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

被引:1
|
作者
Frey, Joseph [2 ]
Khan, Saeed I. [1 ]
Knobler, Carolyn B. [1 ]
Lightner, David A. [3 ]
Maverick, Emily F. [1 ]
Phillips, Daniel J. [4 ]
Rappoport, Zvi [5 ]
Trueblood, Kenneth N. [1 ]
机构
[1] Univ Calif Los Angeles, Los Angeles, CA 90095 USA
[2] Bar Ilan Univ, Dept Chem, IL-52900 Ramat Gan, Israel
[3] Univ Nevada, Reno, NV 89557 USA
[4] Bethany Coll, Bethany, WV 26032 USA
[5] Hebrew Univ Jerusalem, IL-91904 Jerusalem, Israel
来源
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE | 2010年 / 66卷
基金
美国国家科学基金会;
关键词
anisotropic displacement parameters; Hirshfeld test; rotation barriers; helicenes; aromaticity; ANISOTROPIC DISPLACEMENT PARAMETERS; X-RAY-DIFFRACTION; CAMBRIDGE STRUCTURAL DATABASE; PROTON SPIN RELAXATION; CRYSTAL-STRUCTURE; T-BUTYL; GROUP REORIENTATION; MOLECULAR-SOLIDS; ROTATION BARRIERS; TORSIONAL MOTION;
D O I
10.1107/S0108768110040024
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:622 / 638
页数:17
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