Isomeric Hexamers

The octahedron of six lithium atoms is shown. There are six methyl groups occupying six of the eight ocatahederal faces. The two empty faces are shown in red for the three possible isomers: trans with empty faces opposite each other, apical where the empty edges touch at an apex, and edge where they share an edge. Click on the isomer of interest above or make your choice below. A table of energies is also available.

In the sections below the geometry is displayed in a static image and an interactive image. The interactive images, on the right below, require the Chime Plug-In and Netscape 3.01 or better. Microsoft Explorer 3.0 does not support the Plug-In as of yet. The Chemscape Chime Plug-In is available, without charge for academic or personal at-home use. The software is related to the Rasmol molecular viewer which may also be obtained. You may rotate the molecule by dragging the mouse across the surface of the image. Initially, only a wire frame image of the empty faces is presented to you. Many options, including display choices, are available via a menu which is obtained by clicking with the alternative button on the surface of the image.


Trans Apical Edge

Trans

In the trans isomer all six lithium atoms (red spheres) are equivalent to each other. Similarly, the six methyl groups (grey spheres) are equivalent to each other. The six methyl groups are located over six of the eight faces of the distorted lithium octahedron leaving two empty faces. In this isomer the two unoccuppied faces are opposite, trans, to each other. However, the methyl groups are not located over the centers of the faces of the distorted lithium octahedron but have moved towards that edge of the face which is shared with one of the empty faces. This moves the negatively charged methyl groups away from each other, thereby reducing methyl:methyl electrostatic repulsion. Focusing on the six methyls groups it can be seen that they have formed a distorted octahedorn around the lithium atoms which themselves form a distorted octahederon.

Apical Edge







Apical

In the apical isomer the the empty faces (red, pink, pink) meet at the red apex and are indicated by the heavy edges. The methyl groups that nominally over the (blue, pink, pink) faces sharing and edge with the empty faces are actually located nearly over the common edge. We hypothesize that this is to minimize repulsion between the negatively charged methyl groups. The methyl groups take up a nearly octahederal array surrounding the octahederal lithium array.

Trans Edge




Edge

In the edge isomer the empty edges (red, red, pink) share a common (red, red) edge and are shown in heavy outline. The four quivalent methyl groups over the (red, pink, blue) faces make up a rectangle. The symmetry constraints prevent the methyl groups relaxing into a lower energy geometry such as is taken on in the trans or apical isomer. This results in the edge having the highest energy of the three isomers.

Trans Apical