Ba2TmCl7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(7), two equivalent Cl(5), and two equivalent Cl(6) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(3), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(7) atoms. Tm(1) is bonded in a distorted pentagonal bipyramidal geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and one Cl(7) atom. There are seven inequivalent Cl sites. In the first Cl site, Cl(6) is bonded to one Ba(2), two equivalent Ba(1), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the second Cl site, Cl(7) is bonded to one Ba(1), two equivalent Ba(2), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the third Cl site, Cl(1) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the fourth Cl site, Cl(2) is bonded to one Ba(1), two equivalent Ba(2), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the fifth Cl site, Cl(3) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the sixth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the seventh Cl site, Cl(5) is bonded to one Ba(2), two equivalent Ba(1), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra.
Ba2TmCl7 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(7), two equivalent Cl(5), and two equivalent Cl(6) atoms. The Ba(1)-Cl(1) bond length is 3.10 Å. The Ba(1)-Cl(2) bond length is 3.24 Å. The Ba(1)-Cl(3) bond length is 3.31 Å. The Ba(1)-Cl(4) bond length is 3.30 Å. The Ba(1)-Cl(7) bond length is 3.29 Å. There is one shorter (3.17 Å) and one longer (3.18 Å) Ba(1)-Cl(5) bond length. There is one shorter (3.19 Å) and one longer (3.33 Å) Ba(1)-Cl(6) bond length. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(3), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(7) atoms. The Ba(2)-Cl(1) bond length is 3.09 Å. The Ba(2)-Cl(3) bond length is 3.24 Å. The Ba(2)-Cl(4) bond length is 3.37 Å. The Ba(2)-Cl(5) bond length is 3.23 Å. The Ba(2)-Cl(6) bond length is 3.19 Å. There is one shorter (3.24 Å) and one longer (3.25 Å) Ba(2)-Cl(2) bond length. There is one shorter (3.25 Å) and one longer (3.33 Å) Ba(2)-Cl(7) bond length. Tm(1) is bonded in a distorted pentagonal bipyramidal geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and one Cl(7) atom. The Tm(1)-Cl(1) bond length is 2.68 Å. The Tm(1)-Cl(2) bond length is 2.77 Å. The Tm(1)-Cl(3) bond length is 2.64 Å. The Tm(1)-Cl(4) bond length is 2.64 Å. The Tm(1)-Cl(5) bond length is 2.75 Å. The Tm(1)-Cl(6) bond length is 2.68 Å. The Tm(1)-Cl(7) bond length is 2.69 Å. There are seven inequivalent Cl sites. In the first Cl site, Cl(6) is bonded to one Ba(2), two equivalent Ba(1), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the second Cl site, Cl(7) is bonded to one Ba(1), two equivalent Ba(2), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the third Cl site, Cl(1) is bonded in a distorted trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the fourth Cl site, Cl(2) is bonded to one Ba(1), two equivalent Ba(2), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra. In the fifth Cl site, Cl(3) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the sixth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one Tm(1) atom. In the seventh Cl site, Cl(5) is bonded to one Ba(2), two equivalent Ba(1), and one Tm(1) atom to form a mixture of edge and corner-sharing ClBa3Tm tetrahedra.