Cinnamides as Alternatives for Urea in Complexation
J. Phys. Chem. B, Vol. 114, No. 1, 2010 329
As shown in Table 4, within the accuracy of the calculations,
there is no significant difference in the calculated binding
energies of the complexes of compounds 1 and 3 with those of
compounds 2 and 4. Thus, the calculated binding energies do
not show the trend in the association constants of Table 3, which
in any case are for formation of complexes with benzoic acid.
In Figure 20 the optimum geometry structures calculated for
the complexes of compounds 1 and 3 with trans-cinnamic acid
(notation as in Figures 6 and 7) are given, while in Table 5,
calculated values for the geometrical parameters relevant to the
hydrogen bonds are listed, where the labels a-e and ꢁ are as
exemplified in Figure 20 for structure A′-1. As shown in Table
5, the complexes of the unrotated amides (A and C) are found
to be planar. The calculated hydrogen-bond distances for the
case of A′-1, i.e., the values of a, b, and c (1.704, 1.880, and
2.560 Å, respectively) of Table 5 are in good agreement with
the corresponding quantities resulting from the crystallographic
analysis, O-H· · ·N (1.691 Å), N-H· · ·O (1.991 Å), and
C-H· · ·O (2.563 Å). It might be noted that in the results of
the present calculations it is not possible to isolate the
contribution of the olefinic C-H · · · O hydrogen bond to the
stability of the complexes. In fact, while the N-Ha bond (under
e in Table 5) is slightly elongated upon formation of the
hydrogen bond in the complex with the trans-cinnamic acid
(e.g., 1.012 Å in A and 1.026 Å in A′-1), the C-Hc bond is
very slightly shortened upon formation of the complex (e.g.,
1.087 Å in A and 1.086 in A′-1). This was found to be the case
in all the systems calculated and also with the larger basis set.
Finally, in Figure 21 the calculated geometries for the six-
centered hydrogen-bonded structures of Figure 9 are given. As
shown, the two structures are found to be planar with distance
a calculated at 2.229 Å and b at 2.197 Å. These structures are
calculated to be local minima both lying higher in energy by
0.20 eV than the corresponding open structures A and C.
Acknowledgment. We thank CSIR, Government of India for
financial support. T.S. thanks CSIR, New Delhi, India for a
fellowship. We also thank DST, Government of India for
providing facilities in the department under FIST program. I.D.P.
and G.T. acknowledge financial support from the EU FP7,
Capacities Program, NANOHOST project (GA 201729).
Supporting Information Available: CIF files of complex
1-trans-cinnamic acid and compounds 2 and 3. This informa-
tion is available free of charge via the Internet at http://
pubs.acs.org.
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