BaCaI4 crystallizes in the monoclinic P2/c space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent I(1) and four equivalent I(2) atoms. Ca(1) is bonded to two equivalent I(1) and four equivalent I(2) atoms to form distorted edge-sharing CaI6 octahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Ca(1) atom. In the second I site, I(2) is bonded to two equivalent Ba(1) and two equivalent Ca(1) atoms to form a mixture of distorted corner and edge-sharing IBa2Ca2 trigonal pyramids.
BaCaI4 crystallizes in the monoclinic P2/c space group. Ba(1) is bonded in a 8-coordinate geometry to four equivalent I(1) and four equivalent I(2) atoms. There are two shorter (3.46 Å) and two longer (3.59 Å) Ba(1)-I(1) bond lengths. There are two shorter (3.63 Å) and two longer (3.80 Å) Ba(1)-I(2) bond lengths. Ca(1) is bonded to two equivalent I(1) and four equivalent I(2) atoms to form distorted edge-sharing CaI6 octahedra. Both Ca(1)-I(1) bond lengths are 3.08 Å. There are two shorter (3.18 Å) and two longer (3.24 Å) Ca(1)-I(2) bond lengths. There are two inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ba(1) and one Ca(1) atom. In the second I site, I(2) is bonded to two equivalent Ba(1) and two equivalent Ca(1) atoms to form a mixture of distorted corner and edge-sharing IBa2Ca2 trigonal pyramids.