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The extensive CSD searches performed for this review clearly show that it is much easier for functional groups to approach an aromatic ring from the side (and thus away from the π-cloud). All contacts cited in this work involve atoms that lie above the ring, as defined strictly by this imaginary prism whose edges are normal to the mean plane of the aromatic ring.
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In order to keep the typography simple, triple hyphens will indicate nonbonded contacts between groups (e.g. H-Ar, O-C), but short hyphens will be used for covalent bonds (e.g. C-H, C-O).
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11
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4644317294
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C-H bond lengths are systematically underestimated by X-ray crystallography because hydrogen atoms have no core electrons, and the peak of the hydrogen electron density in a covalent C-H bond is displaced slightly toward the carbon.[13] For this reason, C-H bond lengths are often observed to be about 0.96 Å in X-ray structures, and in cases where the hydrogen positions are not refined, riding models which employ similar distances are used. In this review, in order to give more nearly accurate nonbonded distances involving hydrogen atoms, the C-H bond lengths have been "improved"; that is, the bond has been lengthened along the observed C-H bond vector to the standard values observed for that type of bond in neutron diffraction experiments: 1.083 Å for aromatic C-H, 1.092 Å for methylene C-H, and 1.099 Å for methine C-H.[14]
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12
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4644247684
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note
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Nonbonded distances involving aromatic rings have been reported in a variety of ways, some of which I illustrate for compound 3. In Hanson's original report[9] of the crystal structure, in which a C-H bond length of 0.98 Å was observed for the critical hydrogen, he says, "... C(8) lies only 2.71 Å, and H(8) only 2.16 Å, from the plane of the unsubstituted atoms of the para-bridged ring." This was mistranslated into Keehn's review of cyclophane structures[7] as "... 2.71 and 2.16 Å, respectively, from the mean plane of the para-bridged ring." In fact, when the mean plane of the ring is used (all six carbons, not just the unsubstituted ones), the distance is calculated to be 2.08 Å. When an improved[11] C-H bond length of 1.083 Å is also used, the distance to the mean plane drops to 2.03 Å. Finally, the distance of the (improved) hydrogen from the center (or, more properly, the centroid) of the benzene ring is 2.11 Å. This last measure is perhaps the least ambiguous, and it is the distance most often quoted in this review.
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14
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