LiSm3Bi(Ru2O7)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(4) atoms. There are two inequivalent Sm sites. In the first Sm site, Sm(1) 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(6), one O(7), and one O(8) atom. In the second Sm site, Sm(2) is bonded in a distorted body-centered cubic geometry to one O(1), one O(2), one O(5), one O(9), two equivalent O(4), and two equivalent O(8) atoms. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(3), one O(7), two equivalent O(4), and two equivalent O(8) atoms to form distorted corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. In the second Ru site, Ru(2) is bonded to one O(10), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third Ru site, Ru(3) is bonded to one O(3), one O(7), two equivalent O(10), and two equivalent O(6) atoms to form corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. Bi(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(5), one O(9), two equivalent O(10), and two equivalent O(6) atoms. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Sm(2), two equivalent Sm(1), and one Bi(1) atom to form OSm3Bi tetrahedra that share corners with two equivalent O(9)SmBiRu2 tetrahedra, corners with four equivalent O(8)Sm2Ru2 tetrahedra, corners with four equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(3)Sm2Ru2 tetrahedra, and edges with two equivalent O(6)SmBiRu2 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Sm(2), two equivalent Sm(1), and one Bi(1) atom to form distorted OLiSm3Bi trigonal bipyramids that share corners with two equivalent O(3)Sm2Ru2 tetrahedra, corners with four equivalent O(1)Sm3Bi tetrahedra, corners with four equivalent O(6)SmBiRu2 tetrahedra,  an edgeedge with one O(9)SmBiRu2 tetrahedra, and edges with two equivalent O(8)Sm2Ru2 tetrahedra. In the third O site, O(3) is bonded to two equivalent Sm(1), one Ru(1), and one Ru(3) atom to form distorted OSm2Ru2 tetrahedra that share corners with four equivalent O(6)SmBiRu2 tetrahedra, corners with two equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(1)Sm3Bi tetrahedra, and edges with two equivalent O(8)Sm2Ru2 tetrahedra. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Sm(1), one Sm(2), one Ru(1), and one Ru(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Sm(2), two equivalent Ru(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded to one Sm(1), one Ru(2), one Ru(3), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(3)Sm2Ru2 tetrahedra, corners with two equivalent O(6)SmBiRu2 tetrahedra, corners with two equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(8)Sm2Ru2 tetrahedra,  an edgeedge with one O(1)Sm3Bi tetrahedra, and  an edgeedge with one O(9)SmBiRu2 tetrahedra. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Sm(1), one Ru(1), and one Ru(3) atom. In the eighth O site, O(8) is bonded to one Sm(1), one Sm(2), one Ru(1), and one Ru(2) atom to form distorted OSm2Ru2 tetrahedra that share corners with two equivalent O(8)Sm2Ru2 tetrahedra, corners with two equivalent O(1)Sm3Bi tetrahedra, corners with two equivalent O(9)SmBiRu2 tetrahedra,  an edgeedge with one O(3)Sm2Ru2 tetrahedra,  an edgeedge with one O(6)SmBiRu2 tetrahedra, and  an edgeedge with one O(2)LiSm3Bi trigonal bipyramid. In the ninth O site, O(9) is bonded to one Sm(2), two equivalent Ru(2), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(1)Sm3Bi tetrahedra, corners with four equivalent O(8)Sm2Ru2 tetrahedra, edges with two equivalent O(6)SmBiRu2 tetrahedra, and  an edgeedge with one O(2)LiSm3Bi trigonal bipyramid. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one Sm(1), one Ru(2), one Ru(3), and one Bi(1) atom.
