KLi2(RuO2)6 crystallizes in the hexagonal P-6 space group. K(1) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form distorted LiO6 pentagonal pyramids that share corners with six equivalent Ru(1)O6 octahedra, corners with six equivalent Ru(2)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and faces with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 34-67°. In the second Li site, Li(2) is bonded to six equivalent O(1) atoms to form distorted LiO6 pentagonal pyramids that share corners with six equivalent Ru(1)O6 octahedra, corners with six equivalent Ru(2)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and faces with two equivalent Li(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 33-67°. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with four equivalent Ru(2)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 49-51°. In the second Ru site, Ru(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form RuO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and  an edgeedge with one Li(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 49-51°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ru(1), and two equivalent Ru(2) atoms to form distorted OLi2Ru3 trigonal bipyramids that share corners with three equivalent O(3)KRu3 tetrahedra, corners with four equivalent O(1)Li2Ru3 trigonal bipyramids,  an edgeedge with one O(3)KRu3 tetrahedra, edges with two equivalent O(2)Li2Ru3 trigonal bipyramids, and edges with four equivalent O(1)Li2Ru3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Ru(2), and two equivalent Ru(1) atoms to form distorted OLi2Ru3 trigonal bipyramids that share corners with four equivalent O(3)KRu3 tetrahedra, corners with four equivalent O(2)Li2Ru3 trigonal bipyramids, edges with two equivalent O(1)Li2Ru3 trigonal bipyramids, and edges with four equivalent O(2)Li2Ru3 trigonal bipyramids. In the third O site, O(3) is bonded to one K(1), one Ru(1), and two equivalent Ru(2) atoms to form distorted OKRu3 tetrahedra that share corners with four equivalent O(3)KRu3 tetrahedra, corners with three equivalent O(1)Li2Ru3 trigonal bipyramids, corners with four equivalent O(2)Li2Ru3 trigonal bipyramids, and  an edgeedge with one O(1)Li2Ru3 trigonal bipyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent K(1), one Ru(2), and two equivalent Ru(1) atoms.
KLi2(RuO2)6 crystallizes in the hexagonal P-6 space group. K(1) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. All K(1)-O(3) bond lengths are 2.59 Å. All K(1)-O(4) bond lengths are 2.88 Å. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent O(2) atoms to form distorted LiO6 pentagonal pyramids that share corners with six equivalent Ru(1)O6 octahedra, corners with six equivalent Ru(2)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and faces with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 34-67°. All Li(1)-O(2) bond lengths are 2.19 Å. In the second Li site, Li(2) is bonded to six equivalent O(1) atoms to form distorted LiO6 pentagonal pyramids that share corners with six equivalent Ru(1)O6 octahedra, corners with six equivalent Ru(2)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and faces with two equivalent Li(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 33-67°. All Li(2)-O(1) bond lengths are 2.19 Å. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with four equivalent Ru(2)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 49-51°. The Ru(1)-O(1) bond length is 2.06 Å. The Ru(1)-O(3) bond length is 2.01 Å. Both Ru(1)-O(2) bond lengths are 2.08 Å. Both Ru(1)-O(4) bond lengths are 2.02 Å. In the second Ru site, Ru(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form RuO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and  an edgeedge with one Li(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 49-51°. The Ru(2)-O(2) bond length is 2.05 Å. The Ru(2)-O(4) bond length is 2.03 Å. Both Ru(2)-O(1) bond lengths are 2.09 Å. Both Ru(2)-O(3) bond lengths are 2.01 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ru(1), and two equivalent Ru(2) atoms to form distorted OLi2Ru3 trigonal bipyramids that share corners with three equivalent O(3)KRu3 tetrahedra, corners with four equivalent O(1)Li2Ru3 trigonal bipyramids,  an edgeedge with one O(3)KRu3 tetrahedra, edges with two equivalent O(2)Li2Ru3 trigonal bipyramids, and edges with four equivalent O(1)Li2Ru3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Ru(2), and two equivalent Ru(1) atoms to form distorted OLi2Ru3 trigonal bipyramids that share corners with four equivalent O(3)KRu3 tetrahedra, corners with four equivalent O(2)Li2Ru3 trigonal bipyramids, edges with two equivalent O(1)Li2Ru3 trigonal bipyramids, and edges with four equivalent O(2)Li2Ru3 trigonal bipyramids. In the third O site, O(3) is bonded to one K(1), one Ru(1), and two equivalent Ru(2) atoms to form distorted OKRu3 tetrahedra that share corners with four equivalent O(3)KRu3 tetrahedra, corners with three equivalent O(1)Li2Ru3 trigonal bipyramids, corners with four equivalent O(2)Li2Ru3 trigonal bipyramids, and  an edgeedge with one O(1)Li2Ru3 trigonal bipyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent K(1), one Ru(2), and two equivalent Ru(1) atoms.