Ba6CaI14 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one I(3), one I(4), one I(5), two equivalent I(1), and two equivalent I(2) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent I(1), two equivalent I(5), and four equivalent I(4) atoms. Ca(1) is bonded in an octahedral geometry to two equivalent I(5) and four equivalent I(1) atoms. There are five inequivalent I sites. In the first I site, I(4) is bonded in a trigonal non-coplanar geometry to one Ba(1) and two equivalent Ba(2) atoms. In the second I site, I(5) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Ca(1) atom. In the third I site, I(1) is bonded in a 3-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Ca(1) atom. In the fourth I site, I(2) is bonded in a distorted L-shaped geometry to four equivalent Ba(1) atoms. In the fifth I site, I(3) is bonded in a water-like geometry to two equivalent Ba(1) atoms.
Ba6CaI14 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 7-coordinate geometry to one I(3), one I(4), one I(5), two equivalent I(1), and two equivalent I(2) atoms. The Ba(1)-I(3) bond length is 3.29 Å. The Ba(1)-I(4) bond length is 3.52 Å. The Ba(1)-I(5) bond length is 3.76 Å. There is one shorter (3.60 Å) and one longer (4.22 Å) Ba(1)-I(1) bond length. There is one shorter (3.48 Å) and one longer (4.19 Å) Ba(1)-I(2) bond length. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to two equivalent I(1), two equivalent I(5), and four equivalent I(4) atoms. Both Ba(2)-I(1) bond lengths are 3.59 Å. There is one shorter (3.89 Å) and one longer (4.04 Å) Ba(2)-I(5) bond length. There are two shorter (3.45 Å) and two longer (3.46 Å) Ba(2)-I(4) bond lengths. Ca(1) is bonded in an octahedral geometry to two equivalent I(5) and four equivalent I(1) atoms. Both Ca(1)-I(5) bond lengths are 3.08 Å. All Ca(1)-I(1) bond lengths are 3.18 Å. There are five inequivalent I sites. In the first I site, I(4) is bonded in a trigonal non-coplanar geometry to one Ba(1) and two equivalent Ba(2) atoms. In the second I site, I(5) is bonded in a 5-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and one Ca(1) atom. In the third I site, I(1) is bonded in a 3-coordinate geometry to one Ba(2), two equivalent Ba(1), and one Ca(1) atom. In the fourth I site, I(2) is bonded in a distorted L-shaped geometry to four equivalent Ba(1) atoms. In the fifth I site, I(3) is bonded in a water-like geometry to two equivalent Ba(1) atoms.