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Octahedral molecular geometry

physical science Maturity 9-11 Next article →

Octahedral molecular geometry describes a specific spatial arrangement of atoms. In this geometry, six ligands, which are atoms or groups of atoms, surround a single central atom. These six ligands sit at the vertices of an octahedron. An octahedron is a Platonic solid with eight triangular faces. This shape is also called square bipyramidal. While a perfect octahedron is a mathematical concept, molecular octahedrons often feature a central atom with no bonds between the surrounding ligands.

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Sulfur-hexafluoride-3D-vdW

This geometry is central to coordination chemistry. A chemist might use the term "octahedral" even if the bonds are not mathematically perfect. For example, some molecules have bond orientations that deviate from a perfect octahedron but are still called octahedral. The concept was pioneered by Alfred Werner. He developed this idea to explain how coordination compounds are structured. His work allowed scientists to understand isomerism, which is how molecules can have the same parts but different shapes. For these discoveries, Werner won the Nobel Prize in 1913.

When different types of ligands attach to a metal center, they create isomers. Isomers are versions of a molecule that differ in their spatial arrangement. In a complex with two types of ligands, such as MLLb, two main types exist. The cis isomer places the two Lb ligands next to each other. The trans isomer places them 180 degrees apart. For complexes with three identical ligands, such as MLLbLc, facial and meridional isomers appear. A facial isomer, or fac, has the three identical ligands occupying one triangular face of the octahedron. A meridional isomer, or mer, has the three ligands sitting on a plane that passes through the central atom.

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Sulfur-hexafluoride-3D-vdW

Complexity increases rapidly as more different ligands are added. For a complex with three different types of ligands (MLLbLc), there are three possible isomers. If a complex has six entirely different ligands, it can have 30 different isomers. This is much more complex than a tetrahedron, which only has two stereoisomers when it has four different ligands. This variety allows for many different chemical properties. For instance, an octahedral complex with six different ligands has 15 pairs of enantiomers, which are mirror-image versions of the molecule.

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Sulfur-hexafluoride-3D-vdW

Sometimes, the symmetry of an octahedron is not perfect. This can happen due to the Jahn–Teller effect. This phenomenon causes a tetragonal distortion, which reduces the symmetry from Oh to D4h. This means the shape might look stretched or compressed. Other distortions occur when a molecule has a lone pair of electrons. In molecules like XeF6, the lone pair can push the atoms into a monocapped octahedron. This shape is derived from an octahedron by placing a "cap" over one of the triangular faces.

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Sulfur-hexafluoride-3D-vdW

Octahedral units can also link together to form larger structures called bioctahedra. This happens when terminal ligands are replaced by bridging ligands. There are two common ways to fuse these shapes: edge-sharing and face-sharing. Edge-sharing bioctahedra have the formula [M2L8(μ-L)]2. Face-sharing bioctahedra have the formula M2L6(μ-L)3. These patterns can even form infinite polymeric chains. Niobium pentachloride is an example of a compound with bioctahedral structures. Other compounds, like zirconium tetrachloride, form polymers through edge-sharing octahedra.

Sulfur-hexafluoride-3D-vdW
Sulfur-hexafluoride-3D-vdW

At a deeper level, octahedral geometry affects the energy of electrons. In a free ion, the d-orbitals have equal energy, a state called degeneracy. When an octahedral complex forms, this degeneracy is lifted through crystal field splitting. The d-orbitals split into two groups: the eg set and the t2g set. The eg orbitals point directly at the ligands and become destabilized. The t2g orbitals are stabilized. The size of the energy gap between these sets is labeled Δo. This gap depends on the strength of the ligands. Weak field ligands, like iodine, create a small gap, while strong field ligands, like cyanide, create a large gap.

Sulfur-hexafluoride-3D-vdW
Sulfur-hexafluoride-3D-vdW
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