Pr5(RuO6)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded to one O(3), two equivalent O(4), and four equivalent O(1) atoms to form distorted PrO7 pentagonal bipyramids that share corners with two equivalent Pr(3)O6 octahedra,  a cornercorner with one Pr(2)O7 pentagonal bipyramid,  an edgeedge with one Pr(3)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(1)O7 pentagonal bipyramids, and edges with four equivalent Pr(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 58°. In the second Pr site, Pr(2) is bonded to one O(3), two equivalent O(1), and four equivalent O(4) atoms to form distorted PrO7 pentagonal bipyramids that share corners with two equivalent Pr(3)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra,  a cornercorner with one Pr(1)O7 pentagonal bipyramid, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(2)O7 pentagonal bipyramids, and edges with four equivalent Pr(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-58°. In the third Pr site, Pr(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PrO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra, corners with four equivalent Pr(1)O7 pentagonal bipyramids, corners with four equivalent Pr(2)O7 pentagonal bipyramids, and edges with two equivalent Pr(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Ru(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with two equivalent Pr(3)O6 octahedra, corners with two equivalent Pr(2)O7 pentagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(1)O7 pentagonal bipyramids, and edges with two equivalent Pr(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Pr(2), one Pr(3), and two equivalent Pr(1) atoms to form OPr4 tetrahedra that share corners with three equivalent O(3)Pr2Ru2 tetrahedra, corners with four equivalent O(1)Pr4 tetrahedra, corners with six equivalent O(4)Pr3Ru tetrahedra,  an edgeedge with one O(4)Pr3Ru tetrahedra, and edges with three equivalent O(1)Pr4 tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Pr(3) and two equivalent Ru(1) atoms. In the third O site, O(3) is bonded to one Pr(1), one Pr(2), and two equivalent Ru(1) atoms to form distorted OPr2Ru2 tetrahedra that share corners with two equivalent O(4)Pr3Ru tetrahedra, corners with six equivalent O(1)Pr4 tetrahedra,  an edgeedge with one O(3)Pr2Ru2 tetrahedra, and edges with four equivalent O(4)Pr3Ru tetrahedra. In the fourth O site, O(4) is bonded to one Pr(1), two equivalent Pr(2), and one Ru(1) atom to form distorted OPr3Ru tetrahedra that share  a cornercorner with one O(3)Pr2Ru2 tetrahedra, corners with four equivalent O(4)Pr3Ru tetrahedra, corners with six equivalent O(1)Pr4 tetrahedra,  an edgeedge with one O(1)Pr4 tetrahedra, edges with two equivalent O(3)Pr2Ru2 tetrahedra, and edges with two equivalent O(4)Pr3Ru tetrahedra.
Pr5(RuO6)2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Pr sites. In the first Pr site, Pr(1) is bonded to one O(3), two equivalent O(4), and four equivalent O(1) atoms to form distorted PrO7 pentagonal bipyramids that share corners with two equivalent Pr(3)O6 octahedra,  a cornercorner with one Pr(2)O7 pentagonal bipyramid,  an edgeedge with one Pr(3)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(1)O7 pentagonal bipyramids, and edges with four equivalent Pr(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 58°. The Pr(1)-O(3) bond length is 2.47 Å. Both Pr(1)-O(4) bond lengths are 2.53 Å. There are two shorter (2.39 Å) and two longer (2.42 Å) Pr(1)-O(1) bond lengths. In the second Pr site, Pr(2) is bonded to one O(3), two equivalent O(1), and four equivalent O(4) atoms to form distorted PrO7 pentagonal bipyramids that share corners with two equivalent Pr(3)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra,  a cornercorner with one Pr(1)O7 pentagonal bipyramid, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(2)O7 pentagonal bipyramids, and edges with four equivalent Pr(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-58°. The Pr(2)-O(3) bond length is 2.45 Å. Both Pr(2)-O(1) bond lengths are 2.40 Å. There are two shorter (2.40 Å) and two longer (2.52 Å) Pr(2)-O(4) bond lengths. In the third Pr site, Pr(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PrO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra, corners with four equivalent Pr(1)O7 pentagonal bipyramids, corners with four equivalent Pr(2)O7 pentagonal bipyramids, and edges with two equivalent Pr(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Both Pr(3)-O(2) bond lengths are 2.44 Å. All Pr(3)-O(1) bond lengths are 2.42 Å. Ru(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with two equivalent Pr(3)O6 octahedra, corners with two equivalent Pr(2)O7 pentagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Pr(1)O7 pentagonal bipyramids, and edges with two equivalent Pr(2)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Both Ru(1)-O(2) bond lengths are 1.99 Å. Both Ru(1)-O(3) bond lengths are 2.05 Å. Both Ru(1)-O(4) bond lengths are 1.94 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Pr(2), one Pr(3), and two equivalent Pr(1) atoms to form OPr4 tetrahedra that share corners with three equivalent O(3)Pr2Ru2 tetrahedra, corners with four equivalent O(1)Pr4 tetrahedra, corners with six equivalent O(4)Pr3Ru tetrahedra,  an edgeedge with one O(4)Pr3Ru tetrahedra, and edges with three equivalent O(1)Pr4 tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Pr(3) and two equivalent Ru(1) atoms. In the third O site, O(3) is bonded to one Pr(1), one Pr(2), and two equivalent Ru(1) atoms to form distorted OPr2Ru2 tetrahedra that share corners with two equivalent O(4)Pr3Ru tetrahedra, corners with six equivalent O(1)Pr4 tetrahedra,  an edgeedge with one O(3)Pr2Ru2 tetrahedra, and edges with four equivalent O(4)Pr3Ru tetrahedra. In the fourth O site, O(4) is bonded to one Pr(1), two equivalent Pr(2), and one Ru(1) atom to form distorted OPr3Ru tetrahedra that share  a cornercorner with one O(3)Pr2Ru2 tetrahedra, corners with four equivalent O(4)Pr3Ru tetrahedra, corners with six equivalent O(1)Pr4 tetrahedra,  an edgeedge with one O(1)Pr4 tetrahedra, edges with two equivalent O(3)Pr2Ru2 tetrahedra, and edges with two equivalent O(4)Pr3Ru tetrahedra.