Square pyramidal VSEPR structure

We have seen that the VSEPR model fails to predict the angular equilibrium structure of BaF2 and other dihalides of the heavier Group 2 metals or the square pyramidal equilibrium structures of SbPhs and BiPhs. In the next chapter we shall see that the model is of little help for the prediction of structures when the central atom is surrounded by seven electron... 

The heavier atoms of Group 13 appear not to form p -p bonds. Five- and six-coordinate structures (schemes (4) and (5)) are almost entirely restricted to the heavier atoms, although at least one complex containing five-coordinate boron is known. According to VSEPR theory, scheme (4) structures should be trigonal bipyramidal. However, InClf- and TlClf are found to be square pyramidal in crystalline solids. As noted in Section 8.2, this shape (also adopted by MnClf-) is possibly favoured by crystal packing requirements. 

The amended VSEPR model predicts two forms of five-coordination, and experimental chemistry has clearly identified many examples of both forms. These limiting structures are square-based pyramidal (or, simply, square pyramidal) and trigonal bipyramidal (Figure 4.13). The classical square-based pyramidal shape is formed simply by cleaving off one bond from an octahedral shape, which leaves the metal in the same plane as the four square-based ligands. In reality, almost no complexes exhibit this shape, but rather adopt a distorted... 

Finally, it should be noted that the XeF molecule exhibits a definite tendency to donate a fluoride ion and form the XeFj cation, which is isoelectronic and isasmic-tural with IF] as expected from the VSEFR model. The structure of solid XeF is complex, wilh 144 molecules of XeF per unit cell however there are no discrete XeF molecules. The simplest way to view the solid is as pyramidal XeF cations extensively bridged by free fluoride ions. Obviously, these bridges must contain considerably covalent character. They cause the xenon-containing fragments to duster into tetrahedral and octahedral units (Fig. 6.ISa,b). There are 24 tetrahedra and eight octahedra per unit cell, packed very efficiently as pseudospheres into a CujAu structure (Fig, 6.ISc)."-i The structure thus provides us with no information about molecular XeF, but it does reinforce the idea that the VSEPR-correct, square pyramidal XeF] is structurally stable. 

For the most part, the structures of noble-gas compounds follow readily from VSEPR theory. In the gas phase, xenon hexafluoride assumes a nonrigid, slightly distorted octahedral structure, even though it has seven electron pairs around the central xenon atom. In the solid, it is characterized by square pyramidal XeF cations bridged by fluoride ions. XeF is a square antiprism, and XeOF4 is nearly a perfect square pyramid. 

Section 8.13 molecular structure valence shell electron-pair repulsion (VSEPR) model linear structure trigonal planar structure tetrahedral structure trigonal pyramid trigonal bipyramid octahedral structure square planar structure... 

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