Li2Hf2O5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. Hf(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing HfO6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Hf(1) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent Hf(1) atoms to form OLiHf3 trigonal pyramids that share  a cornercorner with one O(3)Li4Hf2 octahedra, corners with four equivalent O(2)LiHf3 trigonal pyramids, edges with two equivalent O(3)Li4Hf2 octahedra, and  an edgeedge with one O(2)LiHf3 trigonal pyramid. The corner-sharing octahedral tilt angles are 84°. In the third O site, O(3) is bonded to four equivalent Li(1) and two equivalent Hf(1) atoms to form distorted OLi4Hf2 octahedra that share corners with two equivalent O(2)LiHf3 trigonal pyramids, edges with two equivalent O(3)Li4Hf2 octahedra, and edges with four equivalent O(2)LiHf3 trigonal pyramids. In the fourth O site, O(4) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Hf(1) atoms.
Li2Hf2O5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.00 Å. There is one shorter (2.12 Å) and one longer (2.52 Å) Li(1)-O(3) bond length. Hf(1) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing HfO6 octahedra. The corner-sharing octahedral tilt angles range from 0-54°. The Hf(1)-O(1) bond length is 2.02 Å. The Hf(1)-O(3) bond length is 2.10 Å. The Hf(1)-O(4) bond length is 2.07 Å. There are a spread of Hf(1)-O(2) bond distances ranging from 2.13-2.15 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Hf(1) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent Hf(1) atoms to form OLiHf3 trigonal pyramids that share  a cornercorner with one O(3)Li4Hf2 octahedra, corners with four equivalent O(2)LiHf3 trigonal pyramids, edges with two equivalent O(3)Li4Hf2 octahedra, and  an edgeedge with one O(2)LiHf3 trigonal pyramid. The corner-sharing octahedral tilt angles are 84°. In the third O site, O(3) is bonded to four equivalent Li(1) and two equivalent Hf(1) atoms to form distorted OLi4Hf2 octahedra that share corners with two equivalent O(2)LiHf3 trigonal pyramids, edges with two equivalent O(3)Li4Hf2 octahedra, and edges with four equivalent O(2)LiHf3 trigonal pyramids. In the fourth O site, O(4) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent Hf(1) atoms.