Pu2S3 crystallizes in the tetragonal I-42d space group. There are three inequivalent Pu sites. In the first Pu site, Pu(1) is bonded to two equivalent S(1), two equivalent S(3), and four equivalent S(2) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. In the second Pu site, Pu(2) is bonded to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. In the third Pu site, Pu(3) is bonded to two equivalent S(1), three equivalent S(2), and three equivalent S(3) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Pu(1), two equivalent Pu(2), and two equivalent Pu(3) atoms to form SPu5 square pyramids that share corners with five equivalent S(2)Pu6 octahedra, corners with four equivalent S(1)Pu5 square pyramids, corners with four equivalent S(3)Pu5 square pyramids, edges with three equivalent S(2)Pu6 octahedra,  an edgeedge with one S(1)Pu5 square pyramid, edges with four equivalent S(3)Pu5 square pyramids,  a faceface with one S(2)Pu6 octahedra, and  a faceface with one S(1)Pu5 square pyramid. The corner-sharing octahedral tilt angles range from 20-50°. In the second S site, S(2) is bonded to one Pu(2), two equivalent Pu(1), and three equivalent Pu(3) atoms to form distorted SPu6 octahedra that share corners with three equivalent S(2)Pu6 octahedra, corners with five equivalent S(1)Pu5 square pyramids, corners with seven equivalent S(3)Pu5 square pyramids, edges with two equivalent S(2)Pu6 octahedra,  an edgeedge with one S(3)Pu5 square pyramid, edges with three equivalent S(1)Pu5 square pyramids, faces with two equivalent S(2)Pu6 octahedra,  a faceface with one S(1)Pu5 square pyramid, and faces with two equivalent S(3)Pu5 square pyramids. The corner-sharing octahedral tilt angles range from 18-49°. In the third S site, S(3) is bonded to one Pu(1), one Pu(2), and three equivalent Pu(3) atoms to form distorted SPu5 square pyramids that share corners with seven equivalent S(2)Pu6 octahedra, corners with four equivalent S(1)Pu5 square pyramids, corners with five equivalent S(3)Pu5 square pyramids,  an edgeedge with one S(2)Pu6 octahedra, edges with four equivalent S(1)Pu5 square pyramids, faces with two equivalent S(2)Pu6 octahedra, and  a faceface with one S(3)Pu5 square pyramid. The corner-sharing octahedral tilt angles range from 13-53°.
Pu2S3 crystallizes in the tetragonal I-42d space group. There are three inequivalent Pu sites. In the first Pu site, Pu(1) is bonded to two equivalent S(1), two equivalent S(3), and four equivalent S(2) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. Both Pu(1)-S(1) bond lengths are 2.77 Å. Both Pu(1)-S(3) bond lengths are 2.96 Å. There are two shorter (2.82 Å) and two longer (2.93 Å) Pu(1)-S(2) bond lengths. In the second Pu site, Pu(2) is bonded to two equivalent S(2), two equivalent S(3), and four equivalent S(1) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. Both Pu(2)-S(2) bond lengths are 2.98 Å. Both Pu(2)-S(3) bond lengths are 2.84 Å. There are two shorter (2.80 Å) and two longer (2.93 Å) Pu(2)-S(1) bond lengths. In the third Pu site, Pu(3) is bonded to two equivalent S(1), three equivalent S(2), and three equivalent S(3) atoms to form a mixture of distorted face, corner, and edge-sharing PuS8 hexagonal bipyramids. There is one shorter (2.79 Å) and one longer (2.95 Å) Pu(3)-S(1) bond length. There are a spread of Pu(3)-S(2) bond distances ranging from 2.79-3.04 Å. There are a spread of Pu(3)-S(3) bond distances ranging from 2.76-2.94 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Pu(1), two equivalent Pu(2), and two equivalent Pu(3) atoms to form SPu5 square pyramids that share corners with five equivalent S(2)Pu6 octahedra, corners with four equivalent S(1)Pu5 square pyramids, corners with four equivalent S(3)Pu5 square pyramids, edges with three equivalent S(2)Pu6 octahedra,  an edgeedge with one S(1)Pu5 square pyramid, edges with four equivalent S(3)Pu5 square pyramids,  a faceface with one S(2)Pu6 octahedra, and  a faceface with one S(1)Pu5 square pyramid. The corner-sharing octahedral tilt angles range from 20-50°. In the second S site, S(2) is bonded to one Pu(2), two equivalent Pu(1), and three equivalent Pu(3) atoms to form distorted SPu6 octahedra that share corners with three equivalent S(2)Pu6 octahedra, corners with five equivalent S(1)Pu5 square pyramids, corners with seven equivalent S(3)Pu5 square pyramids, edges with two equivalent S(2)Pu6 octahedra,  an edgeedge with one S(3)Pu5 square pyramid, edges with three equivalent S(1)Pu5 square pyramids, faces with two equivalent S(2)Pu6 octahedra,  a faceface with one S(1)Pu5 square pyramid, and faces with two equivalent S(3)Pu5 square pyramids. The corner-sharing octahedral tilt angles range from 18-49°. In the third S site, S(3) is bonded to one Pu(1), one Pu(2), and three equivalent Pu(3) atoms to form distorted SPu5 square pyramids that share corners with seven equivalent S(2)Pu6 octahedra, corners with four equivalent S(1)Pu5 square pyramids, corners with five equivalent S(3)Pu5 square pyramids,  an edgeedge with one S(2)Pu6 octahedra, edges with four equivalent S(1)Pu5 square pyramids, faces with two equivalent S(2)Pu6 octahedra, and  a faceface with one S(3)Pu5 square pyramid. The corner-sharing octahedral tilt angles range from 13-53°.