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Concept
Tetrahedral molecular geometry
Summary
In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−) = 109.4712206...° ≈ 109.5° when all four substituents are the same, as in methane () as well as its heavier analogues. Methane and other perfectly symmetrical tetrahedral molecules belong to point group Td, but most tetrahedral molecules have lower symmetry. Tetrahedral molecules can be chiral.
The bond angle for a symmetric tetrahedral molecule such as CH4 may be calculated using the dot product of two vectors. As shown in the diagram, the molecule can be inscribed in a cube with the tetravalent atom (e.g. carbon) at the cube centre which is the origin of coordinates, O. The four monovalent atoms (e.g. hydrogens) are at four corners of the cube (A, B, C, D) chosen so that no two atoms are at adjacent corners linked by only one cube edge. If the edge length of the cube is chosen as 2 units, then the two bonds OA and OB correspond to the vectors a = (1, –1, 1) and b = (1, 1, –1), and the bond angle θ is the angle between these two vectors. This angle may be calculated from the dot product of the two vectors, defined as a • b = ||a|| ||b|| cos θ where ||a|| denotes the length of vector a. As shown in the diagram, the dot product here is –1 and the length of each vector is √3, so that cos θ = –1/3 and the tetrahedral bond angle θ = arccos(–1/3) ≃ 109.47°.
Aside from virtually all saturated organic compounds, most compounds of Si, Ge, and Sn are tetrahedral. Often tetrahedral molecules feature multiple bonding to the outer ligands, as in xenon tetroxide (XeO4), the perchlorate ion (), the sulfate ion (), the phosphate ion (). Thiazyl trifluoride () is tetrahedral, featuring a sulfur-to-nitrogen triple bond.
Other molecules have a tetrahedral arrangement of electron pairs around a central atom; for example ammonia () with the nitrogen atom surrounded by three hydrogens and one lone pair.
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