UCe2S5 crystallizes in the orthorhombic Pnma space group. U(1) is bonded to one S(1), one S(2), one S(4), and four equivalent S(3) atoms to form distorted edge-sharing US7 pentagonal bipyramids. Ce(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 U(1) and four equivalent Ce(1) atoms to form SCe4U square pyramids that share corners with four equivalent S(4)Ce4U square pyramids, corners with five equivalent S(2)Ce4U trigonal bipyramids, corners with eight equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(4)Ce4U square pyramid, edges with two equivalent S(1)Ce4U square pyramids, edges with two equivalent S(2)Ce4U trigonal bipyramids, edges with two equivalent S(3)Ce2U2 trigonal pyramids, and  a faceface with one S(4)Ce4U square pyramid. In the second S site, S(2) is bonded to one U(1) and four equivalent Ce(1) atoms to form distorted SCe4U trigonal bipyramids that share  a cornercorner with one S(4)Ce4U square pyramid, corners with five equivalent S(1)Ce4U square pyramids, corners with four equivalent S(2)Ce4U trigonal bipyramids, corners with four equivalent S(3)Ce2U2 trigonal pyramids, edges with two equivalent S(1)Ce4U square pyramids, edges with four equivalent S(4)Ce4U square pyramids, and edges with four equivalent S(3)Ce2U2 trigonal pyramids. In the third S site, S(3) is bonded to two equivalent U(1) and two equivalent Ce(1) atoms to form distorted SCe2U2 trigonal pyramids that share corners with two equivalent S(4)Ce4U square pyramids, corners with four equivalent S(1)Ce4U square pyramids, corners with two equivalent S(2)Ce4U trigonal bipyramids, corners with six equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(1)Ce4U square pyramid, edges with two equivalent S(4)Ce4U square pyramids, edges with two equivalent S(2)Ce4U trigonal bipyramids, and  an edgeedge with one S(3)Ce2U2 trigonal pyramid. In the fourth S site, S(4) is bonded to one U(1) and four equivalent Ce(1) atoms to form SCe4U square pyramids that share corners with four equivalent S(1)Ce4U square pyramids, corners with four equivalent S(4)Ce4U square pyramids,  a cornercorner with one S(2)Ce4U trigonal bipyramid, corners with four equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(1)Ce4U square pyramid, edges with four equivalent S(2)Ce4U trigonal bipyramids, edges with four equivalent S(3)Ce2U2 trigonal pyramids, and  a faceface with one S(1)Ce4U square pyramid.
UCe2S5 crystallizes in the orthorhombic Pnma space group. U(1) is bonded to one S(1), one S(2), one S(4), and four equivalent S(3) atoms to form distorted edge-sharing US7 pentagonal bipyramids. The U(1)-S(1) bond length is 2.91 Å. The U(1)-S(2) bond length is 2.77 Å. The U(1)-S(4) bond length is 2.81 Å. There are two shorter (2.68 Å) and two longer (2.76 Å) U(1)-S(3) bond lengths. Ce(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 (2.94 Å) and one longer (2.97 Å) Ce(1)-S(1) bond length. There is one shorter (3.00 Å) and one longer (3.09 Å) Ce(1)-S(2) bond length. There is one shorter (2.94 Å) and one longer (2.95 Å) Ce(1)-S(3) bond length. There is one shorter (2.94 Å) and one longer (2.98 Å) Ce(1)-S(4) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded to one U(1) and four equivalent Ce(1) atoms to form SCe4U square pyramids that share corners with four equivalent S(4)Ce4U square pyramids, corners with five equivalent S(2)Ce4U trigonal bipyramids, corners with eight equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(4)Ce4U square pyramid, edges with two equivalent S(1)Ce4U square pyramids, edges with two equivalent S(2)Ce4U trigonal bipyramids, edges with two equivalent S(3)Ce2U2 trigonal pyramids, and  a faceface with one S(4)Ce4U square pyramid. In the second S site, S(2) is bonded to one U(1) and four equivalent Ce(1) atoms to form distorted SCe4U trigonal bipyramids that share  a cornercorner with one S(4)Ce4U square pyramid, corners with five equivalent S(1)Ce4U square pyramids, corners with four equivalent S(2)Ce4U trigonal bipyramids, corners with four equivalent S(3)Ce2U2 trigonal pyramids, edges with two equivalent S(1)Ce4U square pyramids, edges with four equivalent S(4)Ce4U square pyramids, and edges with four equivalent S(3)Ce2U2 trigonal pyramids. In the third S site, S(3) is bonded to two equivalent U(1) and two equivalent Ce(1) atoms to form distorted SCe2U2 trigonal pyramids that share corners with two equivalent S(4)Ce4U square pyramids, corners with four equivalent S(1)Ce4U square pyramids, corners with two equivalent S(2)Ce4U trigonal bipyramids, corners with six equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(1)Ce4U square pyramid, edges with two equivalent S(4)Ce4U square pyramids, edges with two equivalent S(2)Ce4U trigonal bipyramids, and  an edgeedge with one S(3)Ce2U2 trigonal pyramid. In the fourth S site, S(4) is bonded to one U(1) and four equivalent Ce(1) atoms to form SCe4U square pyramids that share corners with four equivalent S(1)Ce4U square pyramids, corners with four equivalent S(4)Ce4U square pyramids,  a cornercorner with one S(2)Ce4U trigonal bipyramid, corners with four equivalent S(3)Ce2U2 trigonal pyramids,  an edgeedge with one S(1)Ce4U square pyramid, edges with four equivalent S(2)Ce4U trigonal bipyramids, edges with four equivalent S(3)Ce2U2 trigonal pyramids, and  a faceface with one S(1)Ce4U square pyramid.