Sn5(S2Cl)2 crystallizes in the orthorhombic Pma2 space group. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(1), three equivalent S(2), and one Cl(2) atom. In the second Sn site, Sn(2) is bonded to two equivalent S(2), three equivalent S(1), and one Cl(1) atom to form a mixture of distorted corner and edge-sharing SnS5Cl octahedra. The corner-sharing octahedral tilt angles range from 4-16°. In the third Sn site, Sn(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(2), one Cl(1), and one Cl(2) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Sn(1) and three equivalent Sn(2) atoms. In the second S site, S(2) is bonded to one Sn(3), two equivalent Sn(2), and three equivalent Sn(1) atoms to form a mixture of corner and edge-sharing SSn6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a single-bond geometry to one Sn(3) and two equivalent Sn(2) atoms. In the second Cl site, Cl(2) is bonded in a single-bond geometry to one Sn(3) and two equivalent Sn(1) atoms.
Sn5(S2Cl)2 crystallizes in the orthorhombic Pma2 space group. There are three inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one S(1), three equivalent S(2), and one Cl(2) atom. The Sn(1)-S(1) bond length is 2.66 Å. There are a spread of Sn(1)-S(2) bond distances ranging from 2.80-3.05 Å. The Sn(1)-Cl(2) bond length is 3.17 Å. In the second Sn site, Sn(2) is bonded to two equivalent S(2), three equivalent S(1), and one Cl(1) atom to form a mixture of distorted corner and edge-sharing SnS5Cl octahedra. The corner-sharing octahedral tilt angles range from 4-16°. There is one shorter (2.84 Å) and one longer (3.14 Å) Sn(2)-S(2) bond length. There are a spread of Sn(2)-S(1) bond distances ranging from 2.65-2.95 Å. The Sn(2)-Cl(1) bond length is 3.18 Å. In the third Sn site, Sn(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent S(2), one Cl(1), and one Cl(2) atom. Both Sn(3)-S(2) bond lengths are 3.06 Å. The Sn(3)-Cl(1) bond length is 2.53 Å. The Sn(3)-Cl(2) bond length is 2.62 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Sn(1) and three equivalent Sn(2) atoms. In the second S site, S(2) is bonded to one Sn(3), two equivalent Sn(2), and three equivalent Sn(1) atoms to form a mixture of corner and edge-sharing SSn6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a single-bond geometry to one Sn(3) and two equivalent Sn(2) atoms. In the second Cl site, Cl(2) is bonded in a single-bond geometry to one Sn(3) and two equivalent Sn(1) atoms.