LiYb4(Ru2O7)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(9), and two equivalent O(4) atoms. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(7), one O(9), two equivalent O(3), and two equivalent O(8) atoms. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. In the third Yb site, Yb(3) is bonded to one O(1), one O(2), one O(7), one O(9), two equivalent O(4), and two equivalent O(6) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Ru(1)O6 octahedra and edges with four equivalent Ru(2)O6 octahedra. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(10), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form RuO6 octahedra that share corners with two equivalent Ru(3)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-47°. In the second Ru site, Ru(2) is bonded to one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, corners with two equivalent Ru(3)O6 octahedra, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-49°. In the third Ru site, Ru(3) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Yb(1), one Yb(3), and two equivalent Yb(2) atoms to form distorted OLiYb4 trigonal bipyramids that share corners with two equivalent O(10)Yb2Ru2 tetrahedra, corners with four equivalent O(8)Yb2Ru2 tetrahedra, corners with four equivalent O(2)Yb4 tetrahedra,  an edgeedge with one O(7)Yb2Ru2 tetrahedra, and edges with two equivalent O(6)Yb2Ru2 tetrahedra. In the second O site, O(2) is bonded to one Yb(1), one Yb(3), and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(7)Yb2Ru2 tetrahedra, corners with four equivalent O(6)Yb2Ru2 tetrahedra, corners with four equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(10)Yb2Ru2 tetrahedra, and edges with two equivalent O(8)Yb2Ru2 tetrahedra. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Yb(1), one Yb(2), one Ru(2), and one Ru(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Yb(2), one Yb(3), one Ru(1), and one Ru(2) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Yb(2), one Ru(1), and one Ru(3) atom. In the sixth O site, O(6) is bonded to one Yb(2), one Yb(3), one Ru(1), and one Ru(2) atom to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(6)Yb2Ru2 tetrahedra, corners with two equivalent O(7)Yb2Ru2 tetrahedra, corners with two equivalent O(2)Yb4 tetrahedra,  an edgeedge with one O(10)Yb2Ru2 tetrahedra,  an edgeedge with one O(8)Yb2Ru2 tetrahedra, and  an edgeedge with one O(1)LiYb4 trigonal bipyramid. In the seventh O site, O(7) is bonded to one Yb(1), one Yb(3), and two equivalent Ru(2) atoms to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(2)Yb4 tetrahedra, corners with four equivalent O(6)Yb2Ru2 tetrahedra, edges with two equivalent O(8)Yb2Ru2 tetrahedra, and  an edgeedge with one O(1)LiYb4 trigonal bipyramid. In the eighth O site, O(8) is bonded to one Yb(1), one Yb(2), one Ru(2), and one Ru(3) atom to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(10)Yb2Ru2 tetrahedra, corners with two equivalent O(8)Yb2Ru2 tetrahedra, corners with two equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(6)Yb2Ru2 tetrahedra,  an edgeedge with one O(7)Yb2Ru2 tetrahedra, and  an edgeedge with one O(2)Yb4 tetrahedra. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Li(1), one Yb(1), one Yb(3), and two equivalent Ru(2) atoms. In the tenth O site, O(10) is bonded to two equivalent Yb(2), one Ru(1), and one Ru(3) atom to form distorted OYb2Ru2 tetrahedra that share corners with four equivalent O(8)Yb2Ru2 tetrahedra, corners with two equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(2)Yb4 tetrahedra, and edges with two equivalent O(6)Yb2Ru2 tetrahedra.
