Bi3(TeCl5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Cl(1), one Cl(10), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted corner-sharing BiCl6 pentagonal pyramids. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to one Cl(4), one Cl(5), one Cl(8), and one Cl(9) atom. In the third Bi site, Bi(3) is bonded to one Cl(1), one Cl(3), one Cl(5), one Cl(7), and two equivalent Cl(2) atoms to form a mixture of distorted corner and edge-sharing BiCl6 pentagonal pyramids. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 3-coordinate geometry to two equivalent Te(2) and one Cl(10) atom. In the second Te site, Te(2) is bonded in an L-shaped geometry to two equivalent Te(1) atoms. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to one Bi(1) and one Bi(3) atom. In the second Cl site, Cl(2) is bonded in a water-like geometry to two equivalent Bi(3) atoms. In the third Cl site, Cl(3) is bonded in a distorted water-like geometry to one Bi(1) and one Bi(3) atom. In the fourth Cl site, Cl(4) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(2) atom. In the fifth Cl site, Cl(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. In the sixth Cl site, Cl(6) is bonded in a single-bond geometry to one Bi(1) atom. In the seventh Cl site, Cl(7) is bonded in a distorted single-bond geometry to one Bi(3) atom. In the eighth Cl site, Cl(8) is bonded in a single-bond geometry to one Bi(2) atom. In the ninth Cl site, Cl(9) is bonded in a single-bond geometry to one Bi(2) atom. In the tenth Cl site, Cl(10) is bonded in a single-bond geometry to one Bi(1) and one Te(1) atom.
Bi3(TeCl5)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Cl(1), one Cl(10), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted corner-sharing BiCl6 pentagonal pyramids. The Bi(1)-Cl(1) bond length is 2.86 Å. The Bi(1)-Cl(10) bond length is 2.63 Å. The Bi(1)-Cl(3) bond length is 2.65 Å. The Bi(1)-Cl(4) bond length is 2.97 Å. The Bi(1)-Cl(5) bond length is 3.02 Å. The Bi(1)-Cl(6) bond length is 2.53 Å. In the second Bi site, Bi(2) is bonded in a 3-coordinate geometry to one Cl(4), one Cl(5), one Cl(8), and one Cl(9) atom. The Bi(2)-Cl(4) bond length is 2.56 Å. The Bi(2)-Cl(5) bond length is 3.16 Å. The Bi(2)-Cl(8) bond length is 2.55 Å. The Bi(2)-Cl(9) bond length is 2.48 Å. In the third Bi site, Bi(3) is bonded to one Cl(1), one Cl(3), one Cl(5), one Cl(7), and two equivalent Cl(2) atoms to form a mixture of distorted corner and edge-sharing BiCl6 pentagonal pyramids. The Bi(3)-Cl(1) bond length is 2.85 Å. The Bi(3)-Cl(3) bond length is 3.00 Å. The Bi(3)-Cl(5) bond length is 2.70 Å. The Bi(3)-Cl(7) bond length is 2.58 Å. There is one shorter (2.72 Å) and one longer (2.83 Å) Bi(3)-Cl(2) bond length. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded in a 3-coordinate geometry to two equivalent Te(2) and one Cl(10) atom. There is one shorter (2.69 Å) and one longer (2.71 Å) Te(1)-Te(2) bond length. The Te(1)-Cl(10) bond length is 3.15 Å. In the second Te site, Te(2) is bonded in an L-shaped geometry to two equivalent Te(1) atoms. There are ten inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a water-like geometry to one Bi(1) and one Bi(3) atom. In the second Cl site, Cl(2) is bonded in a water-like geometry to two equivalent Bi(3) atoms. In the third Cl site, Cl(3) is bonded in a distorted water-like geometry to one Bi(1) and one Bi(3) atom. In the fourth Cl site, Cl(4) is bonded in a bent 120 degrees geometry to one Bi(1) and one Bi(2) atom. In the fifth Cl site, Cl(5) is bonded in a distorted trigonal non-coplanar geometry to one Bi(1), one Bi(2), and one Bi(3) atom. In the sixth Cl site, Cl(6) is bonded in a single-bond geometry to one Bi(1) atom. In the seventh Cl site, Cl(7) is bonded in a distorted single-bond geometry to one Bi(3) atom. In the eighth Cl site, Cl(8) is bonded in a single-bond geometry to one Bi(2) atom. In the ninth Cl site, Cl(9) is bonded in a single-bond geometry to one Bi(2) atom. In the tenth Cl site, Cl(10) is bonded in a single-bond geometry to one Bi(1) and one Te(1) atom.