Bis(1-benzoyl-7-meth­oxy­naphthalen-2-yl) terephthalate

Rei Sakamoto; Daichi Hijikata; Katsuhiro Isozaki; Noriyuki Yonezawa; Akiko Okamoto

doi:10.1107/S1600536813007186

. 2013 Mar 20;69(Pt 4):o557. doi: 10.1107/S1600536813007186

Bis(1-benzoyl-7-methoxynaphthalen-2-yl) terephthalate

Rei Sakamoto ^a, Daichi Hijikata ^a, Katsuhiro Isozaki ^b, Noriyuki Yonezawa ^a, Akiko Okamoto ^a,^*

PMCID: PMC3629609 PMID: 23634096

Abstract

The title molecule, C₄₄H₃₀O₈, lies about a crystallographic inversion centre located at the centre of the central benzene ring. The benzene rings in the benzoyl and the terephthalate units make dihedral angles of 67.05 (7)° and 57.57 (7)°, respectively, with the naphthalene ring system. There is an intramolecular C—H⋯O interaction between the ketonic carbonyl O atom and an H atom on the naphthalene ring system. In the crystal, C—H⋯O interaction of the benzene ring in the benzoyl group and weak C=O⋯π interaction [O⋯centroid = 3.375 (2) Å] of the naphthalene ring with the O atom in the ketonic carbonyl group are observed. These interactions form layers parallel to the bc plane.

Related literature

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶). For the structures of closely related compounds, see: Kato et al. (2010 ▶); Nakaema et al. (2008 ▶); Sakamoto et al. (2012 ▶, 2013 ▶). graphic file with name e-69-0o557-scheme1.jpg

Experimental

Crystal data

C₄₄H₃₀O₈
M _r = 686.72
Monoclinic,
a = 9.977 (5) Å
b = 14.922 (7) Å
c = 11.709 (6) Å
β = 106.610 (5)°
V = 1670.5 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.16 × 0.13 × 0.03 mm

Data collection

Rigaku Saturn70 diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.985, T _max = 0.997
10969 measured reflections
2909 independent reflections
2354 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.122
S = 1.04
2909 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrystalClear (Rigaku, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Click here for additional data file.^{(20.3KB, cif)}

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813007186/rn2113sup1.cif

e-69-0o557-sup1.cif^{(20.3KB, cif)}

Click here for additional data file.^{(142.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007186/rn2113Isup2.hkl

e-69-0o557-Isup2.hkl^{(142.8KB, hkl)}

Click here for additional data file.^{(12.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007186/rn2113Isup3.cml

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—H8⋯O1	0.95	2.41	2.965 (3)	117
C16—H16⋯O1ⁱ	0.95	2.55	3.258 (3)	132

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors express their gratitude to Associate Professor Hikaru Takaya and Professor Masaharu Nakamura, Institute for Chemical Research, Kyoto University, for their kind advice. This work was partially supported by the Collaborative Research Program of Institute for Chemical Research, Kyoto University (grant No. 2012–72).

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of the naphthalene core, 1,8-diaroylnaphthalene compounds have proved to be formed regioselectively by the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009, Okamoto et al., 2011).

Recently, we have reported the X-ray crystal structures of 1,8-diaroylated 2,7-dialkoxynaphthalene, e.g., 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008). Furthermore, we have also determined the crystal structures of 1-monoaroylated 2,7-dialkoxynaphthalene compounds such as (2,7-dimethoxynaphthalen-1-yl)(phenyl)methanone [1-benzoyl-2,7-dimethoxynaphthalene](Kato et al., 2010).

These compounds have non-coplanar structures where the aroyl groups are perpendicularly orientated relative to the naphthalene ring. Crystal structures of the aroylnaphthalene analogues bearing oxybenzoyl groups at the 2,7- positions of the naphthalene ring core namely 1,8-dibenzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2012) and 1-benzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2013), have been previously determined which show the molecules form the tubular arrangements when the benzene ring of the benzoyl group effectively interacts with the carbonyl moiety of the benzoyloxy group and the naphthalene ring through intermolecular C–H···O and C–H···π interactions.

