Ba2CaI6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent I(3) and four equivalent I(1) atoms to form BaI6 octahedra that share corners with two equivalent Ba(2)I6 octahedra, corners with six equivalent Ca(1)I6 octahedra, and edges with two equivalent Ba(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. In the second Ba site, Ba(2) is bonded to two equivalent I(3) and four equivalent I(2) atoms to form BaI6 octahedra that share corners with two equivalent Ba(1)I6 octahedra, corners with two equivalent Ca(1)I6 octahedra, corners with four equivalent Ba(2)I6 octahedra, and edges with two equivalent Ca(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. Ca(1) is bonded to two equivalent I(1), two equivalent I(2), and two equivalent I(3) atoms to form CaI6 octahedra that share corners with two equivalent Ba(2)I6 octahedra, corners with six equivalent Ba(1)I6 octahedra, and edges with two equivalent Ba(2)I6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are three inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one Ca(1) atom. In the second I site, I(2) is bonded in a trigonal planar geometry to two equivalent Ba(2) and one Ca(1) atom. In the third I site, I(3) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one Ca(1) atom.
Ba2CaI6 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to two equivalent I(3) and four equivalent I(1) atoms to form BaI6 octahedra that share corners with two equivalent Ba(2)I6 octahedra, corners with six equivalent Ca(1)I6 octahedra, and edges with two equivalent Ba(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. Both Ba(1)-I(3) bond lengths are 3.47 Å. All Ba(1)-I(1) bond lengths are 3.49 Å. In the second Ba site, Ba(2) is bonded to two equivalent I(3) and four equivalent I(2) atoms to form BaI6 octahedra that share corners with two equivalent Ba(1)I6 octahedra, corners with two equivalent Ca(1)I6 octahedra, corners with four equivalent Ba(2)I6 octahedra, and edges with two equivalent Ca(1)I6 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. Both Ba(2)-I(3) bond lengths are 3.48 Å. There are two shorter (3.45 Å) and two longer (3.46 Å) Ba(2)-I(2) bond lengths. Ca(1) is bonded to two equivalent I(1), two equivalent I(2), and two equivalent I(3) atoms to form CaI6 octahedra that share corners with two equivalent Ba(2)I6 octahedra, corners with six equivalent Ba(1)I6 octahedra, and edges with two equivalent Ba(2)I6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Both Ca(1)-I(1) bond lengths are 3.19 Å. Both Ca(1)-I(2) bond lengths are 3.19 Å. Both Ca(1)-I(3) bond lengths are 3.15 Å. There are three inequivalent I sites. In the first I site, I(1) is bonded in a distorted trigonal planar geometry to two equivalent Ba(1) and one Ca(1) atom. In the second I site, I(2) is bonded in a trigonal planar geometry to two equivalent Ba(2) and one Ca(1) atom. In the third I site, I(3) is bonded in a distorted trigonal planar geometry to one Ba(1), one Ba(2), and one Ca(1) atom.