Thus far, we have used two-dimensional Lewis structures to represent molecules. However, molecular structure is actually three-dimensional, and it is important to be able to describe molecular bonds in terms of their distances, angles, and relative arrangements in space (Figure 7.14). A bond angle is the angle between any two bonds that include a common atom, usually measured in degrees. A bond distance (or bond length) is the distance between the nuclei of two bonded atoms along the straight line joining the nuclei. Bond distances are measured in Ångstroms (1 Å = 10^–10 m) or picometers (1 pm = 10^–12 m, 100 pm = 1 Å).

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VSEPR Theory

Valence shell electron-pair repulsion theory (VSEPR theory) enables us to predict the molecular structure, including approximate bond angles around a central atom, of a molecule from an examination of the number of bonds and lone electron pairs in its Lewis structure. The VSEPR model assumes that electron pairs in the valence shell of a central atom will adopt an arrangement that minimizes repulsions between these electron pairs by maximizing the distance between them. The electrons in the valence shell of a central atom form either bonding pairs of electrons, located primarily between bonded atoms, or lone pairs. The electrostatic repulsion of these electrons is reduced when the various regions of high electron density assume positions as far from each other as possible.

VSEPR theory predicts the arrangement of electron pairs around each central atom and, usually, the correct arrangement of atoms in a molecule. We should understand, however, that the theory only considers electron-pair repulsions. Other interactions, such as nuclear-nuclear repulsions and nuclear-electron attractions, are also involved in the final arrangement that atoms adopt in a particular molecular structure.

As a simple example of VSEPR theory, let us predict the structure of a gaseous BeF₂ molecule. The Lewis structure of BeF₂ (Figure 7.15) shows only two electron pairs around the central beryllium atom. With two bonds and no lone pairs of electrons on the central atom, the bonds are as far apart as possible, and the electrostatic repulsion between these regions of high electron density is reduced to a minimum when they are on opposite sides of the central atom. The bond angle is 180° (Figure 7.15).

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Figure 7.16 illustrates this and other electron-pair geometries that minimize the repulsions among regions of high electron density (bonds and/or lone pairs). Two regions of electron density around a central atom in a molecule form a linear geometry; three regions form a trigonal planar geometry; four regions form a tetrahedral geometry; five regions form a trigonal bipyramidal geometry; and six regions form an octahedral geometry.

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Electron-pair Geometry versus Molecular Structure

It is important to note that electron-pair geometry around a central atom is not the same thing as its molecular structure. The electron-pair geometries shown in Figure 7.16 describe all regions where electrons are located, bonds as well as lone pairs. Molecular structure describes the location of the atoms, not the electrons.

We differentiate between these two situations by naming the geometry that includes all electron pairs the electron-pair geometry. The structure that includes only the placement of the atoms in the molecule is called the molecular structure. The electron-pair geometries will be the same as the molecular structures when there are no lone electron pairs around the central atom, but they will be different when there are lone pairs present on the central atom.

For example, the methane molecule, CH₄, which is the major component of natural gas, has four bonding pairs of electrons around the central carbon atom; the electron-pair geometry is tetrahedral, as is the molecular structure (Figure 7.17). On the other hand, the ammonia molecule, NH₃, also has four electron pairs associated with the nitrogen atom, and thus has a tetrahedral electron-pair geometry. One of these regions, however, is a lone pair, which is not included in the molecular structure, and this lone pair influences the shape of the molecule (Figure 7.18).

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As seen in Figure 7.18, small distortions from the ideal angles in Figure 7.16 can result from differences in repulsion between various regions of electron density. VSEPR theory predicts these distortions by establishing an order of repulsions and an order of the amount of space occupied by different kinds of electron pairs. The order of electron-pair repulsions from greatest to least repulsion (and thus from most space occupied to least) is:

There is a similar trend for the different types of bonds. A lone pair of electrons occupies a larger region of space than the electrons in a triple bond; in turn, electrons in a triple bond occupy more space than those in a double bond, and so on. The order of sizes from largest to smallest is:

Consider formaldehyde, H₂CO, which is used as a preservative for biological and anatomical specimens (Figure 7.14). This molecule has regions of high electron density that consist of two single bonds and one double bond. The basic geometry is trigonal planar with 120° bond angles, but we see that the double bond causes slightly larger angles (121°), and the angle between the single bonds is slightly smaller (118°).

