LiEr4Zr4O14 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms. There are three inequivalent Er sites. In the first Er site, Er(1) is bonded to one O(1), one O(10), two equivalent O(2), and two equivalent O(9) atoms to form a mixture of distorted corner and edge-sharing ErO6 octahedra. The corner-sharing octahedral tilt angles range from 47-74°. In the second Er site, Er(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. In the third Er site, Er(3) is bonded in a 6-coordinate geometry to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms. In the second Zr site, Zr(2) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(2), and two equivalent O(4) atoms. In the third Zr site, Zr(3) is bonded to one O(3), one O(7), one O(8), two equivalent O(5), and two equivalent O(6) atoms to form a mixture of distorted corner and edge-sharing ZrO7 hexagonal pyramids. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Er(1) and two equivalent Zr(1) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with four equivalent O(9)Er3Zr tetrahedra. In the second O site, O(2) is bonded to one Er(2), two equivalent Er(1), and one Zr(2) atom to form distorted OEr3Zr trigonal pyramids that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with two equivalent O(9)Er3Zr tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(9)Er3Zr tetrahedra, and edges with two equivalent O(10)Er2Zr2 tetrahedra. In the third O site, O(3) is bonded to two equivalent Er(2) and two equivalent Zr(3) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids, and  an edgeedge with one O(7)Zr4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Zr(2) atoms. In the fifth O site, O(5) is bonded to one Er(3), one Zr(1), and two equivalent Zr(3) atoms to form OErZr3 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with two equivalent O(9)Er3Zr tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra,  an edgeedge with one O(9)Er3Zr tetrahedra, and edges with two equivalent O(7)Zr4 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Er(2), and two equivalent Zr(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Zr(1) and two equivalent Zr(3) atoms to form OZr4 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra,  an edgeedge with one O(1)Er2Zr2 tetrahedra,  an edgeedge with one O(3)Er2Zr2 tetrahedra, and edges with four equivalent O(5)ErZr3 tetrahedra. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Er(3), and two equivalent Zr(3) atoms. In the ninth O site, O(9) is bonded to one Er(3), two equivalent Er(1), and one Zr(1) atom to form distorted OEr3Zr tetrahedra that share corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with two equivalent O(5)ErZr3 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra, corners with two equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(5)ErZr3 tetrahedra, edges with two equivalent O(1)Er2Zr2 tetrahedra, and  an edgeedge with one O(2)Er3Zr trigonal pyramid. In the tenth O site, O(10) is bonded to two equivalent Er(1) and two equivalent Zr(2) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra, and edges with four equivalent O(2)Er3Zr trigonal pyramids.
LiEr4Zr4O14 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms. Both Li(1)-O(4) bond lengths are 2.46 Å. Both Li(1)-O(6) bond lengths are 1.90 Å. Both Li(1)-O(8) bond lengths are 2.10 Å. There are three inequivalent Er sites. In the first Er site, Er(1) is bonded to one O(1), one O(10), two equivalent O(2), and two equivalent O(9) atoms to form a mixture of distorted corner and edge-sharing ErO6 octahedra. The corner-sharing octahedral tilt angles range from 47-74°. The Er(1)-O(1) bond length is 2.33 Å. The Er(1)-O(10) bond length is 2.13 Å. Both Er(1)-O(2) bond lengths are 2.43 Å. Both Er(1)-O(9) bond lengths are 2.18 Å. In the second Er site, Er(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Both Er(2)-O(2) bond lengths are 2.27 Å. Both Er(2)-O(3) bond lengths are 2.14 Å. Both Er(2)-O(6) bond lengths are 2.46 Å. In the third Er site, Er(3) is bonded in a 6-coordinate geometry to two equivalent O(5), two equivalent O(8), and two equivalent O(9) atoms. Both Er(3)-O(5) bond lengths are 2.29 Å. Both Er(3)-O(8) bond lengths are 2.78 Å. Both Er(3)-O(9) bond lengths are 2.21 Å. