rac-1,2,3,4-Tetra­hydro-1,4-methano­anthracene-6,7-dicarbonitrile

Kew-Yu Chen; Ming-Jen Chang; Tzu-Chien Fang; Ming-Hui Luo; Hsing-Yang Tsai

doi:10.1107/S1600536811047611

. 2011 Nov 16;67(Pt 12):o3312. doi: 10.1107/S1600536811047611

rac-1,2,3,4-Tetrahydro-1,4-methanoanthracene-6,7-dicarbonitrile

Kew-Yu Chen ^a,^*, Ming-Jen Chang ^a, Tzu-Chien Fang ^a, Ming-Hui Luo ^a, Hsing-Yang Tsai ^a

PMCID: PMC3238964 PMID: 22199813

Abstract

The title compound, C₁₇H₁₂N₂, comprises a norbornane unit having a dicyanonaphthalene ring fused on one side. Both cyano groups are twisted slightly out of the plane of the naphthalene ring system [C—C—C—C torsion angle = 1.9 (2)°]. In the crystal, inversion-related molecules are linked by pairs of weak C—H⋯N hydrogen bonds, forming dimers.

Related literature

For the spectroscopy of the title compound and its prepartion, see: Chen et al. (2006 ▶). For the spectroscopy and electronic device applications of rigid oligo-norbornyl compounds, see: Chen et al. (2002 ▶); Chow et al. (2005 ▶); Foitzik et al. (2009 ▶); Jansen et al. (2010 ▶); Tang et al. (2009 ▶). For related structures, see: Çelik et al. (2006 ▶); Chen et al. (2011 ▶); Lough et al. (2006 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₇H₁₂N₂
M _r = 244.29
Triclinic,
a = 6.1019 (4) Å
b = 10.7078 (6) Å
c = 11.3928 (7) Å
α = 65.173 (5)°
β = 84.768 (5)°
γ = 73.900 (5)°
V = 648.82 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 297 K
0.64 × 0.52 × 0.48 mm

Data collection

Bruker SMART 1000 CCD detector diffractometer
5692 measured reflections
2997 independent reflections
1707 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.102
S = 1.00
2997 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047611/xu5368sup1.cif

e-67-o3312-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047611/xu5368Isup2.hkl

e-67-o3312-Isup2.hkl^{(147.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N1ⁱ	0.93	2.61	3.505 (2)	162

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Science Council (NSC 99–2113-M-035–001-MY2) and Feng Chia University in Taiwan.

supplementary crystallographic information

Comment

Donor-acceptor chromophores linked by the rigid norbornane have been synthesized (Foitzik et al., 2009; Jansen et al., 2010; Tang et al., 2009). The highly symmetrical structures reduce the complexity due to the constraint of geometrical and conformational variations. The rates of photoinduced electron transfer reactions across linearly fused oligo-norbornyl spacer groups have been estimated (Chen et al., 2002; Chow et al., 2005). The ET rates were found to correlate well with both D—A distance and solvent polarities. Atoms C11 and C14 of the title compound are chiral centers, but their relative configurations are opposite. The racemate was prepared as a model compound for investigations of the intramolecular electron transfer reactions (Chen et al., 2006).

The structure of the title compound comprises a norbornane unit having a dicyanonaphthalene ring fused on one side (Figure 1). The naphthalene is essentially planar with a maximum deviation of 0.039 (2)° for atom C5. Whereas both cyano groups are slightly twisted out of the plane of the naphthalene ring (1.9 (2)° of C17–C6–C5–C16). The puckering parameters (Cremer & Pople, 1975) of the five-membered rings A (C1/C10/C11/C15/C14) and B (C11–C15) are Q₂ = 0.5621 (17)Å and φ₂ = 287.97 (16)°, and Q₂ = 0.6013 (17)Å and φ₂ = 144.60 (16)°, respectively. These results are slightly different from those of previous studies on other norbornane derivatives (Çelik, et al., 2006; Chen, et al., 2011; Lough, et al., 2006). In the crystal structure (Figure 2), inversion-related molecules are linked by a pair of C—H···N hydrogen bonds (Table 1), forming a cyclic dimers with R₂²(10) graph-set motif (Bernstein et al., 1995). The C—H···π interactions are also observed (2.81 Å of C13—H13B···Cg3 distance, symmetry code: -x, -y, -z + 1, where Cg3 is the centroid of the C1–C3/C8–C10 ring), and further stabilize the crystal structure.

Experimental

The title compound was synthesized according to the literature (Chen et al., 2006). Colorless needle-shaped crystals suitable for the crystallographic studies reported here were isolated over a period of six weeks by slow evaporation from the chloroform solution.