1-Benzoyl­naphthalene-2,7-diyl dibenzoate

Rei Sakamoto; Kosuke Sasagawa; Daichi Hijikata; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S1600536812052026

. 2013 Jan 9;69(Pt 2):o210. doi: 10.1107/S1600536812052026

1-Benzoylnaphthalene-2,7-diyl dibenzoate

Rei Sakamoto ^a, Kosuke Sasagawa ^a, Daichi Hijikata ^a, Akiko Okamoto ^a,^*, Noriyuki Yonezawa ^a

PMCID: PMC3569746 PMID: 23424492

Abstract

In the title compound, C₃₁H₂₀O₅, the phenyl rings of the benzoyloxy and benzoyl groups are twisted away from the naphthalene ring system by 64.27 (6), 73.62 (5) and 80.41 (6)°. In the crystal, C—H⋯O hydrogen bonds and C—H⋯π interactions link the molecules, forming tubular chains parallel to the b axis. The chains are further connected into a three-dimensional network by C—H⋯π interactions and π–π stacking contacts [centroid–centroid distances = 3.622 (10)–3.866 (12) Å].

Related literature

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶). For structures of closely related compounds, see: Kato et al. (2010 ▶); Muto et al. (2011 ▶); Nakaema et al. (2008 ▶); Sakamoto et al. (2012 ▶); Watanabe et al. (2010 ▶). graphic file with name e-69-0o210-scheme1.jpg

Experimental

Crystal data

C₃₁H₂₀O₅
M _r = 472.47
Monoclinic,
a = 16.1318 (3) Å
b = 7.18561 (13) Å
c = 20.7333 (4) Å
β = 99.180 (1)°
V = 2372.56 (7) Å³
Z = 4
Cu Kα radiation
μ = 0.73 mm⁻¹
T = 193 K
0.40 × 0.40 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.759, T _max = 0.811
40057 measured reflections
4282 independent reflections
3753 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.103
S = 1.07
4282 reflections
326 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2010 ▶); 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

Click here for additional data file.^{(23.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812052026/rz5035sup1.cif

e-69-0o210-sup1.cif^{(23.7KB, cif)}

Click here for additional data file.^{(205.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812052026/rz5035Isup2.hkl

e-69-0o210-Isup2.hkl^{(205.6KB, hkl)}

Click here for additional data file.^{(8.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812052026/rz5035Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C26–C31 and C5–C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.95	2.30	3.2183 (16)	164
C14—H14⋯O5ⁱⁱ	0.95	2.60	3.520 (2)	164
C29—H29⋯Cg1ⁱⁱⁱ	0.95	2.72	3.6396 (18)	162
C15—H15⋯Cg2ⁱⁱ	0.95	2.78	3.6397 (19)	150

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors would like to 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 Iron and Steel Institute of Japan (ISIJ) Research Promotion Grant, Tokyo, Japan.

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-diaroylnaphthalenes, e.g., 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008). The two aroyl groups at 1,8-positions of the naphthalene ring in these compounds are perpendicularly attached to the naphthalene ring and oriented in opposite directions. Furthermore, we have also clarified the crystal structures of 1-monoaroylated naphthalene compounds such as (2,7-dimethoxynaphthalene-1-yl)-(phenyl)methanone (Kato et al., 2010) and 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010). These compounds also exhibit essentially the same non-coplanar structure as the 1,8-diaroylated naphthalenes. Besides, the crystal structures of the aroylnaphthalene derivatives bearing benzoic ester moiety at the 2- or 2,7-positions on the naphthalene ring, 7-methoxy-1-(4-nitrobenzoyl)naphthalene-2-yl 4-nitrobenzoate (Muto et al., 2011) and 1,8-dibenzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2012) have been revealed.

The molecular structure of the title compound is displayed in Fig 1. The benzene ring of the benzoyl group is almost orthogonal to the naphthalene ring system forming a dihedral angle of 80.41 (6)° [C10—C1—C11—O1 torsion angle = 83.35 (15)°]. The two carbonyl moieties of the benzoyloxy groups at the 2,7-positions of the naphthalene ring system are in opposite directions relative to one another, as observed in the homologous compound 1,8-dibenzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2012). The phenyl ring of the benzoyloxy group at the 7-position is inclined to form a narrower dihedral angle with the naphthalene ring system [64.27 (6)° and O5—C25—C26—C27 torsion angle = -21.8 (2)°] than the phenyl ring of the benzoyloxy group at the 2-position adjacent to the benzoyl group [73.62 (5)° and O3—C18—C19—C24 torsion angle = -2.1 (2)°]. In the crystal, C–H···O hydrogen bonds between an hydrogen atom of the phenyl ring of the benzoyl group and a carbonyl oxygen of the benzoyloxy group and between an hydrogen atom of the naphthalene ring system and a carbonyl oxygen of the benzoyl group, and weak C–H···π interactions (Table 1) link the molecules into tubular chains running parallel to the b axis (Fig. 2 and 3). Furthermore, the chains are connected into a three-dimensional network by weak C–H···π interactions [C15–H15···Cg2 = 2.78 Å; Cg2 is the centroids of the C5–C10 ring] and π–π contacts [Cg2ⁱⁱⁱ···Cg3, 3.622 (10) Å; Cg4···Cg4^iv = 3.821 (12) Å; Cg4···Cg4^v = 3.866 (12) Å; Cg3 and Cg4 are the centroids of the C1/C4-C9-C10 and C19/C24 rings, respectively; symmetry codes: (iii) 1-x, 1-y, 1-z; (iv) -x, 1-y, 1-z; (v) -x, 2-y, 1-z).

Experimental

The title compound was prepared via condensation reaction of 1-benzoyl-2,7-dihydroxynaphthalene (0.2 mmol, 52.86 mg) obtained by ethyl ether cleavage reaction of 1-benzoyl-2,7-diethoxynaphthalene, benzoyl chloride (0.4 mmol, 0.046 ml), and triethylamine (0.4 mmol, 0.056 ml) in dichloromethane (2.5 ml). After the reaction mixture was stirred at rt for 2 h, it was poured into water (30 ml) and the mixture was extracted with CHCl₃ (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. The crude product was purified by recrystallization from ethyl acetate–hexane (3:1 v/v) and colorless single crystals suitable for X-ray diffraction were obtained (isolated yield 36%).

Spectroscopic data: ¹H NMR δ (400 MHz, CDCl₃): 7.24–7.38 (4H, m), 7.45–7.54 (6H, m), 7.59 (1H, d, J = 2.4 Hz), 7.63 (1H, t, J = 14.8 Hz), 7.74 (2H, d, J = 7.6 Hz), 7.85 (2H, d, J = 7.2 Hz), 8.02 (1H, d, J = 9.2 Hz), 8.08 (1H, d, J = 9.2 Hz), 8.18 (2H, d, J = 7.2 Hz) p.p.m.. ¹³C NMR δ (75 MHz, CDCl₃): 116.33, 121.37, 121.93, 127.64, 128.26, 128.38, 128.51, 128.61, 129.10, 129.52, 129.59, 129.76, 129.87, 130.13, 130.86, 132.06, 133.59, 133.66, 133.76, 137.49, 146.53, 150.09, 164.18, 164.95, 195.32 p.p.m.. IR (KBr): 1739 (OC=O), 1658 (C=O), 1596,1582, 1510 (Ar) cm^-1. m.p. = 422.0–422.8 K. HRMS (m/z): [M+H]⁺ calcd. for C₃₁H₂₀O₅, 473.1390, found, 473.1384.