In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of bonds) between them. The term metamer was formerly used for the same concept. For example, butanol H3C−(CH2)3−OH, methyl propyl ether H3C−(CH2)2−O−CH3, and diethyl ether (H3CCH2−)2O have the same molecular formula C4H10O but are three distinct structural isomers. The concept applies also to polyatomic ions with the same total charge. A classical example is the cyanate ion O=C=N− and the fulminate ion C−≡N+−O−. It is also extended to ionic compounds, so that (for example) ammonium cyanate [NH4]+[O=C=N]− and urea (H2N−)2C=O are considered structural isomers, and so are methylammonium formate [H3C−NH3]+[HCO2]− and ammonium acetate [NH4]+[H3C−CO2]−. Structural isomerism is the most radical type of isomerism. It is opposed to stereoisomerism, in which the atoms and bonding scheme are the same, but only the relative spatial arrangement of the atoms is different. Examples of the latter are the enantiomers, whose molecules are mirror images of each other, and the cis and trans versions of 2-butene. Among the structural isomers, one can distinguish several classes including skeletal isomers, positional isomers (or regioisomers), functional isomers, tautomers, and structural isotopomers.
Skeletal isomerism A skeletal isomer of a compound is a structural isomer that differs from it in the atoms and bonds that are considered to comprise the "skeleton" of the molecule. For organic compounds, such as alkanes, that usually means the carbon atoms and the bonds between them. For example, there are three skeletal isomers of pentane: n-pentane (often called simply "pentane"), isopentane (2-methylbutane) and neopentane (dimethylpropane).
If the skeleton is acyclic, as in the above example, one may use the term chain isomerism.
Position isomerism (regioisomerism)
Position isomers (also positional isomers or regioisomers) are structural isomers that can be viewed as differing only on the position of a functional group, substituent, or some other feature on the same "parent" structure. For example, replacing one of the 12 hydrogen atoms –H by a hydroxyl group –OH on the n-pentane parent molecule can give any of three different position isomers:
Another example of regioisomers are α-linolenic and γ-linolenic acids, both octadecatrienoic acids, each of which has three double bonds, but on different positions along the chain.
Functional isomerism Functional isomers are structural isomers which have different functional groups, resulting in significantly different chemical and physical properties. An example is the pair propanal H3C–CH2–C(=O)-H and acetone H3C–C(=O)–CH3: the first has a –C(=O)H functional group, which makes it an aldehyde, whereas the second has a C–C(=O)–C group, that makes it a ketone. Another example is the pair ethanol H3C–CH2–OH (an alcohol) and dimethyl ether H3C–O–CH2H (an ether). In contrast, 1-propanol and 2-propanol are structural isomers, but not functional isomers, since they have the same significant functional group (the hydroxyl –OH) and are both alcohols. Besides the different chemistry, functional isomers typically have very different infrared spectra. The infrared spectrum is largely determined by the vibration modes of the molecule, and functional groups like hydroxyl and esters have very different vibration modes. Thus 1-propanol and 2-propanol have relatively similar infrared spectra because of the hydroxyl group, which are fairly different from that of methyl ethyl ether.
Structural isotopomers
In chemistry, one usually ignores distinctions between isotopes of the same element. However, in some situations (for instance in Raman, NMR, or microwave spectroscopy) one may treat different isotopes of the same element as different elements. In the second case, two molecules with the same number of atoms of each isotope but distinct bonding schemes are said to be structural isotopomers. Thus, for example, ethene would have no structural isomers under the first interpretation; but replacing two of the hydrogen atoms (1H) by deuterium atoms (2H) may yield any of two structural isotopomers (1,1-dideuteroethene and 1,2-dideuteroethene), if both carbon atoms are the same isotope. If, in addition, the two carbons are different isotopes (say, 12C and 13C), there would be three distinct structural isotopomers, since 1-13C-1,1-dideuteroethene would be different from 1-13C-2,2-dideuteroethene. And, in both cases, the 1,2-dideutero structural isotopomer would occur as two stereoisotopomers, cis and trans.
Structural equivalence and symmetry
Structural equivalence Two molecules (including polyatomic ions) A and B have the same structure if each atom of A can be paired with an atom of B of the same element, in a one-to-one way, so that for every bond in A there is a bond in B, of the same type, between corresponding atoms; and vice versa. This requirement applies also to complex bonds that involve three or more atoms, such as the delocalized bonding in the benzene molecule and other aromatic compounds. Depending on the context, one may require that each atom be paired with an atom of the same isotope, not just of the same element. Two molecules then can be said to be structural isomers (or, if isotopes matter, structural isotopomers) if they have the same molecular formula but do not have the same structure.
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