La4B4I5 crystallizes in the monoclinic Cm space group. There are four inequivalent La sites. In the first La site, La(1) is bonded to two equivalent B(1), two equivalent B(3), one I(1), one I(3), and two equivalent I(5) atoms to form a mixture of distorted edge and corner-sharing LaB4I4 hexagonal bipyramids. In the second La site, La(2) is bonded to two equivalent B(1), two equivalent B(2), one I(2), one I(4), and two equivalent I(5) atoms to form a mixture of distorted edge and corner-sharing LaB4I4 hexagonal bipyramids. In the third La site, La(3) is bonded in a 9-coordinate geometry to one B(2), one B(3), two equivalent B(1), one I(3), two equivalent I(1), and two equivalent I(4) atoms. In the fourth La site, La(4) is bonded in a 9-coordinate geometry to one B(2), one B(3), two equivalent B(1), one I(4), two equivalent I(2), and two equivalent I(3) atoms. There are three inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one La(1), one La(2), one La(3), one La(4), one B(1), one B(2), and one B(3) atom. In the second B site, B(2) is bonded in a 7-coordinate geometry to one La(3), one La(4), two equivalent La(2), one B(3), and two equivalent B(1) atoms. In the third B site, B(3) is bonded in a 7-coordinate geometry to one La(3), one La(4), two equivalent La(1), one B(2), and two equivalent B(1) atoms. There are five inequivalent I sites. In the first I site, I(1) is bonded in a distorted T-shaped geometry to one La(1) and two equivalent La(3) atoms. In the second I site, I(2) is bonded in a distorted T-shaped geometry to one La(2) and two equivalent La(4) atoms. In the third I site, I(3) is bonded in a distorted see-saw-like geometry to one La(1), one La(3), and two equivalent La(4) atoms. In the fourth I site, I(4) is bonded in a distorted see-saw-like geometry to one La(2), one La(4), and two equivalent La(3) atoms. In the fifth I site, I(5) is bonded in a square co-planar geometry to two equivalent La(1) and two equivalent La(2) atoms.
La4B4I5 crystallizes in the monoclinic Cm space group. There are four inequivalent La sites. In the first La site, La(1) is bonded to two equivalent B(1), two equivalent B(3), one I(1), one I(3), and two equivalent I(5) atoms to form a mixture of distorted edge and corner-sharing LaB4I4 hexagonal bipyramids. Both La(1)-B(1) bond lengths are 2.68 Å. Both La(1)-B(3) bond lengths are 2.70 Å. The La(1)-I(1) bond length is 3.28 Å. The La(1)-I(3) bond length is 3.33 Å. Both La(1)-I(5) bond lengths are 3.44 Å. In the second La site, La(2) is bonded to two equivalent B(1), two equivalent B(2), one I(2), one I(4), and two equivalent I(5) atoms to form a mixture of distorted edge and corner-sharing LaB4I4 hexagonal bipyramids. Both La(2)-B(1) bond lengths are 2.68 Å. Both La(2)-B(2) bond lengths are 2.70 Å. The La(2)-I(2) bond length is 3.28 Å. The La(2)-I(4) bond length is 3.33 Å. Both La(2)-I(5) bond lengths are 3.45 Å. In the third La site, La(3) is bonded in a 9-coordinate geometry to one B(2), one B(3), two equivalent B(1), one I(3), two equivalent I(1), and two equivalent I(4) atoms. The La(3)-B(2) bond length is 2.69 Å. The La(3)-B(3) bond length is 2.68 Å. Both La(3)-B(1) bond lengths are 2.86 Å. The La(3)-I(3) bond length is 3.62 Å. Both La(3)-I(1) bond lengths are 3.31 Å. Both La(3)-I(4) bond lengths are 3.35 Å. In the fourth La site, La(4) is bonded in a 9-coordinate geometry to one B(2), one B(3), two equivalent B(1), one I(4), two equivalent I(2), and two equivalent I(3) atoms. The La(4)-B(2) bond length is 2.68 Å. The La(4)-B(3) bond length is 2.69 Å. Both La(4)-B(1) bond lengths are 2.86 Å. The La(4)-I(4) bond length is 3.61 Å. Both La(4)-I(2) bond lengths are 3.31 Å. Both La(4)-I(3) bond lengths are 3.35 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one La(1), one La(2), one La(3), one La(4), one B(1), one B(2), and one B(3) atom. The B(1)-B(1) bond length is 1.61 Å. The B(1)-B(2) bond length is 1.68 Å. The B(1)-B(3) bond length is 1.68 Å. In the second B site, B(2) is bonded in a 7-coordinate geometry to one La(3), one La(4), two equivalent La(2), one B(3), and two equivalent B(1) atoms. The B(2)-B(3) bond length is 1.92 Å. In the third B site, B(3) is bonded in a 7-coordinate geometry to one La(3), one La(4), two equivalent La(1), one B(2), and two equivalent B(1) atoms. There are five inequivalent I sites. In the first I site, I(1) is bonded in a distorted T-shaped geometry to one La(1) and two equivalent La(3) atoms. In the second I site, I(2) is bonded in a distorted T-shaped geometry to one La(2) and two equivalent La(4) atoms. In the third I site, I(3) is bonded in a distorted see-saw-like geometry to one La(1), one La(3), and two equivalent La(4) atoms. In the fourth I site, I(4) is bonded in a distorted see-saw-like geometry to one La(2), one La(4), and two equivalent La(3) atoms. In the fifth I site, I(5) is bonded in a square co-planar geometry to two equivalent La(1) and two equivalent La(2) atoms.