4.6 Molecular Structure and Polarity

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 4.16 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 4.17). 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 4.18).

Figure 4.17 The molecular structure of the methane molecule, CH₄, is shown with a tetrahedral arrangement of the hydrogen atoms. VSEPR structures like this one are often drawn using the wedge and dash notation, in which solid lines represent bonds in the plane of the page, solid wedges represent bonds coming up out of the plane, and dashed lines represent bonds going down into the plane.

Figure 4.18 (a) The electron-pair geometry for the ammonia molecule is tetrahedral with one lone pair and three single bonds. (b) The trigonal pyramidal molecular structure is determined from the electron-pair geometry. (c) The actual bond angles deviate slightly from the idealized angles because the lone pair takes up a larger region of space than do the single bonds, causing the HNH angle to be slightly smaller than 109.5°.

As seen in Figure 4.18, small distortions from the ideal angles in Figure 4.16 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 is:

This order of repulsions determines the amount of space occupied by different regions of electrons. 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 4.14). 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 4.18) 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 4.16) because the lone pair-bonding pair repulsion is greater than the bonding pair-bonding pair repulsion (Figure 4.18). Figure 4.19 illustrates the ideal molecular structures, which are predicted based on the electron-pair geometries for various combinations of lone pairs and bonding pairs.

Figure 4.19 The molecular structures are identical to the electron-pair geometries when there are no lone pairs present (first column). For a particular number of electron pairs (row), the molecular structures for one or more lone pairs are determined based on modifications of the corresponding electron-pair geometry.

According to VSEPR theory, the terminal atom locations (Xs in Figure 4.19) 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 4.20: 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 4.19, 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 4.20). The stable structure is the one that puts the lone pairs in equatorial locations, giving a T-shaped molecular structure.

Figure 4.20 (a) In a trigonal bipyramid, the two axial positions are located directly across from one another, whereas the three equatorial positions are located in a triangular arrangement. (b–d) The two lone pairs (red lines) in ClF₃ have several possible arrangements, but the T-shaped molecular structure (b) is the one actually observed, consistent with the larger lone pairs both occupying equatorial positions.

When a central atom has two lone electron pairs and four bonding regions, we have an octahedral electron-pair geometry. The two lone pairs are on opposite sides of the octahedron (180° apart), giving a square planar molecular structure that minimizes lone pair-lone pair repulsions (Figure 4.19).

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: linear, trigonal planar, tetrahedral, trigonal bipyramidal, or octahedral (Figure 4.19, first column).
4. Use the number of lone pairs to determine the molecular structure (Figure 4.19). 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.

Example 4.11

Predicting Electron-pair Geometry and Molecular Structure: CO₂ and BCl₃

Predict the electron-pair geometry and molecular structure for each of the following:

(a) carbon dioxide, CO₂, a molecule produced by the combustion of fossil fuels

(b) boron trichloride, BCl₃, an important industrial chemical

Solution

(a) We write the Lewis structure of CO₂ as:

This shows us two regions of high electron density around the carbon atom—each double bond counts as one region, and there are no lone pairs on the carbon atom. Using VSEPR theory, we predict that the two regions of electron density arrange themselves on opposite sides of the central atom with a bond angle of 180°. The electron-pair geometry and molecular structure are identical, and CO₂ molecules are linear.

(b) We write the Lewis structure of BCl₃ as:

Thus we see that BCl₃ contains three bonds, and there are no lone pairs of electrons on boron. The arrangement of three regions of high electron density gives a trigonal planar electron-pair geometry. The B–Cl bonds lie in a plane with 120° angles between them. BCl₃ also has a trigonal planar molecular structure (Figure 4.21).

Figure 4.21

The electron-pair geometry and molecular structure of BCl₃ are both trigonal planar. Note that the VSEPR geometry indicates the correct bond angles (120°), unlike the Lewis structure shown above.

Check Your Learning

Carbonate, ${\text{CO}}_3{}^{\text{2−}},$ is a common polyatomic ion found in various materials from eggshells to antacids. What are the electron-pair geometry and molecular structure of this polyatomic ion?

Answer:

The electron-pair geometry is trigonal planar and the molecular structure is trigonal planar. Due to resonance, all three C–O bonds are identical. Whether they are single, double, or an average of the two, each bond counts as one region of electron density.

Example 4.12

Predicting Electron-pair Geometry and Molecular Structure: Ammonium

Two of the top 50 chemicals produced in the United States, ammonium nitrate and ammonium sulfate, both used as fertilizers, contain the ammonium ion. Predict the electron-pair geometry and molecular structure of the ${\text{NH}}_4{}^{\text{+}}$ cation.

Solution

We write the Lewis structure of ${\text{NH}}_4{}^{\text{+}}$ as:

We can see that ${\text{NH}}_4{}^{+}$ contains four bonds from the nitrogen atom to hydrogen atoms and no lone pairs. We expect the four regions of high electron density to arrange themselves so that they point to the corners of a tetrahedron with the central nitrogen atom in the middle (Figure 4.19). Therefore, the electron pair geometry of ${\text{NH}}_4{}^{\text{+}}$ is tetrahedral, and the molecular structure is also tetrahedral (Figure 4.22).

Figure 4.22 The ammonium ion displays a tetrahedral electron-pair geometry as well as a tetrahedral molecular structure.

Check Your Learning

Identify a molecule with trigonal bipyramidal molecular structure.

