Acta Crystallographica Section C

Crystal Structure Communications

Volume 69, Part 9 (September 2013)


organic compounds



Acta Cryst. (2013). C69, 1051-1054    [ doi:10.1107/S0108270113020647 ]

A study of the pyramidality index in tris­(2,4,6-triiso­propyl­phen­yl)phos­phonium perchlorate

R. T. Boeré and Y. Zhang

Abstract: The title compound, C45H70P+·ClO4- or [Tripp3PH+][ClO4-], was produced from the perchlorate salt of the corresponding radical cation Tripp3P·+ through very slow H-atom abstraction reactions in a solution of 1,2-di­meth­oxy­ethane (Tripp is 2,4,6-triiso­propyl­phen­yl). The H atom on the P atom was located in a difference map and was freely refined with an isotropic displacement consistent with full occupancy [P-H = 1.37 (3) Å]. It is the most sterically congested tri­aryl­phospho­nium salt yet to be reported and has a `propeller' arrangement of the three Tripp groups around the P atom, with the protonation site located along the mol­ecular threefold axis. There are short contacts between the flanking isopropyl methine H atoms and the P atom [P...H = 1.99 (2)-2.17 (2) Å]. The sum of the angles around the P atom [[Sigma](C-P-C) = 349.9 (6)°] is a convenient index of pyramidality for tricoordinate centres. This value is significantly larger than in analogous Mes3PH+ salts (Mes is mesityl or 2,4,6-tri­methyl­phen­yl), for which the average of the three reported structures in the literature is [Sigma](C-P-C) = 345.3 (6)°. For comparison, in the ubiquitous Ph3PH+ salts, this parameter has a typical average value of only 333.3 (9)°. The value of [Sigma](C-P-C) in the title compound is midway between that of the neutral phosphane Tripp3P [334.4 (6)°] and the phospho­niumyl radical cation Tripp3P·+ [359.8 (2)°]. This geometrical feature provides additional support for the assignment as a phospho­nium salt.

Formula: C45H70P+·ClO4-

Keywords: crystal structure; tri­aryl­phospho­nium ions; pyramidality index; phospho­niumyl radical cations.


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