Sm2Sn3(PbS4)3 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one S(4), one S(8), two equivalent S(11), two equivalent S(2), and two equivalent S(3) atoms. In the second Sm site, Sm(2) is bonded to one S(5), one S(6), one S(7), two equivalent S(1), and two equivalent S(10) atoms to form distorted SmS7 pentagonal bipyramids that share corners with two equivalent Sn(2)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, edges with two equivalent Sn(2)S6 octahedra, and edges with two equivalent Sm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 49°. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one S(4), one S(6), two equivalent S(11), and two equivalent S(9) atoms. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one S(7), two equivalent S(1), two equivalent S(10), and two equivalent S(9) atoms. In the third Pb site, Pb(3) is bonded in a 7-coordinate geometry to one S(5), two equivalent S(12), two equivalent S(2), and two equivalent S(3) atoms. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(1), one S(2), two equivalent S(4), and two equivalent S(5) atoms to form SnS6 octahedra that share edges with two equivalent Sn(1)S6 octahedra and edges with two equivalent Sm(2)S7 pentagonal bipyramids. In the second Sn site, Sn(2) is bonded to one S(10), one S(9), two equivalent S(6), and two equivalent S(7) atoms to form SnS6 octahedra that share corners with two equivalent Sm(2)S7 pentagonal bipyramids, edges with two equivalent Sn(2)S6 octahedra, and edges with two equivalent Sm(2)S7 pentagonal bipyramids. In the third Sn site, Sn(3) is bonded to one S(11), one S(12), one S(3), and two equivalent S(8) atoms to form corner-sharing SnS5 trigonal bipyramids. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Sm(2), two equivalent Pb(2), and one Sn(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Sm(1), two equivalent Pb(3), and one Sn(1) atom. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Sm(1), two equivalent Pb(3), and one Sn(3) atom. In the fourth S site, S(4) is bonded to one Sm(1), one Pb(1), and two equivalent Sn(1) atoms to form distorted SSmSn2Pb trigonal pyramids that share corners with two equivalent S(9)SnPb4 square pyramids,  a cornercorner with one S(6)SmSn2Pb trigonal pyramid, corners with two equivalent S(4)SmSn2Pb trigonal pyramids, corners with two equivalent S(5)SmSn2Pb trigonal pyramids, and  an edgeedge with one S(5)SmSn2Pb trigonal pyramid. In the fifth S site, S(5) is bonded to one Sm(2), one Pb(3), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing SSmSn2Pb trigonal pyramids. In the sixth S site, S(6) is bonded to one Sm(2), one Pb(1), and two equivalent Sn(2) atoms to form distorted SSmSn2Pb trigonal pyramids that share  a cornercorner with one S(4)SmSn2Pb trigonal pyramid,  a cornercorner with one S(5)SmSn2Pb trigonal pyramid, corners with two equivalent S(6)SmSn2Pb trigonal pyramids, corners with three equivalent S(7)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, and  an edgeedge with one S(7)SmSn2Pb trigonal pyramid. In the seventh S site, S(7) is bonded to one Sm(2), one Pb(2), and two equivalent Sn(2) atoms to form distorted SSmSn2Pb trigonal pyramids that share  a cornercorner with one S(5)SmSn2Pb trigonal pyramid, corners with two equivalent S(7)SmSn2Pb trigonal pyramids, corners with three equivalent S(6)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, and  an edgeedge with one S(6)SmSn2Pb trigonal pyramid. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Sn(3) atoms. In the ninth S site, S(9) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Sn(2) atom to form distorted SSnPb4 square pyramids that share corners with two equivalent S(4)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, edges with two equivalent S(6)SmSn2Pb trigonal pyramids, and edges with two equivalent S(7)SmSn2Pb trigonal pyramids. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to two equivalent Sm(2), two equivalent Pb(2), and one Sn(2) atom. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Sm(1), two equivalent Pb(1), and one Sn(3) atom. In the twelfth S site, S(12) is bonded in a distorted single-bond geometry to two equivalent Pb(3) and one Sn(3) atom.
