1,5,7,8′,11-Penta­meth­oxy-13H-spiro­[dibenzo[a,g]fluorene-13,1′(4′H)-naphthalen]-4′-one toluene monosolvate

Ryo Takeuchi; Atsushi Nagasawa; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S160053681203824X

. 2012 Sep 12;68(Pt 10):o2919. doi: 10.1107/S160053681203824X

1,5,7,8′,11-Pentamethoxy-13H-spiro[dibenzo[a,g]fluorene-13,1′(4′H)-naphthalen]-4′-one toluene monosolvate

Ryo Takeuchi ^a, Atsushi Nagasawa ^a, Akiko Okamoto ^a,^*, Noriyuki Yonezawa ^a

PMCID: PMC3470265 PMID: 23125709

Abstract

In the title compound, C₃₅H₂₈O₆·C₇H₈, the dihedral angle between the mean planes through the naphthalene ring systems of the dibenzo[a,g]fluorene moiety is 22.44 (3)°. The aromatic ring system of the naphthalenone unit is approximately perpendicular to the mean plane of the five-membered ring, forming a dihedral angle of 87.51 (5)°. An intramolecular C—H⋯O hydrogen bond is observed. In the crystal, pairs of C—H⋯π interactions link the molecules, forming inversion dimers.

Related literature

For electrophilic aromatic aroylation of the 2,7-dimethoxynaphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶).

Experimental

Crystal data

C₃₅H₂₈O₆·C₇H₈
M _r = 636.71
Monoclinic,
a = 12.4106 (6) Å
b = 12.4974 (7) Å
c = 21.4941 (11) Å
β = 97.319 (3)°
V = 3306.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.68 mm⁻¹
T = 193 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.773, T _max = 0.876
48937 measured reflections
6036 independent reflections
3696 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.124
S = 0.96
6036 reflections
440 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681203824X/rz2797sup1.cif

e-68-o2919-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203824X/rz2797Isup2.hkl

e-68-o2919-Isup2.hkl^{(289.5KB, hkl)}

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

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O4	0.95	2.22	2.810 (2)	120
C28—H28⋯Cg1ⁱ	0.95	2.65	3.550 (2)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors express their gratitude to Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for technical advice. This work was partially supported by the Sasagawa Scientific Research Grant from the Japan Science Society.

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene (Okamoto & Yonezawa, 2009; Okamoto et al., 2011) and related compounds, we have found a unique trimerization reaction affording the title compound, C₃₅H₂₈O₆.C₇H₈ (Fig. 1). The molecule is composed of dibenzo[a,g]fluorene and naphthalenone units originated from three naphthalene rings. The two units are connected by spiro bonding and configured in an approximately perpendicular fashion. The dihedral angle between the five-membered ring (C1/C2/C11/C12/C21) of the dibenzo[a,g]fluorene unit and the naphthalenone moiety (C21–C25/C30) is 87.51 (5)°. The dibenzo[a,g]fluorene unit is remarkably twisted, the dihedral angle between mean planes through the naphtlhalene ring systems [C1–C10 (Nap1) and C11–C20 (Nap2)] being 22.44 (3)°. This configuration presumably originates from the steric hindrance between the aromatic H3 atom of Nap1 and the O4 methoxy group of Nap2. Between these atoms an intramolecular hydrogen bond is observed (Table 1). In the crystal packing, centrosymmetrically-related molecules are linked into dimers via C—H···π hydrogen interactions (Table 1).

Experimental

1,5-Dimethoxynaphthalene (0.6 mmol), 1,3-dinitrobenzene (0.09 mmol) and CH₂Cl₂ (3 ml) were placed into a dried flask, followed by stirring at room temperature for 5 min under nitrogen atmosphere. To the reaction mixture, TiCl₄ (3.0 mmol) was slowly added. The reaction mixture was poured into ice-cold water after it had been stirred at room temperature for 6 h. The aqueous layer was extracted with CHCl₃ (40 ml). The combined extracts were washed with 2M aqueous NaOH followed by washing with brine. The organic layer thus obtained was dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give the crude product (yield 99%), which was purified by preparative thin layer chromatography [toluene:EtOAc 40:1 v/v]. Transparent yellow single crystals suitable for X-ray diffraction were obtained by crystallization from toluene and hexane [1:1 v/v].