Ba14U2V4S25O crystallizes in the tetragonal I422 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), four equivalent S(3), and one O(1) atom. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. In the third Ba site, Ba(3) is bonded in a distorted body-centered cubic geometry to eight equivalent S(2) atoms. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms. U(1) is bonded to one S(4), four equivalent S(3), and one O(1) atom to form corner-sharing US5O octahedra. The corner-sharing octahedra are not tilted. V(1) is bonded in a tetrahedral geometry to two equivalent S(1) and two equivalent S(2) atoms. There are four inequivalent S sites. In the first S site, S(4) is bonded to four equivalent Ba(2) and two equivalent U(1) atoms to form face-sharing SBa4U2 octahedra. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(4), and one V(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), two equivalent Ba(3), and one V(1) atom. In the fourth S site, S(3) is bonded to one Ba(4), two equivalent Ba(1), two equivalent Ba(2), and one U(1) atom to form distorted SBa5U octahedra that share corners with six equivalent S(3)Ba5U octahedra, edges with two equivalent S(3)Ba5U octahedra,  a faceface with one S(4)Ba4U2 octahedra, and faces with two equivalent S(3)Ba5U octahedra. The corner-sharing octahedral tilt angles range from 8-59°. O(1) is bonded in a linear geometry to four equivalent Ba(1) and two equivalent U(1) atoms.
Ba14U2V4S25O crystallizes in the tetragonal I422 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(2), four equivalent S(3), and one O(1) atom. Both Ba(1)-S(1) bond lengths are 3.42 Å. Both Ba(1)-S(2) bond lengths are 3.26 Å. There are two shorter (3.35 Å) and two longer (3.49 Å) Ba(1)-S(3) bond lengths. The Ba(1)-O(1) bond length is 3.51 Å. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. The Ba(2)-S(4) bond length is 3.44 Å. Both Ba(2)-S(1) bond lengths are 3.44 Å. Both Ba(2)-S(2) bond lengths are 3.25 Å. There are two shorter (3.41 Å) and two longer (3.54 Å) Ba(2)-S(3) bond lengths. In the third Ba site, Ba(3) is bonded in a distorted body-centered cubic geometry to eight equivalent S(2) atoms. There are four shorter (3.47 Å) and four longer (3.52 Å) Ba(3)-S(2) bond lengths. In the fourth Ba site, Ba(4) is bonded in a 8-coordinate geometry to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms. Both Ba(4)-S(2) bond lengths are 3.44 Å. Both Ba(4)-S(3) bond lengths are 3.25 Å. There are two shorter (3.05 Å) and two longer (3.22 Å) Ba(4)-S(1) bond lengths. U(1) is bonded to one S(4), four equivalent S(3), and one O(1) atom to form corner-sharing US5O octahedra. The corner-sharing octahedra are not tilted. The U(1)-S(4) bond length is 2.65 Å. All U(1)-S(3) bond lengths are 2.62 Å. The U(1)-O(1) bond length is 2.17 Å. V(1) is bonded in a tetrahedral geometry to two equivalent S(1) and two equivalent S(2) atoms. Both V(1)-S(1) bond lengths are 2.22 Å. Both V(1)-S(2) bond lengths are 2.27 Å. There are four inequivalent S sites. In the first S site, S(4) is bonded to four equivalent Ba(2) and two equivalent U(1) atoms to form face-sharing SBa4U2 octahedra. In the second S site, S(1) is bonded in a 5-coordinate geometry to one Ba(1), one Ba(2), two equivalent Ba(4), and one V(1) atom. In the third S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(2), one Ba(4), two equivalent Ba(3), and one V(1) atom. In the fourth S site, S(3) is bonded to one Ba(4), two equivalent Ba(1), two equivalent Ba(2), and one U(1) atom to form distorted SBa5U octahedra that share corners with six equivalent S(3)Ba5U octahedra, edges with two equivalent S(3)Ba5U octahedra,  a faceface with one S(4)Ba4U2 octahedra, and faces with two equivalent S(3)Ba5U octahedra. The corner-sharing octahedral tilt angles range from 8-59°. O(1) is bonded in a linear geometry to four equivalent Ba(1) and two equivalent U(1) atoms.