Table 1 Structural parameters of 4a and 2 obtained by X-ray
analyses and DFT calculationsa
of the acetylene units, which serve to reduce steric repulsion.
In the crystal, the distorted conformations are stabilized by
intermolecular C–Hꢀ ꢀ ꢀp interactions.
4a 4a
(Mol-A) (Mol-B)
Calcdb
We thank Dr Ichiro Hisaki (Osaka University) for discussion.
This work was supported by a Grant-in-Aid for Scientific Research,
Ministry of Education, Culture, Sports, Science and Technology,
Japan. T. T. thanks JSPS for his fellowship (21-664).
2
d(C11–C14
)
)
2.812(3) 2.830(3) 2.855 2.853
3.465(3) 3.604(3) 3.351 3.632
122.5(1) 122.4(1) 125.1 122.1
169.7(2) 166.5(2) 174.5 168.9
173.9(2) 176.2(2) 173.6 177.9
170.8(2) 168.7(2) 173.6 168.9
175.5(2) 176.0(2) 174.8 177.9
d(C12–C15
+C1–C9–C8
Notes and references
+C1–C11–C12
+C11–C12–C13
+C8–C14–C15
+C14–C15–C16
%
z Crystal data for 4a: C42H24, M 528.65, triclinic, P1, a = 9.3787(8)
A, b = 10.191(1) A, c = 15.950(2) A, a = 87.263(4)1, b = 88.165(4)1,
g = 67.961(3)1, V = 1411.2(3) A3, Z = 2, Dc = 1.244 g cmꢁ3
independent reflection 6422 (all), T = 113 K, R = 3.8%. CCDC
881969.
,
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+C11–C1–C8–C14 14.4
3.1
0.2
16.9
a
Because of the presence of symmetry, top half of the structure is
b
identical to the bottom half. Optimized using the B3LYP/6-31G*
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that the ring is nearly flat. In this case, the bond angles
+C1–C11–C12 and +C8–C14–C15 are even smaller than those of
Mol-A thus reducing the steric repulsion.
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¨
The theoretically optimized structure obtained by DFT
calculations (B3LYP/6-31G*) possesses the structural features
of Mol-A and Mol-B. Specifically, the twisting mode is more
like that of Mol-A and the bending mode is more like that of
Mol-B (see Fig. S2 and S3 in ESIz). From the DFT calculations
for Mol-A and Mol-B using their atomic coordinates, except
for those of hydrogen atoms which were optimized, they
were found to be significantly unstable (9.06 kcal molꢁ1 and
9.89 kcal molꢁ1, respectively, calculated at the same level of
theory) than the optimized structure. In the crystal structure,
the phenyl moieties are oriented nearly vertical to those of the
neighboring molecules. As a result, the intermolecular C–Hꢀ ꢀ ꢀp
interactions are maximized in the crystal, as shown in Fig. S4 in
ESIz, to stabilize the observed crystal structures.
In summary, we synthesized 1,4,5,8-tetraethynylnaphthalene
derivatives 4a–c for the first time. X-ray structure analysis of 4a
revealed three different modes of distortion, expanding of the
substituents, twisting of the naphthalene skeleton and bending
c
This journal is The Royal Society of Chemistry 2012
Chem. Commun., 2012, 48, 7841–7843 7843