In the ammonia molecule, the three hydrogen atoms attached to the central nitrogen are not arranged in a flat, trigonal planar molecular structure, but rather in a three-dimensional trigonal pyramid (Figure 7.18) with the nitrogen atom at the apex and the three hydrogen atoms forming the base. The ideal bond angles in a trigonal pyramid are based on the tetrahedral electron pair geometry. Again, there are slight deviations from the ideal because lone pairs occupy larger regions of space than do bonding electrons. The H–N–H bond angles in NH₃ are slightly smaller than the 109.5° angle in a regular tetrahedron (Figure 7.16) because the lone pair-bonding pair repulsion is greater than the bonding pair-bonding pair repulsion (Figure 7.18). Figure 7.19 illustrates the ideal molecular structures, which are predicted based on the electron-pair geometries for various combinations of lone pairs and bonding pairs.

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According to VSEPR theory, the terminal atom locations (Xs in Figure 7.19) are equivalent within the linear, trigonal planar, and tetrahedral electron-pair geometries (the first three rows of the table). It does not matter which X is replaced with a lone pair because the molecules can be rotated to convert positions.

For trigonal bipyramidal electron-pair geometries, however, there are two distinct X positions, as shown in Figure 7.20: an axial position (if we hold a model of a trigonal bipyramid by the two axial positions, we have an axis around which we can rotate the model) and an equatorial position (three positions form an equator around the middle of the molecule). As shown in Figure 7.19, the axial position is surrounded by bond angles of 90°, whereas the equatorial position has more space available because of the 120° bond angles. In a trigonal bipyramidal electron-pair geometry, lone pairs always occupy equatorial positions because these more spacious positions can more easily accommodate the larger lone pairs.

Theoretically, we can come up with three possible arrangements for the three bonds and two lone pairs for the ClF₃ molecule (Figure 7.20). The stable structure is the one that puts the lone pairs in equatorial locations (Figure 7.20-b), giving a T-shaped molecular structure.

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When a central atom has two lone electron pairs and four bonding regions, we have an octahedral electron-pair geometry. The two lone pairs should be placed on opposite sides of the octahedron (180° apart) to minimize lone pair-lone pair repulsions. Therefore, an octahedral electron-pair geometry with two lone pairs will always have a square planar molecular structure (Figure 7.19).

Predicting Electron Pair Geometry and Molecular Structure

The following procedure uses VSEPR theory to determine the electron pair geometries and the molecular structures:

1. Write the Lewis structure of the molecule or polyatomic ion.
2. Count the number of regions of electron density (lone pairs and bonds) around the central atom. A single, double, or triple bond counts as one region of electron density.
3. Identify the electron-pair geometry based on the number of regions of electron density. The options are shown in the first column of Figure 7.19:
   • linear
   • trigonal planar
   • tetrahedral
   • trigonal bipyramidal
   • octahedral
4. Use the number of lone pairs to determine the molecular structure (Figure 7.19).
5. If more than one arrangement of lone pairs and chemical bonds is possible, choose the one that will minimize repulsions, remembering that lone pairs occupy more space than multiple bonds, which occupy more space than single bonds.
   • In trigonal bipyramidal arrangements, repulsion is minimized when every lone pair is in an equatorial position.
   • In an octahedral arrangement with two lone pairs, repulsion is minimized when the lone pairs are on opposite sides of the central atom.

The following examples illustrate the use of VSEPR theory to predict the molecular structure of molecules or ions that have no lone pairs of electrons. In this case, the molecular structure is identical to the electron pair geometry.

 

The next several examples illustrate the effect of lone pairs of electrons on molecular structure.

 

 

Molecular Structure for Multicenter Molecules

When a molecule or polyatomic ion has only one central atom, the molecular structure completely describes the shape of the molecule. Larger molecules do not have a single central atom, but are connected by a chain of interior atoms that each possess a “local” geometry. The way these local structures are oriented with respect to each other also influences the molecular shape, but such considerations are largely beyond the scope of this introductory discussion. For our purposes, we will only focus on determining the local structures.