LiYb4(Ru2O7)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(9), and two equivalent O(4) atoms. The Li(1)-O(1) bond length is 1.91 Å. The Li(1)-O(9) bond length is 1.95 Å. Both Li(1)-O(4) bond lengths are 1.96 Å. There are three inequivalent Yb sites. In the first Yb site, Yb(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(7), one O(9), two equivalent O(3), and two equivalent O(8) atoms. The Yb(1)-O(1) bond length is 2.26 Å. The Yb(1)-O(2) bond length is 2.19 Å. The Yb(1)-O(7) bond length is 2.36 Å. The Yb(1)-O(9) bond length is 2.62 Å. Both Yb(1)-O(3) bond lengths are 2.72 Å. Both Yb(1)-O(8) bond lengths are 2.51 Å. In the second Yb site, Yb(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom. The Yb(2)-O(1) bond length is 2.26 Å. The Yb(2)-O(10) bond length is 2.49 Å. The Yb(2)-O(2) bond length is 2.19 Å. The Yb(2)-O(3) bond length is 2.67 Å. The Yb(2)-O(4) bond length is 2.65 Å. The Yb(2)-O(5) bond length is 2.73 Å. The Yb(2)-O(6) bond length is 2.37 Å. The Yb(2)-O(8) bond length is 2.50 Å. In the third Yb site, Yb(3) is bonded to one O(1), one O(2), one O(7), one O(9), two equivalent O(4), and two equivalent O(6) atoms to form distorted YbO8 hexagonal bipyramids that share edges with two equivalent Ru(1)O6 octahedra and edges with four equivalent Ru(2)O6 octahedra. The Yb(3)-O(1) bond length is 2.39 Å. The Yb(3)-O(2) bond length is 2.20 Å. The Yb(3)-O(7) bond length is 2.55 Å. The Yb(3)-O(9) bond length is 2.59 Å. Both Yb(3)-O(4) bond lengths are 2.64 Å. Both Yb(3)-O(6) bond lengths are 2.59 Å. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(10), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form RuO6 octahedra that share corners with two equivalent Ru(3)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-47°. The Ru(1)-O(10) bond length is 1.95 Å. The Ru(1)-O(5) bond length is 1.93 Å. Both Ru(1)-O(4) bond lengths are 1.99 Å. Both Ru(1)-O(6) bond lengths are 1.96 Å. In the second Ru site, Ru(2) is bonded to one O(3), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, corners with two equivalent Ru(3)O6 octahedra, and edges with two equivalent Yb(3)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 43-49°. The Ru(2)-O(3) bond length is 1.94 Å. The Ru(2)-O(4) bond length is 1.99 Å. The Ru(2)-O(6) bond length is 1.96 Å. The Ru(2)-O(7) bond length is 1.98 Å. The Ru(2)-O(8) bond length is 1.95 Å. The Ru(2)-O(9) bond length is 2.02 Å. In the third Ru site, Ru(3) is bonded to one O(10), one O(5), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. The Ru(3)-O(10) bond length is 1.97 Å. The Ru(3)-O(5) bond length is 1.93 Å. Both Ru(3)-O(3) bond lengths are 1.95 Å. Both Ru(3)-O(8) bond lengths are 1.98 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Yb(1), one Yb(3), and two equivalent Yb(2) atoms to form distorted OLiYb4 trigonal bipyramids that share corners with two equivalent O(10)Yb2Ru2 tetrahedra, corners with four equivalent O(8)Yb2Ru2 tetrahedra, corners with four equivalent O(2)Yb4 tetrahedra,  an edgeedge with one O(7)Yb2Ru2 tetrahedra, and edges with two equivalent O(6)Yb2Ru2 tetrahedra. In the second O site, O(2) is bonded to one Yb(1), one Yb(3), and two equivalent Yb(2) atoms to form OYb4 tetrahedra that share corners with two equivalent O(7)Yb2Ru2 tetrahedra, corners with four equivalent O(6)Yb2Ru2 tetrahedra, corners with four equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(10)Yb2Ru2 tetrahedra, and edges with two equivalent O(8)Yb2Ru2 tetrahedra. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Yb(1), one Yb(2), one Ru(2), and one Ru(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Yb(2), one Yb(3), one Ru(1), and one Ru(2) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Yb(2), one Ru(1), and one Ru(3) atom. In the sixth O site, O(6) is bonded to one Yb(2), one Yb(3), one Ru(1), and one Ru(2) atom to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(6)Yb2Ru2 tetrahedra, corners with two equivalent O(7)Yb2Ru2 tetrahedra, corners with two equivalent O(2)Yb4 tetrahedra,  an edgeedge with one O(10)Yb2Ru2 tetrahedra,  an edgeedge with one O(8)Yb2Ru2 tetrahedra, and  an edgeedge with one O(1)LiYb4 trigonal bipyramid. In the seventh O site, O(7) is bonded to one Yb(1), one Yb(3), and two equivalent Ru(2) atoms to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(2)Yb4 tetrahedra, corners with four equivalent O(6)Yb2Ru2 tetrahedra, edges with two equivalent O(8)Yb2Ru2 tetrahedra, and  an edgeedge with one O(1)LiYb4 trigonal bipyramid. In the eighth O site, O(8) is bonded to one Yb(1), one Yb(2), one Ru(2), and one Ru(3) atom to form distorted OYb2Ru2 tetrahedra that share corners with two equivalent O(10)Yb2Ru2 tetrahedra, corners with two equivalent O(8)Yb2Ru2 tetrahedra, corners with two equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(6)Yb2Ru2 tetrahedra,  an edgeedge with one O(7)Yb2Ru2 tetrahedra, and  an edgeedge with one O(2)Yb4 tetrahedra. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Li(1), one Yb(1), one Yb(3), and two equivalent Ru(2) atoms. In the tenth O site, O(10) is bonded to two equivalent Yb(2), one Ru(1), and one Ru(3) atom to form distorted OYb2Ru2 tetrahedra that share corners with four equivalent O(8)Yb2Ru2 tetrahedra, corners with two equivalent O(1)LiYb4 trigonal bipyramids,  an edgeedge with one O(2)Yb4 tetrahedra, and edges with two equivalent O(6)Yb2Ru2 tetrahedra.