O(3)Li3Y3 octahedra, edges with two equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(3)Li3Y3 octahedra, and edges with eight equivalent O(1)Li3Y2Zr octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Y(2), and two equivalent Y(1) atoms to form OLi3Y3 octahedra that share corners with two equivalent O(3)Li3Y3 octahedra, corners with four equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(2)Li3Y2Zr octahedra, edges with two equivalent O(3)Li3Y3 octahedra, and edges with eight equivalent O(1)Li3Y2Zr octahedra. The corner-sharing octahedral tilt angles range from 0-8°.