Ba8Re2(WO8)3 crystallizes in the trigonal R-3m space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent O(1), three equivalent O(4), and six equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Ba(4)O12 cuboctahedra, faces with three equivalent W(1)O6 octahedra, and faces with three equivalent Re(1)O6 octahedra. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to nine equivalent O(2) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(4) atoms. In the fourth Ba site, Ba(4) is bonded to three equivalent O(3) and nine equivalent O(1) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(4)O12 cuboctahedra, corners with three equivalent Re(1)O6 octahedra, faces with three equivalent Ba(4)O12 cuboctahedra, faces with four equivalent Ba(1)O12 cuboctahedra,  a faceface with one W(1)O6 octahedra, and faces with three equivalent Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. There are two inequivalent W sites. In the first W site, W(2) is bonded in an octahedral geometry to six equivalent O(2) atoms. In the second W site, W(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted WO6 octahedra that share corners with three equivalent Re(1)O6 octahedra,  a faceface with one Ba(4)O12 cuboctahedra, and faces with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. Re(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ReO6 octahedra that share corners with three equivalent Ba(4)O12 cuboctahedra, corners with three equivalent W(1)O6 octahedra, faces with three equivalent Ba(1)O12 cuboctahedra, and faces with three equivalent Ba(4)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(1), three equivalent Ba(4), and one Re(1) atom. In the second O site, O(2) is bonded to one Ba(3), three equivalent Ba(2), and one W(2) atom to form a mixture of distorted face, corner, and edge-sharing OBa4W square pyramids. In the third O site, O(3) is bonded to one Ba(4), two equivalent Ba(1), one W(1), and one Re(1) atom to form a mixture of distorted face, corner, and edge-sharing OBa3ReW square pyramids. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(3), and one W(1) atom.
Ba8Re2(WO8)3 crystallizes in the trigonal R-3m space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent O(1), three equivalent O(4), and six equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Ba(4)O12 cuboctahedra, faces with three equivalent W(1)O6 octahedra, and faces with three equivalent Re(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 2.96 Å. All Ba(1)-O(4) bond lengths are 2.70 Å. All Ba(1)-O(3) bond lengths are 2.92 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to nine equivalent O(2) atoms. There are three shorter (2.77 Å) and six longer (2.91 Å) Ba(2)-O(2) bond lengths. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to three equivalent O(2) and six equivalent O(4) atoms. All Ba(3)-O(2) bond lengths are 2.59 Å. All Ba(3)-O(4) bond lengths are 3.08 Å. In the fourth Ba site, Ba(4) is bonded to three equivalent O(3) and nine equivalent O(1) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(4)O12 cuboctahedra, corners with three equivalent Re(1)O6 octahedra, faces with three equivalent Ba(4)O12 cuboctahedra, faces with four equivalent Ba(1)O12 cuboctahedra,  a faceface with one W(1)O6 octahedra, and faces with three equivalent Re(1)O6 octahedra. The corner-sharing octahedral tilt angles are 20°. All Ba(4)-O(3) bond lengths are 2.95 Å. All Ba(4)-O(1) bond lengths are 2.93 Å. There are two inequivalent W sites. In the first W site, W(2) is bonded in an octahedral geometry to six equivalent O(2) atoms. All W(2)-O(2) bond lengths are 1.96 Å. In the second W site, W(1) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form distorted WO6 octahedra that share corners with three equivalent Re(1)O6 octahedra,  a faceface with one Ba(4)O12 cuboctahedra, and faces with three equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. All W(1)-O(3) bond lengths are 2.22 Å. All W(1)-O(4) bond lengths are 1.82 Å. Re(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form ReO6 octahedra that share corners with three equivalent Ba(4)O12 cuboctahedra, corners with three equivalent W(1)O6 octahedra, faces with three equivalent Ba(1)O12 cuboctahedra, and faces with three equivalent Ba(4)O12 cuboctahedra. The corner-sharing octahedral tilt angles are 5°. All Re(1)-O(1) bond lengths are 1.84 Å. All Re(1)-O(3) bond lengths are 2.02 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Ba(1), three equivalent Ba(4), and one Re(1) atom. In the second O site, O(2) is bonded to one Ba(3), three equivalent Ba(2), and one W(2) atom to form a mixture of distorted face, corner, and edge-sharing OBa4W square pyramids. In the third O site, O(3) is bonded to one Ba(4), two equivalent Ba(1), one W(1), and one Re(1) atom to form a mixture of distorted face, corner, and edge-sharing OBa3ReW square pyramids. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Ba(1), two equivalent Ba(3), and one W(1) atom.