Ca(LaI4)2 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded in a 6-coordinate geometry to two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. La(1) is bonded to one I(2), one I(3), two equivalent I(1), and two equivalent I(4) atoms to form a mixture of distorted corner and edge-sharing LaI6 pentagonal pyramids. There are four inequivalent I sites. In the first I site, I(1) is bonded in a bent 120 degrees geometry to two equivalent La(1) atoms. In the second I site, I(2) is bonded in a water-like geometry to one Ca(1) and one La(1) atom. In the third I site, I(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one La(1) atom. In the fourth I site, I(4) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent La(1) atoms.
Ca(LaI4)2 crystallizes in the monoclinic C2/c space group. Ca(1) is bonded in a 6-coordinate geometry to two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. Both Ca(1)-I(2) bond lengths are 3.26 Å. Both Ca(1)-I(3) bond lengths are 3.14 Å. Both Ca(1)-I(4) bond lengths are 3.29 Å. La(1) is bonded to one I(2), one I(3), two equivalent I(1), and two equivalent I(4) atoms to form a mixture of distorted corner and edge-sharing LaI6 pentagonal pyramids. The La(1)-I(2) bond length is 3.13 Å. The La(1)-I(3) bond length is 3.11 Å. There is one shorter (3.17 Å) and one longer (3.20 Å) La(1)-I(1) bond length. There is one shorter (3.23 Å) and one longer (3.30 Å) La(1)-I(4) bond length. There are four inequivalent I sites. In the first I site, I(1) is bonded in a bent 120 degrees geometry to two equivalent La(1) atoms. In the second I site, I(2) is bonded in a water-like geometry to one Ca(1) and one La(1) atom. In the third I site, I(3) is bonded in a bent 150 degrees geometry to one Ca(1) and one La(1) atom. In the fourth I site, I(4) is bonded in a distorted trigonal non-coplanar geometry to one Ca(1) and two equivalent La(1) atoms.