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a distorted body-centered cubic geometry to two equivalent O(1), two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms. Both Zr(1)-O(1) bond lengths are 2.18 Å. Both Zr(1)-O(5) bond lengths are 2.14 Å. Both Zr(1)-O(7) bond lengths are 2.25 Å. Both Zr(1)-O(9) bond lengths are 2.63 Å. In the second Zr site, Zr(2) is bonded in a 6-coordinate geometry to two equivalent O(10), two equivalent O(2), and two equivalent O(4) atoms. Both Zr(2)-O(10) bond lengths are 2.31 Å. Both Zr(2)-O(2) bond lengths are 2.24 Å. Both Zr(2)-O(4) bond lengths are 2.06 Å. In the third Zr site, Zr(3) is bonded to one O(3), one O(7), one O(8), two equivalent O(5), and two equivalent O(6) atoms to form a mixture of distorted corner and edge-sharing ZrO7 hexagonal pyramids. The Zr(3)-O(3) bond length is 2.24 Å. The Zr(3)-O(7) bond length is 2.11 Å. The Zr(3)-O(8) bond length is 2.13 Å. Both Zr(3)-O(5) bond lengths are 2.30 Å. Both Zr(3)-O(6) bond lengths are 2.12 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Er(1) and two equivalent Zr(1) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(7)Zr4 tetrahedra, and edges with four equivalent O(9)Er3Zr tetrahedra. In the second O site, O(2) is bonded to one Er(2), two equivalent Er(1), and one Zr(2) atom to form distorted OEr3Zr trigonal pyramids that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with two equivalent O(9)Er3Zr tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(9)Er3Zr tetrahedra, and edges with two equivalent O(10)Er2Zr2 tetrahedra. In the third O site, O(3) is bonded to two equivalent Er(2) and two equivalent Zr(3) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra, corners with four equivalent O(2)Er3Zr trigonal pyramids, and  an edgeedge with one O(7)Zr4 tetrahedra. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Zr(2) atoms. In the fifth O site, O(5) is bonded to one Er(3), one Zr(1), and two equivalent Zr(3) atoms to form OErZr3 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(3)Er2Zr2 tetrahedra, corners with two equivalent O(9)Er3Zr tetrahedra, corners with four equivalent O(5)ErZr3 tetrahedra,  an edgeedge with one O(9)Er3Zr tetrahedra, and edges with two equivalent O(7)Zr4 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Er(2), and two equivalent Zr(3) atoms. In the seventh O site, O(7) is bonded to two equivalent Zr(1) and two equivalent Zr(3) atoms to form OZr4 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra,  an edgeedge with one O(1)Er2Zr2 tetrahedra,  an edgeedge with one O(3)Er2Zr2 tetrahedra, and edges with four equivalent O(5)ErZr3 tetrahedra. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Er(3), and two equivalent Zr(3) atoms. In the ninth O site, O(9) is bonded to one Er(3), two equivalent Er(1), and one Zr(1) atom to form distorted OEr3Zr tetrahedra that share corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with two equivalent O(5)ErZr3 tetrahedra, corners with two equivalent O(7)Zr4 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra, corners with two equivalent O(2)Er3Zr trigonal pyramids,  an edgeedge with one O(5)ErZr3 tetrahedra, edges with two equivalent O(1)Er2Zr2 tetrahedra, and  an edgeedge with one O(2)Er3Zr trigonal pyramid. In the tenth O site, O(10) is bonded to two equivalent Er(1) and two equivalent Zr(2) atoms to form OEr2Zr2 tetrahedra that share corners with two equivalent O(1)Er2Zr2 tetrahedra, corners with two equivalent O(10)Er2Zr2 tetrahedra, corners with four equivalent O(9)Er3Zr tetrahedra, and edges with four equivalent O(2)Er3Zr trigonal pyramids.