Li2Hf2O5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one O(5) and three equivalent O(1) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), and three equivalent O(5) atoms. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(2) atoms. In the second Hf site, Hf(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), three equivalent Li(1), and one Hf(1) atom to form distorted OLi4Hf trigonal bipyramids that share corners with two equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(5)Li4Hf trigonal bipyramids, corners with three equivalent O(2)Hf4 trigonal pyramids, edges with two equivalent O(1)Li4Hf trigonal bipyramids, and edges with two equivalent O(5)Li4Hf trigonal bipyramids. In the second O site, O(2) is bonded to one Hf(2) and three equivalent Hf(1) atoms to form distorted OHf4 trigonal pyramids that share  a cornercorner with one O(5)Li4Hf trigonal bipyramid, corners with three equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(2)Hf4 trigonal pyramids, and edges with two equivalent O(2)Hf4 trigonal pyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Hf(1), and two equivalent Hf(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Hf(1) and two equivalent Hf(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), three equivalent Li(2), and one Hf(2) atom to form OLi4Hf trigonal bipyramids that share corners with two equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(5)Li4Hf trigonal bipyramids,  a cornercorner with one O(2)Hf4 trigonal pyramid, edges with two equivalent O(1)Li4Hf trigonal bipyramids, and edges with two equivalent O(5)Li4Hf trigonal bipyramids.
Li2Hf2O5 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted see-saw-like geometry to one O(5) and three equivalent O(1) atoms. The Li(1)-O(5) bond length is 2.06 Å. There are a spread of Li(1)-O(1) bond distances ranging from 1.96-2.13 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), and three equivalent O(5) atoms. The Li(2)-O(1) bond length is 2.23 Å. The Li(2)-O(3) bond length is 2.56 Å. There are a spread of Li(2)-O(5) bond distances ranging from 1.97-2.04 Å. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(2) atoms. The Hf(1)-O(1) bond length is 1.92 Å. The Hf(1)-O(3) bond length is 2.14 Å. The Hf(1)-O(4) bond length is 2.05 Å. There are a spread of Hf(1)-O(2) bond distances ranging from 2.04-2.47 Å. In the second Hf site, Hf(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. The Hf(2)-O(2) bond length is 2.31 Å. The Hf(2)-O(5) bond length is 1.97 Å. There is one shorter (2.02 Å) and one longer (2.17 Å) Hf(2)-O(3) bond length. There is one shorter (2.11 Å) and one longer (2.18 Å) Hf(2)-O(4) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), three equivalent Li(1), and one Hf(1) atom to form distorted OLi4Hf trigonal bipyramids that share corners with two equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(5)Li4Hf trigonal bipyramids, corners with three equivalent O(2)Hf4 trigonal pyramids, edges with two equivalent O(1)Li4Hf trigonal bipyramids, and edges with two equivalent O(5)Li4Hf trigonal bipyramids. In the second O site, O(2) is bonded to one Hf(2) and three equivalent Hf(1) atoms to form distorted OHf4 trigonal pyramids that share  a cornercorner with one O(5)Li4Hf trigonal bipyramid, corners with three equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(2)Hf4 trigonal pyramids, and edges with two equivalent O(2)Hf4 trigonal pyramids. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Hf(1), and two equivalent Hf(2) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Hf(1) and two equivalent Hf(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), three equivalent Li(2), and one Hf(2) atom to form OLi4Hf trigonal bipyramids that share corners with two equivalent O(1)Li4Hf trigonal bipyramids, corners with two equivalent O(5)Li4Hf trigonal bipyramids,  a cornercorner with one O(2)Hf4 trigonal pyramid, edges with two equivalent O(1)Li4Hf trigonal bipyramids, and edges with two equivalent O(5)Li4Hf trigonal bipyramids.