LiHo2O3 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ho(2)O5 trigonal bipyramid, corners with six equivalent Li(1)O5 trigonal bipyramids, and edges with three equivalent Ho(2)O5 trigonal bipyramids. There are two inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(3), and three equivalent O(2) atoms. In the second Ho site, Ho(2) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form HoO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with six equivalent Ho(2)O5 trigonal bipyramids, and edges with three equivalent Li(1)O5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ho(1), and three equivalent Ho(2) atoms to form a mixture of corner and edge-sharing OLiHo4 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Ho(2), and three equivalent Ho(1) atoms to form a mixture of corner and edge-sharing OLiHo4 trigonal bipyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to three equivalent Li(1), one Ho(2), and two equivalent Ho(1) atoms.
LiHo2O3 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ho(2)O5 trigonal bipyramid, corners with six equivalent Li(1)O5 trigonal bipyramids, and edges with three equivalent Ho(2)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 2.26 Å. The Li(1)-O(2) bond length is 2.16 Å. There is one shorter (2.16 Å) and two longer (2.35 Å) Li(1)-O(3) bond lengths. There are two inequivalent Ho sites. In the first Ho site, Ho(1) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(3), and three equivalent O(2) atoms. The Ho(1)-O(1) bond length is 2.33 Å. Both Ho(1)-O(3) bond lengths are 2.37 Å. There is one shorter (2.24 Å) and two longer (2.32 Å) Ho(1)-O(2) bond lengths. In the second Ho site, Ho(2) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form HoO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 trigonal bipyramid, corners with six equivalent Ho(2)O5 trigonal bipyramids, and edges with three equivalent Li(1)O5 trigonal bipyramids. The Ho(2)-O(2) bond length is 2.30 Å. The Ho(2)-O(3) bond length is 2.24 Å. There is one shorter (2.27 Å) and two longer (2.29 Å) Ho(2)-O(1) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ho(1), and three equivalent Ho(2) atoms to form a mixture of corner and edge-sharing OLiHo4 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Ho(2), and three equivalent Ho(1) atoms to form a mixture of corner and edge-sharing OLiHo4 trigonal bipyramids. In the third O site, O(3) is bonded in a 6-coordinate geometry to three equivalent Li(1), one Ho(2), and two equivalent Ho(1) atoms.