Sm2Mn3(SbS3)4 crystallizes in the monoclinic C2/m space group. Sm(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(3) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(1), two equivalent S(5), and three equivalent S(6) atoms to form MnS6 octahedra that share  a cornercorner with one Mn(2)S6 octahedra, corners with two equivalent Sb(1)S5 square pyramids, edges with four equivalent Mn(1)S6 octahedra, and edges with three equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 44°. In the second Mn site, Mn(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of corner and edge-sharing MnS6 octahedra. The corner-sharing octahedral tilt angles are 44°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one S(5), two equivalent S(4), and two equivalent S(6) atoms to form SbS5 square pyramids that share corners with two equivalent Mn(1)S6 octahedra, edges with three equivalent Mn(1)S6 octahedra, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Sb(2) atoms. In the second S site, S(2) is bonded to two equivalent Sm(1), two equivalent Mn(2), and one Sb(2) atom to form SSm2Mn2Sb trigonal bipyramids that share corners with two equivalent S(5)Sm2Mn2Sb square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids, corners with two equivalent S(3)Sm3Sb2 trigonal bipyramids,  an edgeedge with one S(5)Sm2Mn2Sb square pyramid, edges with three equivalent S(2)Sm2Mn2Sb trigonal bipyramids, and edges with three equivalent S(3)Sm3Sb2 trigonal bipyramids. In the third S site, S(3) is bonded to three equivalent Sm(1) and two equivalent Sb(2) atoms to form distorted SSm3Sb2 trigonal bipyramids that share corners with four equivalent S(5)Sm2Mn2Sb square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids,  an edgeedge with one S(5)Sm2Mn2Sb square pyramid, edges with three equivalent S(2)Sm2Mn2Sb trigonal bipyramids, and edges with four equivalent S(3)Sm3Sb2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Sm(1), one Sb(2), and two equivalent Sb(1) atoms. In the fifth S site, S(5) is bonded to two equivalent Sm(1), two equivalent Mn(1), and one Sb(1) atom to form SSm2Mn2Sb square pyramids that share corners with two equivalent S(6)Mn3Sb2 square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids, corners with four equivalent S(3)Sm3Sb2 trigonal bipyramids, edges with two equivalent S(5)Sm2Mn2Sb square pyramids, edges with three equivalent S(6)Mn3Sb2 square pyramids,  an edgeedge with one S(2)Sm2Mn2Sb trigonal bipyramid, and  an edgeedge with one S(3)Sm3Sb2 trigonal bipyramid. In the sixth S site, S(6) is bonded to three equivalent Mn(1) and two equivalent Sb(1) atoms to form SMn3Sb2 square pyramids that share corners with two equivalent S(5)Sm2Mn2Sb square pyramids, edges with three equivalent S(5)Sm2Mn2Sb square pyramids, and edges with four equivalent S(6)Mn3Sb2 square pyramids.
Sm2Mn3(SbS3)4 crystallizes in the monoclinic C2/m space group. Sm(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(3) atoms. The Sm(1)-S(4) bond length is 2.93 Å. Both Sm(1)-S(2) bond lengths are 2.95 Å. Both Sm(1)-S(5) bond lengths are 2.98 Å. There are two shorter (2.88 Å) and one longer (2.95 Å) Sm(1)-S(3) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(1), two equivalent S(5), and three equivalent S(6) atoms to form MnS6 octahedra that share  a cornercorner with one Mn(2)S6 octahedra, corners with two equivalent Sb(1)S5 square pyramids, edges with four equivalent Mn(1)S6 octahedra, and edges with three equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 44°. The Mn(1)-S(1) bond length is 2.48 Å. Both Mn(1)-S(5) bond lengths are 2.75 Å. There is one shorter (2.43 Å) and two longer (2.59 Å) Mn(1)-S(6) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form a mixture of corner and edge-sharing MnS6 octahedra. The corner-sharing octahedral tilt angles are 44°. Both Mn(2)-S(1) bond lengths are 2.44 Å. All Mn(2)-S(2) bond lengths are 2.68 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one S(5), two equivalent S(4), and two equivalent S(6) atoms to form SbS5 square pyramids that share corners with two equivalent Mn(1)S6 octahedra, edges with three equivalent Mn(1)S6 octahedra, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles are 7°. The Sb(1)-S(5) bond length is 2.50 Å. Both Sb(1)-S(4) bond lengths are 2.62 Å. Both Sb(1)-S(6) bond lengths are 2.92 Å. In the second Sb site, Sb(2) is bonded in a 6-coordinate geometry to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms. The Sb(2)-S(2) bond length is 2.55 Å. The Sb(2)-S(4) bond length is 3.13 Å. Both Sb(2)-S(1) bond lengths are 2.67 Å. Both Sb(2)-S(3) bond lengths are 2.86 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Sb(2) atoms. In the second S site, S(2) is bonded to two equivalent Sm(1), two equivalent Mn(2), and one Sb(2) atom to form SSm2Mn2Sb trigonal bipyramids that share corners with two equivalent S(5)Sm2Mn2Sb square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids, corners with two equivalent S(3)Sm3Sb2 trigonal bipyramids,  an edgeedge with one S(5)Sm2Mn2Sb square pyramid, edges with three equivalent S(2)Sm2Mn2Sb trigonal bipyramids, and edges with three equivalent S(3)Sm3Sb2 trigonal bipyramids. In the third S site, S(3) is bonded to three equivalent Sm(1) and two equivalent Sb(2) atoms to form distorted SSm3Sb2 trigonal bipyramids that share corners with four equivalent S(5)Sm2Mn2Sb square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids,  an edgeedge with one S(5)Sm2Mn2Sb square pyramid, edges with three equivalent S(2)Sm2Mn2Sb trigonal bipyramids, and edges with four equivalent S(3)Sm3Sb2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Sm(1), one Sb(2), and two equivalent Sb(1) atoms. In the fifth S site, S(5) is bonded to two equivalent Sm(1), two equivalent Mn(1), and one Sb(1) atom to form SSm2Mn2Sb square pyramids that share corners with two equivalent S(6)Mn3Sb2 square pyramids, corners with two equivalent S(2)Sm2Mn2Sb trigonal bipyramids, corners with four equivalent S(3)Sm3Sb2 trigonal bipyramids, edges with two equivalent S(5)Sm2Mn2Sb square pyramids, edges with three equivalent S(6)Mn3Sb2 square pyramids,  an edgeedge with one S(2)Sm2Mn2Sb trigonal bipyramid, and  an edgeedge with one S(3)Sm3Sb2 trigonal bipyramid. In the sixth S site, S(6) is bonded to three equivalent Mn(1) and two equivalent Sb(1) atoms to form SMn3Sb2 square pyramids that share corners with two equivalent S(5)Sm2Mn2Sb square pyramids, edges with three equivalent S(5)Sm2Mn2Sb square pyramids, and edges with four equivalent S(6)Mn3Sb2 square pyramids.