Atoms, Ions, and Molecules

Structural and Spatial Isomers

Structural and spatial isomers are variations of molecules.
An isomer is one of two or more molecules that have the same molecular formula but different arrangements of atoms and bonds. Isomerism is often not possible in small molecules, such as water and carbon dioxide, but it becomes possible in larger molecules because the number of possible isomers increases greatly with the number of available atoms. There are two main types of isomerism. A structural isomer is one of two or more molecules that have the same molecular formula but different bond structures. Butane and isobutane, for example, both have the molecular formula C4H10. The arrangements of atoms and the shapes of the molecules, however, are different. Butane is a chain of four carbon atoms, but isobutane is a chain of three carbon atoms with a carbon atom attached to the central carbon atom. Although they have the same molecular formulas, butane and isobutane have different shapes and different chemical properties.

Structural Isomerism of Butane and Isobutane

Butane and isobutane are structural isomers because they both consist of 4 carbon atoms and 10 hydrogen atoms but have different arrangements of the atoms.
Another example of structural isomers is 1-butyne and 1,3-butadiene. Both of these compounds have the chemical formula C4H6, but their atoms are arranged differently. Two of 1-butyne's carbon atoms are connected by a triple-bond, but 1,3-butadiene has two double bonds.

Structural Isomerism of 1-Butyne and 1,3-Butadiene

The compounds 1-butyne and 1,3-butadiene are structural isomers because they both have four carbon atoms and six hydrogen atoms but different arrangements of atoms and types of bonds.
A spatial isomer, or stereoisomer, is one of two or more molecules that have the same molecular formula and bond structure but different arrangements of atoms. Spatial isomerism can occur in various ways. Consider the molecule bromoiodomethane (CH2BrI). In this molecule, two hydrogen atoms, one bromine atom, and one iodine atom are bonded to a central carbon. A mirror image shows that rotating the molecule results in the original molecule. The mirror image can be rotated 180 degrees and superimposed on its mirror image, so there is no isomerism in this case.

Molecule without Isomerism

The mirror image of a bromoiodomethane (CH2BrI) molecule is same as the original molecule.
When a carbon atom has four different atoms attached to it, this situation changes. Consider fluorochlorobromomethane (CHBrClF), a compound with one bromine, one chlorine, one fluorine, and one hydrogen atom bonded to a central carbon. These four atoms can be attached to the carbon in two different ways, forming two enantiomers. An enantiomer has a mirror image that is not superimposable on itself. The molecules look similar but cannot be superimposed on each other regardless of how they are rotated.

Two Enantiomers of Fluorochlorobromomethane (CHBrClF)

The mirror image shows that two forms of fluorochlorobromomethane (CHBrClF) cannot be rotated to produce each other. When two molecules have different orientations around a central atom, they form enantiomers.
Another way spatial isomerism can occur is around double bonds. Molecules generally can rotate freely around single bonds, but this is not possible around a double bond because it has a fixed geometry. When carbon atoms have single bonds, they can rotate freely. Two molecules are cistrans isomers if they have the same molecular formula and the same bond structure but the atoms differ in position around a rigid, or fixed, part of the molecule. Both of the isomers have exactly the same atoms joined up in exactly the same order. That means the van der Waals dispersion forces between the molecules will be identical in both cases. The difference between the two is that the cis isomer is a polar molecule and has its functional groups on the same side of its carbon chain, whereas the trans isomer is nonpolar and has its functional groups on opposite sides of the carbon chain. Consider the compound 1,2-dichloroethene. In a molecule of cis-1,2-dichloroethene, the chlorine atoms are on the same side of the carbon-carbon double bond. In trans-1,2-dichloroethene, the chlorine atoms are on opposite sides on the double bond.

Cis-1,2-dichloroethene and Trans-1,2-dichloroethene Showing Cis−Trans Isomerism

Cis-1,2-dichloroethene and trans-1,2-dichloroethene are cis−trans isomers because of differences in the placements of the chlorine and hydrogen atoms with respect to the carbon-carbon double bond.