IB ChemistryStructure 22.22.2.13
2.2.13HL

Expanded Octet Geometries

5 and 6 electron domain shapes for Period 3+ central atoms.

🟣 This is Higher Level (HL) content.

Five Electron Domains (Trigonal Bipyramidal Base)

The base geometry is asymmetric – 3 equatorial positions (120° apart) and 2 axial positions (90° from equator). Lone pairs always occupy equatorial positions to minimise repulsion.

BP LP Molecular Shape Example Bond Angles
5 0 Trigonal bipyramidal PCl₅ 90° & 120°
4 1 See-saw SF₄ ~102° & ~173°
3 2 T-shaped ClF₃ < 90°
2 3 Linear XeF₂, I₃⁻ 180°

Six Electron Domains (Octahedral Base)

All six positions are equivalent (all 90° apart). When lone pairs are present, they adopt trans positions (opposite each other, 180° apart) to minimise LP–LP repulsion.

BP LP Molecular Shape Example Bond Angles
6 0 Octahedral SF₆ 90°
5 1 Square pyramidal BrF₅ < 90°
4 2 Square planar XeF₄ 90°

⚠️ Examiner Trap – Lone Pair Placement

In trigonal bipyramidal systems, lone pairs always go equatorial. In octahedral systems with 2 LP, they go trans (180° apart, not adjacent). Getting this wrong leads to incorrect molecular geometry predictions.

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