8-(Biphenyl-2-yl)-7,9-diphenyl-8H-cyclo­penta­[a]acenaphthylen-8-ol

Peter G Jones; Marc Debeaux; Henning Hopf; Wolfgang Kowalsky; Hans-Hermann Johannes

doi:10.1107/S1600536809011222

. 2009 Mar 31;65(Pt 4):o927. doi: 10.1107/S1600536809011222

8-(Biphenyl-2-yl)-7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-ol

Peter G Jones ^a,^*, Marc Debeaux ^b, Henning Hopf ^c, Wolfgang Kowalsky ^b, Hans-Hermann Johannes ^b

PMCID: PMC2968992 PMID: 21582628

Abstract

In the title compound, C₃₉H₂₆O, the cyclopenta[a]acenaphthylene skeleton displays the expected distortions, with formal sp ² bond angles as high as C—C—C = 142.50 (10)°. The OH group forms intermolecular hydrogen bonds via x-axis translation to the centroid (Cg) of the pendant phenyl ring of the biphenyl system, with H⋯Cg = 2.41 Å and O—H⋯Cg = 153°.

Related literature

For related literature, see: Saragi et al. (2007 ▶); Velusamy et al. (2007 ▶).

Experimental

Crystal data

C₃₉H₂₆O
M _r = 510.60
Monoclinic,
a = 7.3837 (4) Å
b = 18.4001 (12) Å
c = 19.2505 (12) Å
β = 97.549 (3)°
V = 2592.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 103 K
0.35 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.893, T _max = 0.985
53233 measured reflections
7857 independent reflections
6335 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.125
S = 1.02
7857 reflections
365 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011222/bt2916sup1.cif

e-65-0o927-sup1.cif^{(29.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011222/bt2916Isup2.hkl

e-65-0o927-Isup2.hkl^{(384.4KB, hkl)}

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

Acknowledgments

The authors thank the Bundesministerium für Bildung und Forschung (BMBF 01 BD 0687) for financial support.

supplementary crystallographic information

Comment

The title compound (I) is a derivative of 7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one, an interesting starting compound for optoelectronic materials (Velusamy et al., 2007). Spiro compounds with orthogonally fixed aromatic moieties are known to form stable molecular glasses, an important prerequisite of materials for optoelectronic applications (Saragi et al., 2007). We have synthesized the title compound by addition of biphenyl-2-yl lithium (III) to the ketone II with a view to generating a corresponding spiro compound, which could combine both attractive electronic properties and amorphous stability, by further cyclocondensation.

The molecule of I is shown in Fig. 1. The cyclopenta[a]acenaphthylene skeleton displays the expected distortions, with formally sp² angles as high as C7—C6B—C6A 142.50 (10)°. The 15 atoms of this skeleton are reasonably coplanar (r.m.s.d. 0.09 Å) but a better description is of the fused cyclopentadiene (r.m.s.d. 0.030 Å) subtending an interplanar angle of 10.52 (1)° with the ten atoms of the naphthalenoid moiety plus the atoms C6B and C9A (r.m.s.d. 0.037 Å). With the phenyl rings C10–15, C16–21, C22–27 it subtends angles of 33.50 (4), 30.51 (4) and 83.89 (4)° respectively. The biphenyl interplanar angle is 76.93 (4)°.

The OH group does not form intermolecular hydrogen bonds with its counterparts in neighbouring molecules, presumably for steric reasons. Instead, the acceptor is the centroid of ring C28–33, with H01···Cent 2.41 Å, O—H01···Cent 153°, operator x - 1,y,z.

Experimental

2-Bromobiphenyl (900 mg, 3.86 mmol) in dry THF (10 ml) was treated with a 1.6 M solution of n-butyl lithium in n-hexane (2.81 ml, 4.50 mmol) at -80 °C. The mixture was stirred for 1 h at -80 °C and added to a suspension of 7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one (1.38 g, 3.86 mmol) in dry THF (25 ml). After 4 h of stirring under reflux, a saturated aqueous solution of ammonium chloride (50 ml) was added. Extraction with dichloromethane (3 × 50 ml), drying (MgSO₄) and concentration afforded the crude product, which was purified by flash chromatography on silica gel (CH₂Cl₂/n-hexane, 1:1; R_f= 0.32). The title compound was obtained as a yellow microcrystalline solid (597 mg, 30%), mp 244 °C. Elemental analysis: calculated for C₃₉H₂₆O: C 91.73, H 5.13%; found: C 91.79, 5.07%. Spectroscopic analysis: ¹H NMR (400 MHz, CDCl₃) δ = 8.29 (dd, J = 8.1, 1.3, 1 H), 7.75 (d, J = 7.1, 2 H), 7.68–7.62 (m, 6 H), 7.48–7.39 (m, 3 H), 7.37–7.24 (m, 7 H), 6.92 (dd, J = 7.5, 1.4, 1 H), 6.83 (dd, J = 7.9, 1.5, 2 H), 6.47 (dd, J = 7.7, 7.7, 2 H), 6.27–6.21 (m, 1 H), 2.50 p.p.m. (s, 1 H, OH); ¹³C NMR (101 MHz, CDCl₃) δ = 145.2 (s), 144.1 (s), 141.0 (s), 140.5 (s), 140.4 (s), 137.1 (s), 134.4 (s), 132.4 (s), 131.6 (s), 131.4 (d), 128.8 (d), 128.2 (d), 128.1 (d), 127.7 (d), 127.5 (d), 127.4 (d), 127.4 (d), 127.1 (d), 126.0 (d), 125.6 (d), 125.5 (d), 119.2 (d), 96.3 p.p.m. (s).