Thermal motion of tert-butyl groups III. tert-Butyl substituents in aromatic hydrocarbons, the view from the bottom of the well.

ABSTRACT

The rigidity of the tert-butyl group (TBG) as a substituent in aromatic hydrocarbons is investigated, with a modified Hirshfeld test of anisotropic displacement parameters (ADPs) as a primary criterion. Four new structures are analyzed, along with low-temperature studies of a previously published crowded supermesityl dimer; three of the five structures meet the primary test. Most of the TBGs meet the Hirshfeld test at 100 K, and the ADPs are improved by omitting low-order data in the final refinement. The three most precise structures yield a wide variation in libration amplitudes (and in estimated rotation barriers) for 13 unique TBGs. A similar range of values is found in analyses of structures in the Cambridge Crystallographic Database. The libration amplitudes are calculated with the program THMA14C, with each TBG as an attached rigid group (ARG). Packing analysis suggests that large ADPs, especially for some individual TBG methyl groups, correspond to voids in the crystal. Published barriers to TBG reorientation, determined by solid-state NMR spin-lattice relaxation methods, for six related crystalline compounds are compared with barriers calculated from their crystal structure data.