LiHoO2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted T-shaped geometry to one O(2) and two equivalent O(1) atoms. Ho(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing HoO6 octahedra. The corner-sharing octahedral tilt angles range from 17-35°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and three equivalent Ho(1) atoms to form distorted OLi2Ho3 square pyramids that share corners with two equivalent O(1)Li2Ho3 square pyramids, corners with seven equivalent O(2)LiHo3 tetrahedra, edges with three equivalent O(1)Li2Ho3 square pyramids, and edges with two equivalent O(2)LiHo3 tetrahedra. In the second O site, O(2) is bonded to one Li(1) and three equivalent Ho(1) atoms to form distorted OLiHo3 tetrahedra that share corners with seven equivalent O(1)Li2Ho3 square pyramids, corners with four equivalent O(2)LiHo3 tetrahedra, edges with two equivalent O(1)Li2Ho3 square pyramids, and  an edgeedge with one O(2)LiHo3 tetrahedra.
LiHoO2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a distorted T-shaped geometry to one O(2) and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 1.90 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) Li(1)-O(1) bond length. Ho(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing HoO6 octahedra. The corner-sharing octahedral tilt angles range from 17-35°. There are a spread of Ho(1)-O(1) bond distances ranging from 2.27-2.33 Å. There are a spread of Ho(1)-O(2) bond distances ranging from 2.19-2.26 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and three equivalent Ho(1) atoms to form distorted OLi2Ho3 square pyramids that share corners with two equivalent O(1)Li2Ho3 square pyramids, corners with seven equivalent O(2)LiHo3 tetrahedra, edges with three equivalent O(1)Li2Ho3 square pyramids, and edges with two equivalent O(2)LiHo3 tetrahedra. In the second O site, O(2) is bonded to one Li(1) and three equivalent Ho(1) atoms to form distorted OLiHo3 tetrahedra that share corners with seven equivalent O(1)Li2Ho3 square pyramids, corners with four equivalent O(2)LiHo3 tetrahedra, edges with two equivalent O(1)Li2Ho3 square pyramids, and  an edgeedge with one O(2)LiHo3 tetrahedra.