configuration

—configurational, configurative /keuhn fig"yeuhr euh tiv, -yeuh ray'tiv/, adj. —configurationally, adv.

/keuhn fig'yeuh ray"sheuhn/, n.

1. the relative disposition or arrangement of the parts or elements of a thing.

2. external form, as resulting from this; conformation.

3. Astron.

a. the relative position or aspect of heavenly bodies.

b. a group of stars.

4. Chem. an atomic spatial arrangement that is fixed by the chemical bonding in a molecule and that cannot be altered without breaking bonds (contrasted with conformation).

5. Computers. the totality of a computer and the devices connected to it: A common microcomputer configuration consists of a computer, two disk drives, a monitor, and a printer.

[1550-60; < LL configuration- (s. of configuratio), equiv. to L configurat(us) shaped like its model, ptp. of configurare to mold, shape (con- CON- + figur(a) FIGURE + -atus -ATE¹) + -ion- -ION]

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In chemistry, the arrangement in space of the atoms in a molecule.

It is especially important in organic chemistry (see organic compound), in which each carbon atom in a molecule can form from two to four covalent bonds (see bonding) with as many as four other atoms. A carbon atom with four single bonds, for example, lies at the centre of a tetrahedron, with one bond extending to each corner; if three or all four atoms bonded to the carbon are different, the structure that results has two different mirror-image (see optical activity; isomer) forms, similar to left-and right-handed gloves. Configuration issues also apply to some inorganic compounds. Until late in the 20th century, chemists struggled to determine the true three-dimensional form (absolute configuration) of a molecule experimentally, but modern optical and chemical methods have greatly simplified the task. The term electronic configuration refers to the number of electrons in the various shells of an atom, which defines its chemical reactivity and the type of bonding in which it participates.

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▪ molecular structure

      in chemistry, the spatial arrangement of atoms in a molecule. The configuration is usually depicted by means of a three-dimensional model (a ball-and-stick model), a perspective drawing, or a plane projection diagram.

      Until late in the 20th century, the experimental determination of absolute or actual configuration (i.e., the true three-dimensional form of the molecule) was a difficult process; therefore, there were few substances with known absolute configurations (e.g., tartaric acid). Many configurations were, for convenience, assigned by correlation with glyceraldehyde, for which the following configurations (as represented by plane projection diagrams) have been determined:

      The configuration of d-glyceraldehyde, in which the hydroxyl group is attached to the right of the asymmetric carbon centre (starred in the formulas), is designated as D, and the configuration of l-glyceraldehyde, in which the hydroxyl group is to the left of the asymmetric carbon, is designated as L. Thus, the complete designation of d-glyceraldehyde is given by D-d-glyceraldehyde (d to specify configuration and d to specify the direction of optical rotation); and that of l-glyceraldehyde, L-l-glyceraldehyde.

      Today, optical and chemical methods make it possible to determine the absolute configuration of practically any molecule. In the most modern scheme for specifying absolute configurations, D-d-glyceraldehyde is designated (R)-(+)-glyceraldehyde, and L-l-glyceraldehyde is (S)-(-)-glyceraldehyde. The letters R and S denote the absolute configurations at the asymmetric carbon atoms according to a set of rules that assign priorities to the four attached atoms or groups, and the + and - signs indicate the directions of the optical rotations.

      Compounds are then assigned D or L configurations on the basis of their genetic relationship with the appropriate form of glyceraldehyde. In the imagined transformation of glyceraldehyde to the substance whose configuration is in question, it is assumed that none of the steps involved causes any change in the configuration at the asymmetric carbon. For compounds containing several asymmetric carbon atoms, it is essential to specify which carbon atom was compared with glyceraldehyde. When the R-S system is used, the absolute configuration must be stated for each asymmetric carbon atom in the molecule.

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