Li3GdO3 crystallizes in the trigonal P-3c1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2) and three equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Gd(2)O6 octahedra,  a cornercorner with one Gd(3)O6 octahedra, corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(3)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 25-57°. In the second Li site, Li(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Gd(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(2)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-57°. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Gd(2)O6 octahedra,  a cornercorner with one Gd(3)O6 octahedra, corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-57°. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form GdO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(3)O6 octahedra, edges with two equivalent Gd(2)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. In the second Gd site, Gd(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form GdO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with six equivalent Li(2)O4 tetrahedra, edges with three equivalent Gd(1)O6 octahedra, edges with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent Li(3)O4 tetrahedra. In the third Gd site, Gd(3) is bonded to six equivalent O(1) atoms to form GdO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(3)O4 tetrahedra, edges with three equivalent Gd(1)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), three equivalent Li(1), one Gd(1), and one Gd(3) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), one Gd(1), and one Gd(2) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids. In the third O site, O(3) is bonded to two equivalent Li(2), two equivalent Li(3), one Gd(1), and one Gd(2) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids.
Li3GdO3 crystallizes in the trigonal P-3c1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2) and three equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Gd(2)O6 octahedra,  a cornercorner with one Gd(3)O6 octahedra, corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(3)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 25-57°. The Li(1)-O(2) bond length is 2.18 Å. There are a spread of Li(1)-O(1) bond distances ranging from 1.97-2.10 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Gd(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(2)O6 octahedra,  an edgeedge with one Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 24-57°. There is one shorter (1.99 Å) and one longer (2.09 Å) Li(2)-O(2) bond length. There is one shorter (1.97 Å) and one longer (2.19 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share  a cornercorner with one Gd(2)O6 octahedra,  a cornercorner with one Gd(3)O6 octahedra, corners with two equivalent Gd(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(1)O6 octahedra,  an edgeedge with one Gd(2)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-57°. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(2) bond length is 1.97 Å. There is one shorter (1.99 Å) and one longer (2.10 Å) Li(3)-O(3) bond length. There are three inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form GdO6 octahedra that share corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Gd(3)O6 octahedra, edges with two equivalent Gd(2)O6 octahedra, edges with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. Both Gd(1)-O(1) bond lengths are 2.32 Å. Both Gd(1)-O(2) bond lengths are 2.33 Å. Both Gd(1)-O(3) bond lengths are 2.33 Å. In the second Gd site, Gd(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form GdO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with six equivalent Li(2)O4 tetrahedra, edges with three equivalent Gd(1)O6 octahedra, edges with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent Li(3)O4 tetrahedra. All Gd(2)-O(2) bond lengths are 2.34 Å. All Gd(2)-O(3) bond lengths are 2.33 Å. In the third Gd site, Gd(3) is bonded to six equivalent O(1) atoms to form GdO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Li(3)O4 tetrahedra, edges with three equivalent Gd(1)O6 octahedra, and edges with six equivalent Li(1)O4 tetrahedra. All Gd(3)-O(1) bond lengths are 2.34 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), three equivalent Li(1), one Gd(1), and one Gd(3) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), two equivalent Li(2), one Gd(1), and one Gd(2) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids. In the third O site, O(3) is bonded to two equivalent Li(2), two equivalent Li(3), one Gd(1), and one Gd(2) atom to form a mixture of distorted corner and edge-sharing OLi4Gd2 pentagonal pyramids.