Ba9Sm6Cl34 crystallizes in the tetragonal I4/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one Cl(2), one Cl(4), one Cl(6), two equivalent Cl(3), two equivalent Cl(5), and three equivalent Cl(1) atoms. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to eight equivalent Cl(3) atoms. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to four equivalent Cl(1) and four equivalent Cl(5) atoms. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. There are six inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to one Ba(2), two equivalent Ba(1), and one Sm(2) atom to form ClBa3Sm tetrahedra that share corners with two equivalent Cl(2)Ba2Sm2 tetrahedra, corners with two equivalent Cl(6)Ba4 tetrahedra, corners with four equivalent Cl(1)Ba3Sm tetrahedra, corners with four equivalent Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(2)Ba2Sm2 tetrahedra,  an edgeedge with one Cl(1)Ba3Sm tetrahedra, and edges with three equivalent Cl(3)Ba3Sm tetrahedra. In the second Cl site, Cl(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent Sm(2) atoms. In the third Cl site, Cl(5) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one Sm(1), and one Sm(2) atom. In the fourth Cl site, Cl(6) is bonded to four equivalent Ba(1) atoms to form ClBa4 tetrahedra that share corners with four equivalent Cl(1)Ba3Sm tetrahedra, corners with eight equivalent Cl(3)Ba3Sm tetrahedra, edges with two equivalent Cl(2)Ba2Sm2 tetrahedra, and edges with four equivalent Cl(1)Ba3Sm tetrahedra. In the fifth Cl site, Cl(1) is bonded to three equivalent Ba(1) and one Sm(1) atom to form ClBa3Sm tetrahedra that share  a cornercorner with one Cl(6)Ba4 tetrahedra, corners with three equivalent Cl(2)Ba2Sm2 tetrahedra, corners with three equivalent Cl(1)Ba3Sm tetrahedra, corners with four equivalent Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(6)Ba4 tetrahedra, and edges with three equivalent Cl(1)Ba3Sm tetrahedra. In the sixth Cl site, Cl(2) is bonded to two equivalent Ba(1) and two equivalent Sm(2) atoms to form ClBa2Sm2 tetrahedra that share corners with four equivalent Cl(3)Ba3Sm tetrahedra, corners with six equivalent Cl(1)Ba3Sm tetrahedra,  an edgeedge with one Cl(2)Ba2Sm2 tetrahedra,  an edgeedge with one Cl(6)Ba4 tetrahedra, and edges with two equivalent Cl(3)Ba3Sm tetrahedra.
Ba9Sm6Cl34 crystallizes in the tetragonal I4/m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one Cl(2), one Cl(4), one Cl(6), two equivalent Cl(3), two equivalent Cl(5), and three equivalent Cl(1) atoms. The Ba(1)-Cl(2) bond length is 3.14 Å. The Ba(1)-Cl(4) bond length is 3.59 Å. The Ba(1)-Cl(6) bond length is 3.28 Å. There is one shorter (3.22 Å) and one longer (3.27 Å) Ba(1)-Cl(3) bond length. There is one shorter (3.44 Å) and one longer (3.46 Å) Ba(1)-Cl(5) bond length. There are a spread of Ba(1)-Cl(1) bond distances ranging from 3.14-3.44 Å. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to eight equivalent Cl(3) atoms. All Ba(2)-Cl(3) bond lengths are 3.15 Å. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 8-coordinate geometry to four equivalent Cl(1) and four equivalent Cl(5) atoms. All Sm(1)-Cl(1) bond lengths are 2.87 Å. All Sm(1)-Cl(5) bond lengths are 2.88 Å. In the second Sm site, Sm(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. Both Sm(2)-Cl(2) bond lengths are 2.89 Å. Both Sm(2)-Cl(3) bond lengths are 2.87 Å. There is one shorter (2.81 Å) and one longer (2.84 Å) Sm(2)-Cl(4) bond length. Both Sm(2)-Cl(5) bond lengths are 2.93 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to one Ba(2), two equivalent Ba(1), and one Sm(2) atom to form ClBa3Sm tetrahedra that share corners with two equivalent Cl(2)Ba2Sm2 tetrahedra, corners with two equivalent Cl(6)Ba4 tetrahedra, corners with four equivalent Cl(1)Ba3Sm tetrahedra, corners with four equivalent Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(2)Ba2Sm2 tetrahedra,  an edgeedge with one Cl(1)Ba3Sm tetrahedra, and edges with three equivalent Cl(3)Ba3Sm tetrahedra. In the second Cl site, Cl(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Ba(1) and two equivalent Sm(2) atoms. In the third Cl site, Cl(5) is bonded in a 4-coordinate geometry to two equivalent Ba(1), one Sm(1), and one Sm(2) atom. In the fourth Cl site, Cl(6) is bonded to four equivalent Ba(1) atoms to form ClBa4 tetrahedra that share corners with four equivalent Cl(1)Ba3Sm tetrahedra, corners with eight equivalent Cl(3)Ba3Sm tetrahedra, edges with two equivalent Cl(2)Ba2Sm2 tetrahedra, and edges with four equivalent Cl(1)Ba3Sm tetrahedra. In the fifth Cl site, Cl(1) is bonded to three equivalent Ba(1) and one Sm(1) atom to form ClBa3Sm tetrahedra that share  a cornercorner with one Cl(6)Ba4 tetrahedra, corners with three equivalent Cl(2)Ba2Sm2 tetrahedra, corners with three equivalent Cl(1)Ba3Sm tetrahedra, corners with four equivalent Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(3)Ba3Sm tetrahedra,  an edgeedge with one Cl(6)Ba4 tetrahedra, and edges with three equivalent Cl(1)Ba3Sm tetrahedra. In the sixth Cl site, Cl(2) is bonded to two equivalent Ba(1) and two equivalent Sm(2) atoms to form ClBa2Sm2 tetrahedra that share corners with four equivalent Cl(3)Ba3Sm tetrahedra, corners with six equivalent Cl(1)Ba3Sm tetrahedra,  an edgeedge with one Cl(2)Ba2Sm2 tetrahedra,  an edgeedge with one Cl(6)Ba4 tetrahedra, and edges with two equivalent Cl(3)Ba3Sm tetrahedra.