Perchlorophenalenyl radical, C13Cl9: a modulated structure with nine threefold-symmetric molecules in the asymmetric unit

by Koutentis, P. A.; Haddon, Robert C.; Oakley, Richard T.; Cordes, A. Wallace; Brock, C. P.

The odd-alternant perchlorophenalenyl radical, C13Cl9, forms molecular stacks centered on crystallographic threefold rotation axes, but the spacing within the stacks (3.78 Angstrom) is too large to allow good overlap of the orbitals in which the spin density is localized. The radical is ruffled because of the intramolecular repulsions between alpha Cl atoms (the Cl . . . Cl peri interactions); the average displacement of an alpha Cl atom from the molecular plane is similar to0.7 Angstrom. The deviations from molecular planarity do not, however, determine the spacing within the stacks, which is determined instead by interactions between stacks. The modulations found in the P3c1 super-structure are a response to the short interstack contacts that would occur in the average pseudocell structure (R (3) over barm, c' = c/6). The primary modulation is a pattern of enantiomeric alternation; a secondary modulation involves small rotations of the molecules around their threefold axes. The number (9) of independent molecules in the true cell is exceptionally large because of the conflict between the preference within the molecular stacks for threefold rotational symmetry and the preference in directions perpendicular to the stack axes for twofold alternation of enantiomers. The structural complexity reduces the precision of the distances and angles determined, but the average values found are in excellent agreement with those calculated by density functional theory.

Journal
Acta Crystallographica Section B-Structural Science
Volume
57
Year
2001
Start Page
680
ISBN/ISSN
0108-7681
DOI
10.1107/S0108768101011193