Cs3BiCl6 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 Cl(1), one Cl(3), one Cl(4), one Cl(6), two equivalent Cl(2), and two equivalent Cl(5) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one Cl(1), one Cl(5), two equivalent Cl(3), three equivalent Cl(4), and three equivalent Cl(6) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(2) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in an octahedral geometry to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(6) atoms. In the second Bi site, Bi(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(5) atoms. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Cs(1), one Cs(2), two equivalent Cs(3), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(3), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), and one Bi(1) atom. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one Bi(1) atom. In the fifth Cl site, Cl(5) is bonded to one Cs(2), one Cs(3), two equivalent Cs(1), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one Bi(1) atom.
Cs3BiCl6 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 Cl(1), one Cl(3), one Cl(4), one Cl(6), two equivalent Cl(2), and two equivalent Cl(5) atoms. The Cs(1)-Cl(1) bond length is 3.42 Å. The Cs(1)-Cl(3) bond length is 3.60 Å. The Cs(1)-Cl(4) bond length is 3.69 Å. The Cs(1)-Cl(6) bond length is 3.42 Å. There is one shorter (3.43 Å) and one longer (3.47 Å) Cs(1)-Cl(2) bond length. There is one shorter (3.61 Å) and one longer (3.78 Å) Cs(1)-Cl(5) bond length. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one Cl(1), one Cl(5), two equivalent Cl(3), three equivalent Cl(4), and three equivalent Cl(6) atoms. The Cs(2)-Cl(1) bond length is 3.74 Å. The Cs(2)-Cl(5) bond length is 3.89 Å. There is one shorter (3.65 Å) and one longer (3.94 Å) Cs(2)-Cl(3) bond length. There are a spread of Cs(2)-Cl(4) bond distances ranging from 3.62-4.20 Å. There are a spread of Cs(2)-Cl(6) bond distances ranging from 3.62-4.12 Å. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(2) atoms. The Cs(3)-Cl(3) bond length is 3.55 Å. The Cs(3)-Cl(4) bond length is 3.40 Å. The Cs(3)-Cl(5) bond length is 3.41 Å. The Cs(3)-Cl(6) bond length is 3.67 Å. There is one shorter (3.69 Å) and one longer (3.73 Å) Cs(3)-Cl(1) bond length. There is one shorter (3.54 Å) and one longer (3.55 Å) Cs(3)-Cl(2) bond length. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in an octahedral geometry to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(6) atoms. Both Bi(1)-Cl(3) bond lengths are 2.70 Å. Both Bi(1)-Cl(4) bond lengths are 2.72 Å. Both Bi(1)-Cl(6) bond lengths are 2.74 Å. In the second Bi site, Bi(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(5) atoms. Both Bi(2)-Cl(1) bond lengths are 2.73 Å. Both Bi(2)-Cl(2) bond lengths are 2.73 Å. Both Bi(2)-Cl(5) bond lengths are 2.72 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Cs(1), one Cs(2), two equivalent Cs(3), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the second Cl site, Cl(2) is bonded to two equivalent Cs(1), two equivalent Cs(3), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), two equivalent Cs(2), and one Bi(1) atom. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one Bi(1) atom. In the fifth Cl site, Cl(5) is bonded to one Cs(2), one Cs(3), two equivalent Cs(1), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing ClCs4Bi trigonal bipyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Cs(1), one Cs(3), three equivalent Cs(2), and one Bi(1) atom.