Sm6Ge3S14 crystallizes in the trigonal P3 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(2), one S(3), two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one S(3) and three equivalent S(1) atoms. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one S(4) and three equivalent S(2) atoms. In the third Ge site, Ge(3) is bonded in an octahedral geometry to three equivalent S(5) and three equivalent S(6) 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 Sm(2), two equivalent Sm(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Sm(1), two equivalent Sm(2), and one Ge(2) atom. In the third S site, S(3) is bonded to three equivalent Sm(1) and one Ge(1) atom to form corner-sharing SSm3Ge tetrahedra. In the fourth S site, S(4) is bonded to three equivalent Sm(2) and one Ge(2) atom to form corner-sharing SSm3Ge tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Sm(1), two equivalent Sm(2), and one Ge(3) atom to form distorted SSm4Ge trigonal bipyramids that share corners with two equivalent S(3)Sm3Ge tetrahedra, corners with two equivalent S(4)Sm3Ge tetrahedra, corners with two equivalent S(5)Sm4Ge trigonal bipyramids, and edges with two equivalent S(5)Sm4Ge trigonal bipyramids. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Sm(1), two equivalent Sm(2), and one Ge(3) atom.
Sm6Ge3S14 crystallizes in the trigonal P3 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(2), one S(3), two equivalent S(1), two equivalent S(5), and two equivalent S(6) atoms. The Sm(1)-S(2) bond length is 3.03 Å. The Sm(1)-S(3) bond length is 3.01 Å. There is one shorter (2.85 Å) and one longer (2.94 Å) Sm(1)-S(1) bond length. There is one shorter (2.91 Å) and one longer (3.15 Å) Sm(1)-S(5) bond length. Both Sm(1)-S(6) bond lengths are 2.84 Å. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to one S(1), one S(4), two equivalent S(2), two equivalent S(5), and two equivalent S(6) atoms. The Sm(2)-S(1) bond length is 2.99 Å. The Sm(2)-S(4) bond length is 2.99 Å. There is one shorter (2.85 Å) and one longer (2.93 Å) Sm(2)-S(2) bond length. There is one shorter (2.83 Å) and one longer (2.87 Å) Sm(2)-S(5) bond length. There is one shorter (2.90 Å) and one longer (3.15 Å) Sm(2)-S(6) bond length. There are three inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one S(3) and three equivalent S(1) atoms. The Ge(1)-S(3) bond length is 2.17 Å. All Ge(1)-S(1) bond lengths are 2.23 Å. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one S(4) and three equivalent S(2) atoms. The Ge(2)-S(4) bond length is 2.18 Å. All Ge(2)-S(2) bond lengths are 2.23 Å. In the third Ge site, Ge(3) is bonded in an octahedral geometry to three equivalent S(5) and three equivalent S(6) atoms. All Ge(3)-S(5) bond lengths are 2.64 Å. All Ge(3)-S(6) bond lengths are 2.72 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 Sm(2), two equivalent Sm(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one Sm(1), two equivalent Sm(2), and one Ge(2) atom. In the third S site, S(3) is bonded to three equivalent Sm(1) and one Ge(1) atom to form corner-sharing SSm3Ge tetrahedra. In the fourth S site, S(4) is bonded to three equivalent Sm(2) and one Ge(2) atom to form corner-sharing SSm3Ge tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Sm(1), two equivalent Sm(2), and one Ge(3) atom to form distorted SSm4Ge trigonal bipyramids that share corners with two equivalent S(3)Sm3Ge tetrahedra, corners with two equivalent S(4)Sm3Ge tetrahedra, corners with two equivalent S(5)Sm4Ge trigonal bipyramids, and edges with two equivalent S(5)Sm4Ge trigonal bipyramids. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Sm(1), two equivalent Sm(2), and one Ge(3) atom.