(6RS,9SR)-6,7-Dibromo-1,2,3,4-tetra­hydro-1,4-methano­anthracene

Kew-Yu Chen; Ming-Jen Chang; Tzu-Chien Fang

doi:10.1107/S1600536811013572

. 2011 Apr 16;67(Pt 5):o1147. doi: 10.1107/S1600536811013572

(6RS,9SR)-6,7-Dibromo-1,2,3,4-tetrahydro-1,4-methanoanthracene

Kew-Yu Chen ^a,^*, Ming-Jen Chang ^a, Tzu-Chien Fang ^a

PMCID: PMC3089252 PMID: 21754455

Abstract

The title compound, C₁₅H₁₂Br₂, comprises a norbornane unit having a dibromonaphthalene ring fused on one side. Both Br atoms are twisted slightly out of the plane of the naphthalene ring system with a Br—C—C—Br torsion angle of 5.3 (5)°. In the crystal, molecules are linked by weak intermolecular C—H⋯Br hydrogen bonds, forming an infinite C(9) chain along [110].

Related literature

For the spectroscopy of the title compound and its preparation, 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 ▶); Lewis et al. (1997 ▶); Roest et al. (1996 ▶). For related structures, see: Çelik et al. (2006 ▶); Chiou et al. (2001 ▶); Chow et al. (1999 ▶); Lough et al. (2006 ▶). For the C—H⋯Br hydrogen bond, see: Desiraju & Steiner (2001 ▶); Farrugia et al. (2007 ▶); Kuś & Jones (2003 ▶); Yang et al. (2007 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₂Br₂
M _r = 352.07
Monoclinic,
a = 23.437 (3) Å
b = 6.3565 (8) Å
c = 18.416 (2) Å
β = 111.781 (2)°
V = 2547.6 (6) Å³
Z = 8
Mo Kα radiation
μ = 6.34 mm⁻¹
T = 297 K
0.56 × 0.48 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.399, T _max = 1.000
6895 measured reflections
2501 independent reflections
1817 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.144
S = 0.96
2501 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536811013572/nr2004sup1.cif

e-67-o1147-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013572/nr2004Isup2.hkl

e-67-o1147-Isup2.hkl^{(123KB, 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
C8—H8A⋯Br2ⁱ	0.97	3.00 (1)	3.843 (16)	146 (1)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the National Science Council of the Republic of China is gratefully acknowledged.

supplementary crystallographic information

Comment

Electron donor (D)–acceptor (A) chromophores linked by rigid, covalent spacers (S), forming D–S–A dyads, have attracted considerable attention due to their potential applications in the design of molecular devices (Lewis et al., 1997; Roest et al., 1996). Numerous types of spacers have been reported (Chiou et al., 2001; Chow et al., 1999). However, rigid linear rod-shaped structures are not commonly seen. 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 C6 and C9 of the title compound are chiral centers, but their relative configurations are opposite (6R,9S or 6S,9R). The racemate was prepared as a model compound for investigations of the intramolecular electron transfer reactions (Chen et al., 2006).

The ORTEP diagram of the title compound is shown in Figure 1. The puckering parameters (Cremer & Pople, 1975) of the five-membered rings A (C5/C6/C15/C9/C10) and B (C6–C9/C15) are Q₂ = 0.560 (6)Å and φ₂ = 71.0 (5)°, and Q₂ = 0.602 (6)Å and φ₂ = 144.7 (6)°, respectively. These results are slightly different from those of previous studies on other norbornane derivatives (Çelik, et al., 2006; Lough, et al., 2006). In addition, the naphthalene ring is essentially planar with a maximum deviation of 0.052 (2)Å for atom C5. Whereas both bromine atoms are slightly twisted out of the plane of the naphthalene ring (5.3 (5)° of Br1—C1—C14—Br2, Table 1). In the crystal structure (Figure 2), the molecules are linked by weak intermolecular C—H···Br (2.998 (2)Å of C8—H8A···Br2 distance and 146 (1)° of C8—H8A—Br2, Table 2) hydrogen bonds (Desiraju et al., 2001; Farrugia et al., 2007; Kuś et al., 2003; Yang et al., 2007) to form an infinite two-dimensional chain, generating a C(9) motif (Bernstein et al., 1995).

Experimental

A mixture of α,α,α',α'-4,5- hexabromo-o-xylene (4.3 mmol), norbornene (4.3 mmol), sodium iodide (30 mmol), and dry DMF (50 ml) was stirred at 65 ^oC for 24 h. The reaction mixture was poured into cold water (350 ml) containing sodium bisfulfite (5.0 g). The yellow precipitate was purified by chromatography (silica gel column, hexane:ethyl acetate = 6:1) and finally by recrystallization. Colorless needle-shaped crystals suitable for the crystallographic studies reported here were isolated over a period of five weeks by slow evaporation from a chloroform solution.