Ba2RuBiO6 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent O(2), three equivalent O(3), and six equivalent O(1) atoms to form distorted BaO12 cuboctahedra that share corners with nine equivalent Ba(1)O12 cuboctahedra, corners with three equivalent Ru(1)O6 octahedra,  a faceface with one Ba(1)O12 cuboctahedra, faces with three equivalent Ba(2)O12 cuboctahedra, faces with three equivalent Ba(3)O12 cuboctahedra, faces with three equivalent Ru(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the second Ba site, Ba(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(2)O12 cuboctahedra, corners with six equivalent Ba(3)O12 cuboctahedra, faces with six equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Bi(1)O6 octahedra, and faces with six equivalent Ru(1)O6 octahedra. In the third Ba site, Ba(3) is bonded to six equivalent O(1) and six equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(2)O12 cuboctahedra, corners with six equivalent Ba(3)O12 cuboctahedra, faces with six equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ru(1)O6 octahedra, and faces with six equivalent Bi(1)O6 octahedra. Ru(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form RuO6 octahedra that share corners with three equivalent Ba(1)O12 cuboctahedra, corners with three equivalent Bi(1)O6 octahedra,  a faceface with one Ba(3)O12 cuboctahedra, faces with three equivalent Ba(1)O12 cuboctahedra, faces with three equivalent Ba(2)O12 cuboctahedra, and  a faceface with one Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Bi(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form BiO6 octahedra that share corners with three equivalent Ru(1)O6 octahedra, corners with three equivalent Bi(1)O6 octahedra,  a faceface with one Ba(2)O12 cuboctahedra, faces with three equivalent Ba(3)O12 cuboctahedra, and faces with four equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), one Ru(1), and one Bi(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Ru(1) atoms to form a mixture of distorted corner and face-sharing OBa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°. In the third O site, O(3) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(3), and two equivalent Bi(1) atoms.
Ba2RuBiO6 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent O(2), three equivalent O(3), and six equivalent O(1) atoms to form distorted BaO12 cuboctahedra that share corners with nine equivalent Ba(1)O12 cuboctahedra, corners with three equivalent Ru(1)O6 octahedra,  a faceface with one Ba(1)O12 cuboctahedra, faces with three equivalent Ba(2)O12 cuboctahedra, faces with three equivalent Ba(3)O12 cuboctahedra, faces with three equivalent Ru(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. All Ba(1)-O(2) bond lengths are 2.90 Å. All Ba(1)-O(3) bond lengths are 3.46 Å. All Ba(1)-O(1) bond lengths are 3.07 Å. In the second Ba site, Ba(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(2)O12 cuboctahedra, corners with six equivalent Ba(3)O12 cuboctahedra, faces with six equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Bi(1)O6 octahedra, and faces with six equivalent Ru(1)O6 octahedra. All Ba(2)-O(1) bond lengths are 2.99 Å. All Ba(2)-O(2) bond lengths are 3.07 Å. In the third Ba site, Ba(3) is bonded to six equivalent O(1) and six equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(2)O12 cuboctahedra, corners with six equivalent Ba(3)O12 cuboctahedra, faces with six equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ru(1)O6 octahedra, and faces with six equivalent Bi(1)O6 octahedra. All Ba(3)-O(1) bond lengths are 3.28 Å. All Ba(3)-O(3) bond lengths are 3.07 Å. Ru(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form RuO6 octahedra that share corners with three equivalent Ba(1)O12 cuboctahedra, corners with three equivalent Bi(1)O6 octahedra,  a faceface with one Ba(3)O12 cuboctahedra, faces with three equivalent Ba(1)O12 cuboctahedra, faces with three equivalent Ba(2)O12 cuboctahedra, and  a faceface with one Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Ru(1)-O(1) bond lengths are 1.94 Å. All Ru(1)-O(2) bond lengths are 2.12 Å. Bi(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form BiO6 octahedra that share corners with three equivalent Ru(1)O6 octahedra, corners with three equivalent Bi(1)O6 octahedra,  a faceface with one Ba(2)O12 cuboctahedra, faces with three equivalent Ba(3)O12 cuboctahedra, and faces with four equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-10°. All Bi(1)-O(1) bond lengths are 2.42 Å. All Bi(1)-O(3) bond lengths are 2.17 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), one Ru(1), and one Bi(1) atom. In the second O site, O(2) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Ru(1) atoms to form a mixture of distorted corner and face-sharing OBa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-60°. In the third O site, O(3) is bonded in a distorted linear geometry to two equivalent Ba(1), two equivalent Ba(3), and two equivalent Bi(1) atoms.