Ba5La2Cl16 crystallizes in the orthorhombic Ccce space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form distorted BaCl8 hexagonal bipyramids that share corners with two equivalent La(1)Cl6 octahedra and edges with two equivalent La(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(4), and four equivalent Cl(3) atoms. In the third Ba site, Ba(3) is bonded in a distorted body-centered cubic geometry to four equivalent Cl(2) and four equivalent Cl(3) atoms. La(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms to form LaCl6 octahedra that share corners with two equivalent Ba(1)Cl8 hexagonal bipyramids and edges with two equivalent Ba(1)Cl8 hexagonal bipyramids. There are four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms to form a mixture of distorted corner and edge-sharing ClBa4 tetrahedra. In the second Cl site, Cl(4) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one La(1) atom. In the third Cl site, Cl(1) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one La(1) atom. In the fourth Cl site, Cl(2) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(3), and one La(1) atom.
Ba5La2Cl16 crystallizes in the orthorhombic Ccce space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(4) atoms to form distorted BaCl8 hexagonal bipyramids that share corners with two equivalent La(1)Cl6 octahedra and edges with two equivalent La(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 64°. Both Ba(1)-Cl(1) bond lengths are 3.27 Å. Both Ba(1)-Cl(2) bond lengths are 3.23 Å. Both Ba(1)-Cl(3) bond lengths are 3.31 Å. Both Ba(1)-Cl(4) bond lengths are 3.22 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(4), and four equivalent Cl(3) atoms. Both Ba(2)-Cl(1) bond lengths are 3.16 Å. Both Ba(2)-Cl(4) bond lengths are 3.24 Å. There are two shorter (3.13 Å) and two longer (3.71 Å) Ba(2)-Cl(3) bond lengths. In the third Ba site, Ba(3) is bonded in a distorted body-centered cubic geometry to four equivalent Cl(2) and four equivalent Cl(3) atoms. All Ba(3)-Cl(2) bond lengths are 3.06 Å. All Ba(3)-Cl(3) bond lengths are 3.51 Å. La(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(4) atoms to form LaCl6 octahedra that share corners with two equivalent Ba(1)Cl8 hexagonal bipyramids and edges with two equivalent Ba(1)Cl8 hexagonal bipyramids. Both La(1)-Cl(1) bond lengths are 2.76 Å. Both La(1)-Cl(2) bond lengths are 2.75 Å. Both La(1)-Cl(4) bond lengths are 2.82 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms to form a mixture of distorted corner and edge-sharing ClBa4 tetrahedra. In the second Cl site, Cl(4) is bonded in a trigonal non-coplanar geometry to one Ba(1), one Ba(2), and one La(1) atom. In the third Cl site, Cl(1) is bonded in a 3-coordinate geometry to one Ba(1), one Ba(2), and one La(1) atom. In the fourth Cl site, Cl(2) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(3), and one La(1) atom.