As a part of our ongoing studies on the molecular structures of these kinds of homologous molecules, the X-ray crystal structure of the title compound composed of two 1-benzoylnaphthalene units and a terephthalate moiety is reported on herein.

The molecular structure of the title compound is displayed in Fig. 1. The molecule lies on a centre of inversion so that the asymmetric unit contains one-half of the molecules. The benzene rings in the benzoyl group and the terephthalate moiety are twisted away from the naphthalene ring. Two kinds of intramolecular C–H···O interactions, one intramolecular C–H···O interaction between the naphthalene ring and the benzoyl group (C8–H8···O1 = 2.41 Å) and another one between the benzene ring and the ethereal oxygen of the terephthalate moiety (C22–H22···O3 = 2.39 Å), contribute to stabilization of the twisted orientation of each benzene ring against the naphthalene ring (Fig. 1).

The dihedral angles of the benzene ring in the benzoyl group and the terephthalate moiety with the naphthalene ring are 67.05 (7)° [C9–C1–C11–O1 and O1–C11–C12–C17, torsion angles = -45.1 (3) and -26.3 (3)° for benzoyl group] and 57.57 (7)° [O4–C19–C20–C21, O4–C19–O3–C2, and C3–C2–O3–C19, torsion angles = 2.9 (3), 4.0 (5), and -66.8 (9)° for terephthalate moiety].

In the case of the homologous molecule, 1-benzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2013), the corresponding dihedral angles are slightly larger than those of the title compound [80.41 (6)° and 73.62 (5)°].

In the crystal (Fig. 2), the ketonic carbonyl oxygen forms intermolecular C–H···O interaction with the benzene ring of the benzoyl goup [C16–H16···O1ⁱ = 2.55 Å; symmetry code: x, 1/2 - y, -1/2 + z] and weak intermolecular C=O···π interaction with the naphthalene ring [C11–O1···Cg1ⁱⁱ = 3.38 Å; Cg1 is the centroids of the C1/C4–C9–C10 rings].

Consequently, the molecules are arranged in laminae along the bc-plane (Fig. 3).

Experimental

The title compound was prepared by treatment of a mixture of (2-hydroxy-7-methoxynaphthalen-1-yl)(phenyl)methanone (0.4 mmol, 111 mg), terephthaloyl dichloride (0.22 mmol, 44.7 mg), and triethylamine (0.44 mmol, 0.062 ml) in dichloromethane (1.0 ml). After the reaction mixture was stirred at rt for 3 h, it was poured into water (30 ml) and the mixture was extracted with chloroform (10 ml×3). The combined extracts were washed with brine. The organic layers thus obtained were dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give cake (yield 63%). The crude product was purified by recrystallization from chloroform and colorless single crystals suitable for X-ray diffraction were obtained.

Spectroscopic data: ¹H NMR δ (500 MHz, CDCl₃): 3.76 (6H, s), 7.02 (2H, dd, J=9.2, 2.3 Hz), 7.20 (2H, dd, J=9.2, 2.3 Hz), 7.33–7.39 (6H, m), 7.50 (2H, t, J=7.4 Hz), 7.66 (4H, s), 7.81–7.85 (6H, m), 7.96 (2H, d, J=8.6 Hz) p.p.m..

¹³C NMR δ (75 MHz, CDCl₃): 55.30, 103.37, 118.54, 119.32, 126.63, 127.18, 128.68, 129.43, 129.71, 129.83, 130.95, 132.84, 133.75, 137.78, 146.33, 158.99, 163.38, 195.98 p.p.m..

IR (KBr): 1729 (OC=O), 1663 (C=O), 1624,1595, 1510 (Ar) cm^-1. m.p. = 484.2–484.8 K.

Anal. Calcd for C₄₄H₃₀O₈ 3.5H₂O: C, 70.49; H, 4.97; Found: C, 70.40; H, 4.73.