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The CH/π interaction is a weak molecular force occurring between CH groups and π-groups. A study was carried out by use of the Cambridge Structural Database in order to obtain insights into the nature of the CH/π interaction and to examine its role in the crystal packing. The proportion of organic molecules bearing at least one CH/π interaction in their crystal structures has been found considerable. The CH hydrogen atoms tend to point toward the center of the aromatic ring. A number of short CH/π distances have been shown in the crystal structures of organic compounds. Moreover, the mean CH/π distance decreases as the acidity of the CH group increases. These results suggest that the CH/π interaction is not simply due to the dispersion force but involves other types of interactions, which are orientation-dependent and effective at wider ranges. It was suggested that the CH/π interaction constitutes one of the important factors in controlling the crystal packing of molecules.

Spatial distribution of CH hydrogen atoms with reference to a six-membered carbon aromatic ring was analyzed in the crystal structures deposited in the Cambridge Structural Database (CSD). The crystal data showed the propensity that the CH hydrogen atoms lie above the center of the aromatic ring to form interatomic CH/π contacts. Investigation of the effects of the CH proton acidity on the strength and the structure of the CH/π interaction has demonstrated that the distance between the hydrogen atom and the π plane (Dpln) decreases with increase of the CH proton acidity (Dpln: CCH3 ≅ sp2-CH > sp-CH ≅ Cl2CH2 > Cl3CH), and that the C–H···π access angle (α) tends to approach 180° in the same order. Further, a negative correlation has been found between Dpln and α. The directional preferences are in accord with the property of conventional hydrogen bond, indicating a hydrogen-bond-like character of the CH/π interaction. In order to elucidate the intrinsic nature of the CH/π interaction, ab initio calculations [MP2/6-311++G(d,p)] were carried out for methane/benzene, ethylene/benzene, and acetylene/benzene complexes. Potential surfaces obtained for the three model supramolecules are consistent with the results from the CSD analyses.

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A statistical study was carried out to investigate the role of the CH/π interaction in the crystal structure of transition metal compounds. Thus, short CH/π distances were surveyed in crystal structures deposited in the Cambridge Structural Database. Among organometallic entries bearing C 6 or C 5 aromatic rings, a substantial part of the structures has been found to have intermolecular CH/π contacts shorter than the van der Waals distance. Further, in many structures short intramolecular CH/π contacts have been found. Interligand and intraligand CH/π interactions were also surveyed in co-