Cs3LaBr6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(2), one Br(3), one Br(5), one Br(6), two equivalent Br(1), and two equivalent Br(4) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one Br(1), one Br(3), two equivalent Br(5), two equivalent Br(6), and three equivalent Br(2) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Br(1), one Br(2), one Br(5), one Br(6), two equivalent Br(3), and two equivalent Br(4) atoms. There are two inequivalent La sites. In the first La site, La(1) is bonded in an octahedral geometry to two equivalent Br(1), two equivalent Br(3), and two equivalent Br(4) atoms. In the second La site, La(2) is bonded in an octahedral geometry to two equivalent Br(2), two equivalent Br(5), and two equivalent Br(6) atoms. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded to one Cs(2), one Cs(3), two equivalent Cs(1), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrCs4La trigonal bipyramids. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one La(2) atom. In the third Br site, Br(3) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), and one La(1) atom. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(3), and one La(1) atom. In the fifth Br site, Br(5) is bonded in a 1-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), and one La(2) atom. In the sixth Br site, Br(6) is bonded to one Cs(1), one Cs(3), two equivalent Cs(2), and one La(2) atom to form a mixture of distorted edge, face, and corner-sharing BrCs4La square pyramids.
Cs3LaBr6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(2), one Br(3), one Br(5), one Br(6), two equivalent Br(1), and two equivalent Br(4) atoms. The Cs(1)-Br(2) bond length is 3.56 Å. The Cs(1)-Br(3) bond length is 3.58 Å. The Cs(1)-Br(5) bond length is 3.75 Å. The Cs(1)-Br(6) bond length is 3.75 Å. There is one shorter (3.82 Å) and one longer (3.96 Å) Cs(1)-Br(1) bond length. There is one shorter (3.70 Å) and one longer (3.72 Å) Cs(1)-Br(4) bond length. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to one Br(1), one Br(3), two equivalent Br(5), two equivalent Br(6), and three equivalent Br(2) atoms. The Cs(2)-Br(1) bond length is 3.83 Å. The Cs(2)-Br(3) bond length is 4.22 Å. There is one shorter (3.84 Å) and one longer (4.28 Å) Cs(2)-Br(5) bond length. There is one shorter (3.75 Å) and one longer (3.92 Å) Cs(2)-Br(6) bond length. There are a spread of Cs(2)-Br(2) bond distances ranging from 3.74-4.31 Å. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Br(1), one Br(2), one Br(5), one Br(6), two equivalent Br(3), and two equivalent Br(4) atoms. The Cs(3)-Br(1) bond length is 3.59 Å. The Cs(3)-Br(2) bond length is 3.80 Å. The Cs(3)-Br(5) bond length is 3.84 Å. The Cs(3)-Br(6) bond length is 3.60 Å. There is one shorter (3.75 Å) and one longer (3.99 Å) Cs(3)-Br(3) bond length. There is one shorter (3.60 Å) and one longer (3.64 Å) Cs(3)-Br(4) bond length. There are two inequivalent La sites. In the first La site, La(1) is bonded in an octahedral geometry to two equivalent Br(1), two equivalent Br(3), and two equivalent Br(4) atoms. Both La(1)-Br(1) bond lengths are 2.96 Å. Both La(1)-Br(3) bond lengths are 2.93 Å. Both La(1)-Br(4) bond lengths are 2.96 Å. In the second La site, La(2) is bonded in an octahedral geometry to two equivalent Br(2), two equivalent Br(5), and two equivalent Br(6) atoms. Both La(2)-Br(2) bond lengths are 2.96 Å. Both La(2)-Br(5) bond lengths are 2.91 Å. Both La(2)-Br(6) bond lengths are 2.95 Å. There are six inequivalent Br sites. In the first Br site, Br(1) is bonded to one Cs(2), one Cs(3), two equivalent Cs(1), and one La(1) atom to form a mixture of distorted edge and corner-sharing BrCs4La trigonal bipyramids. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one La(2) atom. In the third Br site, Br(3) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(2), two equivalent Cs(3), and one La(1) atom. In the fourth Br site, Br(4) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(3), and one La(1) atom. In the fifth Br site, Br(5) is bonded in a 1-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), and one La(2) atom. In the sixth Br site, Br(6) is bonded to one Cs(1), one Cs(3), two equivalent Cs(2), and one La(2) atom to form a mixture of distorted edge, face, and corner-sharing BrCs4La square pyramids.