LiSm3Bi(Ru2O7)2 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(4) atoms. The Li(1)-O(2) bond length is 2.41 Å. The Li(1)-O(5) bond length is 1.89 Å. The Li(1)-O(7) bond length is 2.63 Å. Both Li(1)-O(4) bond lengths are 1.90 Å. There are two inequivalent Sm sites. In the first Sm site, Sm(1) 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(6), one O(7), and one O(8) atom. The Sm(1)-O(1) bond length is 2.24 Å. The Sm(1)-O(10) bond length is 2.79 Å. The Sm(1)-O(2) bond length is 2.27 Å. The Sm(1)-O(3) bond length is 2.48 Å. The Sm(1)-O(4) bond length is 2.62 Å. The Sm(1)-O(6) bond length is 2.43 Å. The Sm(1)-O(7) bond length is 2.60 Å. The Sm(1)-O(8) bond length is 2.40 Å. In the second Sm site, Sm(2) is bonded in a distorted body-centered cubic geometry to one O(1), one O(2), one O(5), one O(9), two equivalent O(4), and two equivalent O(8) atoms. The Sm(2)-O(1) bond length is 2.23 Å. The Sm(2)-O(2) bond length is 2.36 Å. The Sm(2)-O(5) bond length is 2.68 Å. The Sm(2)-O(9) bond length is 2.48 Å. Both Sm(2)-O(4) bond lengths are 2.53 Å. Both Sm(2)-O(8) bond lengths are 2.56 Å. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(3), one O(7), two equivalent O(4), and two equivalent O(8) atoms to form distorted corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The Ru(1)-O(3) bond length is 2.06 Å. The Ru(1)-O(7) bond length is 2.03 Å. Both Ru(1)-O(4) bond lengths are 2.10 Å. Both Ru(1)-O(8) bond lengths are 2.01 Å. In the second Ru site, Ru(2) is bonded to one O(10), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form distorted corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The Ru(2)-O(10) bond length is 1.97 Å. The Ru(2)-O(4) bond length is 2.10 Å. The Ru(2)-O(5) bond length is 2.03 Å. The Ru(2)-O(6) bond length is 2.05 Å. The Ru(2)-O(8) bond length is 2.02 Å. The Ru(2)-O(9) bond length is 2.03 Å. In the third Ru site, Ru(3) is bonded to one O(3), one O(7), two equivalent O(10), and two equivalent O(6) atoms to form corner-sharing RuO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Ru(3)-O(3) bond length is 2.09 Å. The Ru(3)-O(7) bond length is 2.02 Å. Both Ru(3)-O(10) bond lengths are 1.97 Å. Both Ru(3)-O(6) bond lengths are 2.08 Å. Bi(1) is bonded in a 8-coordinate geometry to one O(1), one O(2), one O(5), one O(9), two equivalent O(10), and two equivalent O(6) atoms. The Bi(1)-O(1) bond length is 2.27 Å. The Bi(1)-O(2) bond length is 2.30 Å. The Bi(1)-O(5) bond length is 2.72 Å. The Bi(1)-O(9) bond length is 2.41 Å. Both Bi(1)-O(10) bond lengths are 2.67 Å. Both Bi(1)-O(6) bond lengths are 2.45 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Sm(2), two equivalent Sm(1), and one Bi(1) atom to form OSm3Bi tetrahedra that share corners with two equivalent O(9)SmBiRu2 tetrahedra, corners with four equivalent O(8)Sm2Ru2 tetrahedra, corners with four equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(3)Sm2Ru2 tetrahedra, and edges with two equivalent O(6)SmBiRu2 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Sm(2), two equivalent Sm(1), and one Bi(1) atom to form distorted OLiSm3Bi trigonal bipyramids that share corners with two equivalent O(3)Sm2Ru2 tetrahedra, corners with four equivalent O(1)Sm3Bi tetrahedra, corners with four equivalent O(6)SmBiRu2 tetrahedra,  an edgeedge with one O(9)SmBiRu2 tetrahedra, and edges with two equivalent O(8)Sm2Ru2 tetrahedra. In the third O site, O(3) is bonded to two equivalent Sm(1), one Ru(1), and one Ru(3) atom to form distorted OSm2Ru2 tetrahedra that share corners with four equivalent O(6)SmBiRu2 tetrahedra, corners with two equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(1)Sm3Bi tetrahedra, and edges with two equivalent O(8)Sm2Ru2 tetrahedra. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one Sm(1), one Sm(2), one Ru(1), and one Ru(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Li(1), one Sm(2), two equivalent Ru(2), and one Bi(1) atom. In the sixth O site, O(6) is bonded to one Sm(1), one Ru(2), one Ru(3), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(3)Sm2Ru2 tetrahedra, corners with two equivalent O(6)SmBiRu2 tetrahedra, corners with two equivalent O(2)LiSm3Bi trigonal bipyramids,  an edgeedge with one O(8)Sm2Ru2 tetrahedra,  an edgeedge with one O(1)Sm3Bi tetrahedra, and  an edgeedge with one O(9)SmBiRu2 tetrahedra. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), two equivalent Sm(1), one Ru(1), and one Ru(3) atom. In the eighth O site, O(8) is bonded to one Sm(1), one Sm(2), one Ru(1), and one Ru(2) atom to form distorted OSm2Ru2 tetrahedra that share corners with two equivalent O(8)Sm2Ru2 tetrahedra, corners with two equivalent O(1)Sm3Bi tetrahedra, corners with two equivalent O(9)SmBiRu2 tetrahedra,  an edgeedge with one O(3)Sm2Ru2 tetrahedra,  an edgeedge with one O(6)SmBiRu2 tetrahedra, and  an edgeedge with one O(2)LiSm3Bi trigonal bipyramid. In the ninth O site, O(9) is bonded to one Sm(2), two equivalent Ru(2), and one Bi(1) atom to form distorted OSmBiRu2 tetrahedra that share corners with two equivalent O(1)Sm3Bi tetrahedra, corners with four equivalent O(8)Sm2Ru2 tetrahedra, edges with two equivalent O(6)SmBiRu2 tetrahedra, and  an edgeedge with one O(2)LiSm3Bi trigonal bipyramid. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one Sm(1), one Ru(2), one Ru(3), and one Bi(1) atom.