NdBi3(Ru2O7)2 crystallizes in the trigonal R-3m space group. Nd(1) is bonded to two equivalent O(1) and six equivalent O(3) atoms to form distorted NdO8 hexagonal bipyramids that share edges with six equivalent Bi(1)O8 hexagonal bipyramids and edges with six equivalent Ru(2)O6 octahedra. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to six equivalent O(2) atoms to form RuO6 octahedra that share corners with six equivalent Ru(2)O6 octahedra and edges with six equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. In the second Ru site, Ru(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, edges with two equivalent Nd(1)O8 hexagonal bipyramids, and edges with four equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and four equivalent O(2) atoms to form distorted BiO8 hexagonal bipyramids that share edges with two equivalent Nd(1)O8 hexagonal bipyramids, edges with four equivalent Bi(1)O8 hexagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Ru(2)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Nd(1) and three equivalent Bi(1) atoms to form ONdBi3 tetrahedra that share corners with four equivalent O(1)NdBi3 tetrahedra, corners with six equivalent O(2)Bi2Ru2 tetrahedra, corners with six equivalent O(3)NdBiRu2 tetrahedra, edges with three equivalent O(2)Bi2Ru2 tetrahedra, and edges with three equivalent O(3)NdBiRu2 tetrahedra. In the second O site, O(2) is bonded to one Ru(1), one Ru(2), and two equivalent Bi(1) atoms to form distorted OBi2Ru2 tetrahedra that share corners with two equivalent O(1)NdBi3 tetrahedra, corners with four equivalent O(3)NdBiRu2 tetrahedra, corners with eight equivalent O(2)Bi2Ru2 tetrahedra,  an edgeedge with one O(1)NdBi3 tetrahedra, edges with two equivalent O(2)Bi2Ru2 tetrahedra, and edges with two equivalent O(3)NdBiRu2 tetrahedra. In the third O site, O(3) is bonded to one Nd(1), two equivalent Ru(2), and one Bi(1) atom to form distorted ONdBiRu2 tetrahedra that share corners with two equivalent O(1)NdBi3 tetrahedra, corners with four equivalent O(2)Bi2Ru2 tetrahedra, corners with eight equivalent O(3)NdBiRu2 tetrahedra,  an edgeedge with one O(1)NdBi3 tetrahedra, edges with two equivalent O(2)Bi2Ru2 tetrahedra, and edges with two equivalent O(3)NdBiRu2 tetrahedra.
NdBi3(Ru2O7)2 crystallizes in the trigonal R-3m space group. Nd(1) is bonded to two equivalent O(1) and six equivalent O(3) atoms to form distorted NdO8 hexagonal bipyramids that share edges with six equivalent Bi(1)O8 hexagonal bipyramids and edges with six equivalent Ru(2)O6 octahedra. Both Nd(1)-O(1) bond lengths are 2.26 Å. All Nd(1)-O(3) bond lengths are 2.57 Å. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to six equivalent O(2) atoms to form RuO6 octahedra that share corners with six equivalent Ru(2)O6 octahedra and edges with six equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. All Ru(1)-O(2) bond lengths are 2.01 Å. In the second Ru site, Ru(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form RuO6 octahedra that share corners with two equivalent Ru(1)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra, edges with two equivalent Nd(1)O8 hexagonal bipyramids, and edges with four equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 48°. Both Ru(2)-O(2) bond lengths are 2.03 Å. All Ru(2)-O(3) bond lengths are 2.01 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(3), and four equivalent O(2) atoms to form distorted BiO8 hexagonal bipyramids that share edges with two equivalent Nd(1)O8 hexagonal bipyramids, edges with four equivalent Bi(1)O8 hexagonal bipyramids, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Ru(2)O6 octahedra. Both Bi(1)-O(1) bond lengths are 2.25 Å. Both Bi(1)-O(3) bond lengths are 2.57 Å. All Bi(1)-O(2) bond lengths are 2.56 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Nd(1) and three equivalent Bi(1) atoms to form ONdBi3 tetrahedra that share corners with four equivalent O(1)NdBi3 tetrahedra, corners with six equivalent O(2)Bi2Ru2 tetrahedra, corners with six equivalent O(3)NdBiRu2 tetrahedra, edges with three equivalent O(2)Bi2Ru2 tetrahedra, and edges with three equivalent O(3)NdBiRu2 tetrahedra. In the second O site, O(2) is bonded to one Ru(1), one Ru(2), and two equivalent Bi(1) atoms to form distorted OBi2Ru2 tetrahedra that share corners with two equivalent O(1)NdBi3 tetrahedra, corners with four equivalent O(3)NdBiRu2 tetrahedra, corners with eight equivalent O(2)Bi2Ru2 tetrahedra,  an edgeedge with one O(1)NdBi3 tetrahedra, edges with two equivalent O(2)Bi2Ru2 tetrahedra, and edges with two equivalent O(3)NdBiRu2 tetrahedra. In the third O site, O(3) is bonded to one Nd(1), two equivalent Ru(2), and one Bi(1) atom to form distorted ONdBiRu2 tetrahedra that share corners with two equivalent O(1)NdBi3 tetrahedra, corners with four equivalent O(2)Bi2Ru2 tetrahedra, corners with eight equivalent O(3)NdBiRu2 tetrahedra,  an edgeedge with one O(1)NdBi3 tetrahedra, edges with two equivalent O(2)Bi2Ru2 tetrahedra, and edges with two equivalent O(3)NdBiRu2 tetrahedra.