BaU2S5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), and four equivalent S(4) atoms. U(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1) and four equivalent U(1) atoms to form SBaU4 square pyramids that share corners with four equivalent S(1)BaU4 square pyramids, corners with four equivalent S(3)BaU4 square pyramids, corners with four equivalent S(4)Ba2U2 tetrahedra,  a cornercorner with one S(2)BaU4 trigonal bipyramid,  an edgeedge with one S(3)BaU4 square pyramid, edges with four equivalent S(4)Ba2U2 tetrahedra, edges with four equivalent S(2)BaU4 trigonal bipyramids, and  a faceface with one S(3)BaU4 square pyramid. In the second S site, S(2) is bonded to one Ba(1) and four equivalent U(1) atoms to form distorted SBaU4 trigonal bipyramids that share  a cornercorner with one S(1)BaU4 square pyramid, corners with five equivalent S(3)BaU4 square pyramids, corners with four equivalent S(4)Ba2U2 tetrahedra, corners with four equivalent S(2)BaU4 trigonal bipyramids, edges with two equivalent S(3)BaU4 square pyramids, edges with four equivalent S(1)BaU4 square pyramids, and edges with four equivalent S(4)Ba2U2 tetrahedra. In the third S site, S(3) is bonded to one Ba(1) and four equivalent U(1) atoms to form SBaU4 square pyramids that share corners with four equivalent S(1)BaU4 square pyramids, corners with eight equivalent S(4)Ba2U2 tetrahedra, corners with five equivalent S(2)BaU4 trigonal bipyramids,  an edgeedge with one S(1)BaU4 square pyramid, edges with two equivalent S(3)BaU4 square pyramids, edges with two equivalent S(4)Ba2U2 tetrahedra, edges with two equivalent S(2)BaU4 trigonal bipyramids, and  a faceface with one S(1)BaU4 square pyramid. In the fourth S site, S(4) is bonded to two equivalent Ba(1) and two equivalent U(1) atoms to form SBa2U2 tetrahedra that share corners with two equivalent S(1)BaU4 square pyramids, corners with four equivalent S(3)BaU4 square pyramids, corners with six equivalent S(4)Ba2U2 tetrahedra, corners with two equivalent S(2)BaU4 trigonal bipyramids,  an edgeedge with one S(3)BaU4 square pyramid, edges with two equivalent S(1)BaU4 square pyramids,  an edgeedge with one S(4)Ba2U2 tetrahedra, and edges with two equivalent S(2)BaU4 trigonal bipyramids.
BaU2S5 crystallizes in the orthorhombic Pnma space group. Ba(1) is bonded in a 7-coordinate geometry to one S(1), one S(2), one S(3), and four equivalent S(4) atoms. The Ba(1)-S(1) bond length is 3.10 Å. The Ba(1)-S(2) bond length is 3.07 Å. The Ba(1)-S(3) bond length is 3.08 Å. There are two shorter (2.95 Å) and two longer (3.01 Å) Ba(1)-S(4) bond lengths. U(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There is one shorter (2.86 Å) and one longer (2.90 Å) U(1)-S(1) bond length. There is one shorter (2.95 Å) and one longer (3.00 Å) U(1)-S(2) bond length. There is one shorter (2.96 Å) and one longer (3.28 Å) U(1)-S(3) bond length. There is one shorter (2.62 Å) and one longer (2.68 Å) U(1)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1) and four equivalent U(1) atoms to form SBaU4 square pyramids that share corners with four equivalent S(1)BaU4 square pyramids, corners with four equivalent S(3)BaU4 square pyramids, corners with four equivalent S(4)Ba2U2 tetrahedra,  a cornercorner with one S(2)BaU4 trigonal bipyramid,  an edgeedge with one S(3)BaU4 square pyramid, edges with four equivalent S(4)Ba2U2 tetrahedra, edges with four equivalent S(2)BaU4 trigonal bipyramids, and  a faceface with one S(3)BaU4 square pyramid. In the second S site, S(2) is bonded to one Ba(1) and four equivalent U(1) atoms to form distorted SBaU4 trigonal bipyramids that share  a cornercorner with one S(1)BaU4 square pyramid, corners with five equivalent S(3)BaU4 square pyramids, corners with four equivalent S(4)Ba2U2 tetrahedra, corners with four equivalent S(2)BaU4 trigonal bipyramids, edges with two equivalent S(3)BaU4 square pyramids, edges with four equivalent S(1)BaU4 square pyramids, and edges with four equivalent S(4)Ba2U2 tetrahedra. In the third S site, S(3) is bonded to one Ba(1) and four equivalent U(1) atoms to form SBaU4 square pyramids that share corners with four equivalent S(1)BaU4 square pyramids, corners with eight equivalent S(4)Ba2U2 tetrahedra, corners with five equivalent S(2)BaU4 trigonal bipyramids,  an edgeedge with one S(1)BaU4 square pyramid, edges with two equivalent S(3)BaU4 square pyramids, edges with two equivalent S(4)Ba2U2 tetrahedra, edges with two equivalent S(2)BaU4 trigonal bipyramids, and  a faceface with one S(1)BaU4 square pyramid. In the fourth S site, S(4) is bonded to two equivalent Ba(1) and two equivalent U(1) atoms to form SBa2U2 tetrahedra that share corners with two equivalent S(1)BaU4 square pyramids, corners with four equivalent S(3)BaU4 square pyramids, corners with six equivalent S(4)Ba2U2 tetrahedra, corners with two equivalent S(2)BaU4 trigonal bipyramids,  an edgeedge with one S(3)BaU4 square pyramid, edges with two equivalent S(1)BaU4 square pyramids,  an edgeedge with one S(4)Ba2U2 tetrahedra, and edges with two equivalent S(2)BaU4 trigonal bipyramids.