Answer:

Any molecule with five electron pairs around the central atoms including no lone pairs will be trigonal bipyramidal. PF₅ is a common example.

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

Example 4.13

Predicting Electron-pair Geometry and Molecular Structure: Lone Pairs on the Central Atom

Predict the electron-pair geometry and molecular structure of a water molecule.

Solution

The Lewis structure of H₂O indicates that there are four regions of high electron density around the oxygen atom: two lone pairs and two chemical bonds:

We predict that these four regions are arranged in a tetrahedral fashion (Figure 4.23), as indicated in Figure 4.19. Thus, the electron-pair geometry is tetrahedral and the molecular structure is bent with an angle slightly less than 109.5°. In fact, the bond angle is 104.5°.

Figure 4.23 (a) H₂O has four regions of electron density around the central atom, so it has a tetrahedral electron-pair geometry. (b) Two of the electron regions are lone pairs, so the molecular structure is bent.

Check Your Learning

The hydronium ion, H₃O⁺, forms when acids are dissolved in water. Predict the electron-pair geometry and molecular structure of this cation.

Answer:

electron pair geometry: tetrahedral; molecular structure: trigonal pyramidal

Example 4.14

Predicting Electron-pair Geometry and Molecular Structure: SF₄

Sulfur tetrafluoride, SF₄, is extremely valuable for the preparation of fluorine-containing compounds used as herbicides (i.e., SF₄ is used as a fluorinating agent). Predict the electron-pair geometry and molecular structure of a SF₄ molecule.

Solution

The Lewis structure of SF₄ indicates five regions of electron density around the sulfur atom: one lone pair and four bonding pairs:

We expect these five regions to adopt a trigonal bipyramidal electron-pair geometry. To minimize lone pair repulsions, the lone pair occupies one of the equatorial positions. The molecular structure (Figure 4.24) is that of a seesaw (Figure 4.19).

Figure 4.24 (a) SF4 has a trigonal bipyramidal arrangement of the five regions of electron density. (b) One of the regions is a lone pair, which results in a seesaw-shaped molecular structure.

Check Your Learning

Predict the electron pair geometry and molecular structure for molecules of XeF₂.

Answer:

The electron-pair geometry is trigonal bipyramidal. The molecular structure is linear.

Example 4.15

Predicting Electron-pair Geometry and Molecular Structure: XeF₄

Of all the noble gases, xenon is the most reactive, frequently reacting with elements such as oxygen and fluorine. Predict the electron-pair geometry and molecular structure of the XeF₄ molecule.

Solution

The Lewis structure of XeF₄ indicates six regions of high electron density around the xenon atom: two lone pairs and four bonds:

These six regions adopt an octahedral arrangement (Figure 4.19), which is the electron-pair geometry. To minimize repulsions, the lone pairs should be on opposite sides of the central atom (Figure 4.25). The five atoms are all in the same plane and have a square planar molecular structure.

Figure 4.25 (a) XeF₄ adopts an octahedral arrangement with two lone pairs (red lines) and four bonds in the electron-pair geometry. (b) The molecular structure is square planar with the lone pairs directly across from one another.

Check Your Learning

In a certain molecule, the central atom has three lone pairs and two bonds. What will the electron pair geometry and molecular structure be?

Answer:

electron pair geometry: trigonal bipyramidal; molecular structure: linear

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.

Example 4.16

Predicting Structure in Multicenter Molecules

The Lewis structure for the simplest amino acid, glycine, H₂NCH₂CO₂H, is shown here. Predict the local geometry for the nitrogen atom, the two carbon atoms, and the oxygen atom with a hydrogen atom attached:

Solution

Consider each central atom independently. The electron-pair geometries:

• nitrogen––four regions of electron density; tetrahedral
• carbon (CH₂)––four regions of electron density; tetrahedral
• carbon (CO₂)—three regions of electron density; trigonal planar
• oxygen (OH)—four regions of electron density; tetrahedral

The local structures:

• nitrogen––three bonds, one lone pair; trigonal pyramidal
• carbon (CH₂)—four bonds, no lone pairs; tetrahedral
• carbon (CO₂)—three bonds (double bond counts as one bond), no lone pairs; trigonal planar
• oxygen (OH)—two bonds, two lone pairs; bent (109°)

Check Your Learning

Another amino acid is alanine, which has the Lewis structure shown here. Predict the electron-pair geometry and local structure of the nitrogen atom, the three carbon atoms, and the oxygen atom with hydrogen attached:

Answer:

electron-pair geometries: nitrogen––tetrahedral; carbon (CH)—tetrahedral; carbon (CH₃)—tetrahedral; carbon (CO₂)—trigonal planar; oxygen (OH)—tetrahedral; local structures: nitrogen—trigonal pyramidal; carbon (CH)—tetrahedral; carbon (CH₃)—tetrahedral; carbon (CO₂)—trigonal planar; oxygen (OH)—bent (109°)

Properties of Polar Molecules

Polar molecules tend to align when placed in an electric field with the positive end of the molecule oriented toward the negative plate and the negative end toward the positive plate (Figure 4.28). We can use an electrically charged object to attract polar molecules, but nonpolar molecules are not attracted. Also, polar solvents are better at dissolving polar substances, and nonpolar solvents are better at dissolving nonpolar substances.

Figure 4.28 (a) Molecules are always randomly distributed in the liquid state in the absence of an electric field. (b) When an electric field is applied, polar molecules like HF will align to the dipoles with the field direction.