KAlBr4 crystallizes in the monoclinic P2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(4) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. Al(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), one Br(3), and one Br(4) atom. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one K(2), and one Al(1) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to one K(1), one K(2), and one Al(1) atom. In the third Br site, Br(3) is bonded in a distorted single-bond geometry to one K(2) and one Al(1) atom. In the fourth Br site, Br(4) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one Al(1) atom.
KAlBr4 crystallizes in the monoclinic P2/c space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(4) atoms. Both K(1)-Br(1) bond lengths are 3.36 Å. Both K(1)-Br(2) bond lengths are 3.36 Å. Both K(1)-Br(4) bond lengths are 3.45 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent Br(1), two equivalent Br(2), two equivalent Br(3), and two equivalent Br(4) atoms. Both K(2)-Br(1) bond lengths are 3.44 Å. Both K(2)-Br(2) bond lengths are 3.47 Å. Both K(2)-Br(3) bond lengths are 3.47 Å. Both K(2)-Br(4) bond lengths are 3.52 Å. Al(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), one Br(3), and one Br(4) atom. The Al(1)-Br(1) bond length is 2.32 Å. The Al(1)-Br(2) bond length is 2.32 Å. The Al(1)-Br(3) bond length is 2.30 Å. The Al(1)-Br(4) bond length is 2.31 Å. There are four inequivalent Br sites. In the first Br site, Br(1) is bonded in a distorted trigonal non-coplanar geometry to one K(1), one K(2), and one Al(1) atom. In the second Br site, Br(2) is bonded in a 3-coordinate geometry to one K(1), one K(2), and one Al(1) atom. In the third Br site, Br(3) is bonded in a distorted single-bond geometry to one K(2) and one Al(1) atom. In the fourth Br site, Br(4) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one Al(1) atom.