LiPrO2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 trigonal pyramids that share corners with five equivalent Pr(1)O7 pentagonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Pr(1)O7 pentagonal bipyramids, and  a faceface with one Pr(1)O7 pentagonal bipyramid. Pr(1) is bonded to three equivalent O(2) and four equivalent O(1) atoms to form distorted PrO7 pentagonal bipyramids that share corners with four equivalent Pr(1)O7 pentagonal bipyramids, corners with five equivalent Li(1)O4 trigonal pyramids, edges with seven equivalent Pr(1)O7 pentagonal bipyramids, edges with three equivalent Li(1)O4 trigonal pyramids, and  a faceface with one Li(1)O4 trigonal pyramid. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and four equivalent Pr(1) atoms to form a mixture of distorted corner, edge, and face-sharing OLi2Pr4 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1) and three equivalent Pr(1) atoms.
LiPrO2 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 trigonal pyramids that share corners with five equivalent Pr(1)O7 pentagonal bipyramids, corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Pr(1)O7 pentagonal bipyramids, and  a faceface with one Pr(1)O7 pentagonal bipyramid. There is one shorter (2.10 Å) and one longer (2.13 Å) Li(1)-O(1) bond length. There is one shorter (1.90 Å) and one longer (1.97 Å) Li(1)-O(2) bond length. Pr(1) is bonded to three equivalent O(2) and four equivalent O(1) atoms to form distorted PrO7 pentagonal bipyramids that share corners with four equivalent Pr(1)O7 pentagonal bipyramids, corners with five equivalent Li(1)O4 trigonal pyramids, edges with seven equivalent Pr(1)O7 pentagonal bipyramids, edges with three equivalent Li(1)O4 trigonal pyramids, and  a faceface with one Li(1)O4 trigonal pyramid. There are a spread of Pr(1)-O(2) bond distances ranging from 2.39-2.49 Å. There are a spread of Pr(1)-O(1) bond distances ranging from 2.46-2.54 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1) and four equivalent Pr(1) atoms to form a mixture of distorted corner, edge, and face-sharing OLi2Pr4 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1) and three equivalent Pr(1) atoms.