Supplementary Material Available: Observed and calculated structure factors for 5b, Tables I-IV and VI for positional and thermal parameters, bond distances, bond angles, and torsion angles for 5b, and Figure 7, an ortep drawing giving a view of 5b (27 pages). Ordering information is given on any current masthead page.
Me2Py)]', 2.299 (2);19 [PtCl3(caffeine)]-, 2.294 (2); [PtCl3-CO]-, 2.289 (3).20 Thus the structural trans influence of caffeine is slightly less than that of Me2SO or a chloro ligand, similar to that of other heterocyclic nitrogen donors and slightly greater than that of CO.The triphenylmethylphosphonium cation is tetrahedral with the phenyl rings arranged as the blades of a propeller, as is usually found for this cation.21-27 The phosphorus atom does not lie in any of the phenyl planes (Table VII). Smaller deviations of 0.013-0.136 A have been reported before. [23][24][25] Several workers have stated that the P-CH3 bond is expected to be longer than the P-C6H5 bond because of the differing hybridization of the carbon atoms. 22,23,27,28 The P-CH3 bond has been observed to be longer in several structures,22,23,25 including the compound reported here, where the P-CH3 bond (1.786 (6) Á) is insignificantly longer than the average of the P-C6H5 bonds (1.780 (10) A). However, in all cases the differences in the P-CH3 and P-C6H5 bond lengths are small enough to be accounted for by experimental error.We have averaged the P-CH3 and P-C6H5 lengths found in all reported structures of the [P(C6H5)3CH3]+ cation for which the standard deviations are less than 0.01 A.22-24,28
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