PtBi6Cl12(Bi)6 is Indium-like structured and crystallizes in the triclinic P1 space group. The structure is zero-dimensional and consists of one Bi cluster and one PtBi6Cl12 cluster. In the Bi cluster, there are six inequivalent Bi sites. In the first Bi site, Bi(4) is bonded in a 3-coordinate geometry to one Bi(11), one Bi(12), and one Bi(5) atom. In the second Bi site, Bi(5) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(11), one Bi(12), and one Bi(4) atom. In the third Bi site, Bi(9) is bonded in a 3-coordinate geometry to one Bi(10), one Bi(11), and one Bi(12) atom. In the fourth Bi site, Bi(10) is bonded in a 4-coordinate geometry to one Bi(11), one Bi(12), one Bi(5), and one Bi(9) atom. In the fifth Bi site, Bi(11) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(4), one Bi(5), and one Bi(9) atom. In the sixth Bi site, Bi(12) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(4), one Bi(5), and one Bi(9) atom. In the PtBi6Cl12 cluster, Pt(1) is bonded in an octahedral geometry to one Bi(1), one Bi(2), one Bi(3), one Bi(6), one Bi(7), and one Bi(8) atom. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Pt(1), one Cl(11), one Cl(3), one Cl(8), and one Cl(9) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. In the second Bi site, Bi(2) is bonded to one Pt(1), one Cl(1), one Cl(2), one Cl(5), and one Cl(8) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. In the third Bi site, Bi(3) is bonded to one Pt(1), one Cl(10), one Cl(12), one Cl(2), and one Cl(7) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. In the fourth Bi site, Bi(6) is bonded to one Pt(1), one Cl(12), one Cl(4), one Cl(6), and one Cl(9) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. In the fifth Bi site, Bi(7) is bonded to one Pt(1), one Cl(3), one Cl(5), one Cl(6), and one Cl(7) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. In the sixth Bi site, Bi(8) is bonded to one Pt(1), one Cl(1), one Cl(10), one Cl(11), and one Cl(4) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in an L-shaped geometry to one Bi(2) and one Bi(8) atom. In the second Cl site, Cl(2) is bonded in an L-shaped geometry to one Bi(2) and one Bi(3) atom. In the third Cl site, Cl(3) is bonded in an L-shaped geometry to one Bi(1) and one Bi(7) atom. In the fourth Cl site, Cl(4) is bonded in an L-shaped geometry to one Bi(6) and one Bi(8) atom. In the fifth Cl site, Cl(5) is bonded in an L-shaped geometry to one Bi(2) and one Bi(7) atom. In the sixth Cl site, Cl(6) is bonded in an L-shaped geometry to one Bi(6) and one Bi(7) atom. In the seventh Cl site, Cl(7) is bonded in an L-shaped geometry to one Bi(3) and one Bi(7) atom. In the eighth Cl site, Cl(8) is bonded in an L-shaped geometry to one Bi(1) and one Bi(2) atom. In the ninth Cl site, Cl(9) is bonded in an L-shaped geometry to one Bi(1) and one Bi(6) atom. In the tenth Cl site, Cl(10) is bonded in an L-shaped geometry to one Bi(3) and one Bi(8) atom. In the eleventh Cl site, Cl(11) is bonded in an L-shaped geometry to one Bi(1) and one Bi(8) atom. In the twelfth Cl site, Cl(12) is bonded in an L-shaped geometry to one Bi(3) and one Bi(6) atom.