Sm2Sn3(PbS4)3 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to one S(4), one S(8), two equivalent S(11), two equivalent S(2), and two equivalent S(3) atoms. The Sm(1)-S(4) bond length is 3.18 Å. The Sm(1)-S(8) bond length is 3.23 Å. Both Sm(1)-S(11) bond lengths are 2.92 Å. Both Sm(1)-S(2) bond lengths are 2.90 Å. Both Sm(1)-S(3) bond lengths are 2.88 Å. In the second Sm site, Sm(2) is bonded to one S(5), one S(6), one S(7), two equivalent S(1), and two equivalent S(10) atoms to form distorted SmS7 pentagonal bipyramids that share corners with two equivalent Sn(2)S6 octahedra, edges with two equivalent Sn(1)S6 octahedra, edges with two equivalent Sn(2)S6 octahedra, and edges with two equivalent Sm(2)S7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 49°. The Sm(2)-S(5) bond length is 2.87 Å. The Sm(2)-S(6) bond length is 2.86 Å. The Sm(2)-S(7) bond length is 2.87 Å. Both Sm(2)-S(1) bond lengths are 2.84 Å. Both Sm(2)-S(10) bond lengths are 2.86 Å. There are three inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 6-coordinate geometry to one S(4), one S(6), two equivalent S(11), and two equivalent S(9) atoms. The Pb(1)-S(4) bond length is 3.02 Å. The Pb(1)-S(6) bond length is 3.07 Å. Both Pb(1)-S(11) bond lengths are 3.10 Å. Both Pb(1)-S(9) bond lengths are 2.96 Å. In the second Pb site, Pb(2) is bonded in a 7-coordinate geometry to one S(7), two equivalent S(1), two equivalent S(10), and two equivalent S(9) atoms. The Pb(2)-S(7) bond length is 3.14 Å. Both Pb(2)-S(1) bond lengths are 3.21 Å. Both Pb(2)-S(10) bond lengths are 3.11 Å. Both Pb(2)-S(9) bond lengths are 2.96 Å. In the third Pb site, Pb(3) is bonded in a 7-coordinate geometry to one S(5), two equivalent S(12), two equivalent S(2), and two equivalent S(3) atoms. The Pb(3)-S(5) bond length is 2.90 Å. Both Pb(3)-S(12) bond lengths are 3.02 Å. Both Pb(3)-S(2) bond lengths are 3.17 Å. Both Pb(3)-S(3) bond lengths are 3.20 Å. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one S(1), one S(2), two equivalent S(4), and two equivalent S(5) atoms to form SnS6 octahedra that share edges with two equivalent Sn(1)S6 octahedra and edges with two equivalent Sm(2)S7 pentagonal bipyramids. The Sn(1)-S(1) bond length is 2.57 Å. The Sn(1)-S(2) bond length is 2.55 Å. Both Sn(1)-S(4) bond lengths are 2.61 Å. Both Sn(1)-S(5) bond lengths are 2.66 Å. In the second Sn site, Sn(2) is bonded to one S(10), one S(9), two equivalent S(6), and two equivalent S(7) atoms to form SnS6 octahedra that share corners with two equivalent Sm(2)S7 pentagonal bipyramids, edges with two equivalent Sn(2)S6 octahedra, and edges with two equivalent Sm(2)S7 pentagonal bipyramids. The Sn(2)-S(10) bond length is 2.56 Å. The Sn(2)-S(9) bond length is 2.55 Å. Both Sn(2)-S(6) bond lengths are 2.64 Å. Both Sn(2)-S(7) bond lengths are 2.63 Å. In the third Sn site, Sn(3) is bonded to one S(11), one S(12), one S(3), and two equivalent S(8) atoms to form corner-sharing SnS5 trigonal bipyramids. The Sn(3)-S(11) bond length is 2.58 Å. The Sn(3)-S(12) bond length is 2.45 Å. The Sn(3)-S(3) bond length is 2.57 Å. Both Sn(3)-S(8) bond lengths are 2.49 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to two equivalent Sm(2), two equivalent Pb(2), and one Sn(1) atom. In the second S site, S(2) is bonded in a 3-coordinate geometry to two equivalent Sm(1), two equivalent Pb(3), and one Sn(1) atom. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Sm(1), two equivalent Pb(3), and one Sn(3) atom. In the fourth S site, S(4) is bonded to one Sm(1), one Pb(1), and two equivalent Sn(1) atoms to form distorted SSmSn2Pb trigonal pyramids that share corners with two equivalent S(9)SnPb4 square pyramids,  a cornercorner with one S(6)SmSn2Pb trigonal pyramid, corners with two equivalent S(4)SmSn2Pb trigonal pyramids, corners with two equivalent S(5)SmSn2Pb trigonal pyramids, and  an edgeedge with one S(5)SmSn2Pb trigonal pyramid. In the fifth S site, S(5) is bonded to one Sm(2), one Pb(3), and two equivalent Sn(1) atoms to form a mixture of distorted corner and edge-sharing SSmSn2Pb trigonal pyramids. In the sixth S site, S(6) is bonded to one Sm(2), one Pb(1), and two equivalent Sn(2) atoms to form distorted SSmSn2Pb trigonal pyramids that share  a cornercorner with one S(4)SmSn2Pb trigonal pyramid,  a cornercorner with one S(5)SmSn2Pb trigonal pyramid, corners with two equivalent S(6)SmSn2Pb trigonal pyramids, corners with three equivalent S(7)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, and  an edgeedge with one S(7)SmSn2Pb trigonal pyramid. In the seventh S site, S(7) is bonded to one Sm(2), one Pb(2), and two equivalent Sn(2) atoms to form distorted SSmSn2Pb trigonal pyramids that share  a cornercorner with one S(5)SmSn2Pb trigonal pyramid, corners with two equivalent S(7)SmSn2Pb trigonal pyramids, corners with three equivalent S(6)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, and  an edgeedge with one S(6)SmSn2Pb trigonal pyramid. In the eighth S site, S(8) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Sn(3) atoms. In the ninth S site, S(9) is bonded to two equivalent Pb(1), two equivalent Pb(2), and one Sn(2) atom to form distorted SSnPb4 square pyramids that share corners with two equivalent S(4)SmSn2Pb trigonal pyramids, edges with two equivalent S(9)SnPb4 square pyramids, edges with two equivalent S(6)SmSn2Pb trigonal pyramids, and edges with two equivalent S(7)SmSn2Pb trigonal pyramids. In the tenth S site, S(10) is bonded in a 5-coordinate geometry to two equivalent Sm(2), two equivalent Pb(2), and one Sn(2) atom. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Sm(1), two equivalent Pb(1), and one Sn(3) atom. In the twelfth S site, S(12) is bonded in a distorted single-bond geometry to two equivalent Pb(3) and one Sn(3) atom.