PtBi6Cl12(Bi)6 is Indium-like structured and crystallizes in the triclinic P1 space group. The structure is zero-dimensional and consists of one Bi cluster and one PtBi6Cl12 cluster. In the Bi cluster, there are six inequivalent Bi sites. In the first Bi site, Bi(4) is bonded in a 3-coordinate geometry to one Bi(11), one Bi(12), and one Bi(5) atom. The Bi(4)-Bi(11) bond length is 3.14 Å. The Bi(4)-Bi(12) bond length is 3.07 Å. The Bi(4)-Bi(5) bond length is 2.94 Å. In the second Bi site, Bi(5) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(11), one Bi(12), and one Bi(4) atom. The Bi(5)-Bi(10) bond length is 3.27 Å. The Bi(5)-Bi(11) bond length is 3.21 Å. The Bi(5)-Bi(12) bond length is 3.29 Å. In the third Bi site, Bi(9) is bonded in a 3-coordinate geometry to one Bi(10), one Bi(11), and one Bi(12) atom. The Bi(9)-Bi(10) bond length is 2.94 Å. The Bi(9)-Bi(11) bond length is 3.15 Å. The Bi(9)-Bi(12) bond length is 3.08 Å. In the fourth Bi site, Bi(10) is bonded in a 4-coordinate geometry to one Bi(11), one Bi(12), one Bi(5), and one Bi(9) atom. The Bi(10)-Bi(11) bond length is 3.18 Å. The Bi(10)-Bi(12) bond length is 3.28 Å. In the fifth Bi site, Bi(11) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(4), one Bi(5), and one Bi(9) atom. In the sixth Bi site, Bi(12) is bonded in a 4-coordinate geometry to one Bi(10), one Bi(4), one Bi(5), and one Bi(9) atom. In the PtBi6Cl12 cluster, Pt(1) is bonded in an octahedral geometry to one Bi(1), one Bi(2), one Bi(3), one Bi(6), one Bi(7), and one Bi(8) atom. The Pt(1)-Bi(1) bond length is 2.75 Å. The Pt(1)-Bi(2) bond length is 2.75 Å. The Pt(1)-Bi(3) bond length is 2.75 Å. The Pt(1)-Bi(6) bond length is 2.75 Å. The Pt(1)-Bi(7) bond length is 2.76 Å. The Pt(1)-Bi(8) bond length is 2.75 Å. There are six inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Pt(1), one Cl(11), one Cl(3), one Cl(8), and one Cl(9) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(1)-Cl(11) bond length is 2.83 Å. The Bi(1)-Cl(3) bond length is 2.82 Å. The Bi(1)-Cl(8) bond length is 2.82 Å. The Bi(1)-Cl(9) bond length is 2.79 Å. In the second Bi site, Bi(2) is bonded to one Pt(1), one Cl(1), one Cl(2), one Cl(5), and one Cl(8) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(2)-Cl(1) bond length is 2.80 Å. The Bi(2)-Cl(2) bond length is 2.79 Å. The Bi(2)-Cl(5) bond length is 2.82 Å. The Bi(2)-Cl(8) bond length is 2.84 Å. In the third Bi site, Bi(3) is bonded to one Pt(1), one Cl(10), one Cl(12), one Cl(2), and one Cl(7) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(3)-Cl(10) bond length is 2.85 Å. The Bi(3)-Cl(12) bond length is 2.81 Å. The Bi(3)-Cl(2) bond length is 2.81 Å. The Bi(3)-Cl(7) bond length is 2.78 Å. In the fourth Bi site, Bi(6) is bonded to one Pt(1), one Cl(12), one Cl(4), one Cl(6), and one Cl(9) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(6)-Cl(12) bond length is 2.85 Å. The Bi(6)-Cl(4) bond length is 2.80 Å. The Bi(6)-Cl(6) bond length is 2.83 Å. The Bi(6)-Cl(9) bond length is 2.78 Å. In the fifth Bi site, Bi(7) is bonded to one Pt(1), one Cl(3), one Cl(5), one Cl(6), and one Cl(7) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(7)-Cl(3) bond length is 2.83 Å. The Bi(7)-Cl(5) bond length is 2.81 Å. The Bi(7)-Cl(6) bond length is 2.80 Å. The Bi(7)-Cl(7) bond length is 2.80 Å. In the sixth Bi site, Bi(8) is bonded to one Pt(1), one Cl(1), one Cl(10), one Cl(11), and one Cl(4) atom to form a mixture of corner and edge-sharing BiPtCl4 square pyramids. The Bi(8)-Cl(1) bond length is 2.79 Å. The Bi(8)-Cl(10) bond length is 2.78 Å. The Bi(8)-Cl(11) bond length is 2.86 Å. The Bi(8)-Cl(4) bond length is 2.84 Å. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in an L-shaped geometry to one Bi(2) and one Bi(8) atom. In the second Cl site, Cl(2) is bonded in an L-shaped geometry to one Bi(2) and one Bi(3) atom. In the third Cl site, Cl(3) is bonded in an L-shaped geometry to one Bi(1) and one Bi(7) atom. In the fourth Cl site, Cl(4) is bonded in an L-shaped geometry to one Bi(6) and one Bi(8) atom. In the fifth Cl site, Cl(5) is bonded in an L-shaped geometry to one Bi(2) and one Bi(7) atom. In the sixth Cl site, Cl(6) is bonded in an L-shaped geometry to one Bi(6) and one Bi(7) atom. In the seventh Cl site, Cl(7) is bonded in an L-shaped geometry to one Bi(3) and one Bi(7) atom. In the eighth Cl site, Cl(8) is bonded in an L-shaped geometry to one Bi(1) and one Bi(2) atom. In the ninth Cl site, Cl(9) is bonded in an L-shaped geometry to one Bi(1) and one Bi(6) atom. In the tenth Cl site, Cl(10) is bonded in an L-shaped geometry to one Bi(3) and one Bi(8) atom. In the eleventh Cl site, Cl(11) is bonded in an L-shaped geometry to one Bi(1) and one Bi(8) atom. In the twelfth Cl site, Cl(12) is bonded in an L-shaped geometry to one Bi(3) and one Bi(6) atom.