7-Meth­oxy-1-(4-nitro­benzo­yl)naph­thalen-2-yl 4-nitro­benzoate

Toyokazu Muto; Daichi Hijikata; Akiko Okamoto; Hideaki Oike; Noriyuki Yonezawa

doi:10.1107/S1600536811027619

. 2011 Jul 16;67(Pt 8):o2040. doi: 10.1107/S1600536811027619

7-Methoxy-1-(4-nitrobenzoyl)naphthalen-2-yl 4-nitrobenzoate

Toyokazu Muto ^a, Daichi Hijikata ^a, Akiko Okamoto ^a,^*, Hideaki Oike ^a, Noriyuki Yonezawa ^a

PMCID: PMC3213489 PMID: 22091068

Abstract

In the title compound, C₂₅H₁₆N₂O₈, the dihedral angle between the naphthalene ring system and the benzene ring of the nitrophenyl ketone unit is 82.64 (7)°. The bridging ester O—C(=O)—C plane makes dihedral angles of 42.12 (8) and 11.47 (9)°, respectively, with the naphthalene ring system and the benzene ring of the nitrophenyl ester unit. In the crystal, two types of weak intermolecular C—H⋯O interactions are observed.

Related literature

For electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009 ▶). For the structures of closely related compounds, see: Muto et al. (2010 ▶); Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008 ▶); Mitsui, Nakaema, Noguchi & Yonezawa (2008 ▶); Mitsui et al. (2009 ▶); Nagasawa et al. (2010 ▶); Watanabe et al. (2010 ▶).

Experimental

Crystal data

C₂₅H₁₆N₂O₈
M _r = 472.40
Triclinic,
a = 7.30691 (15) Å
b = 10.2555 (2) Å
c = 14.7645 (3) Å
α = 84.750 (1)°
β = 86.278 (1)°
γ = 74.079 (1)°
V = 1058.57 (4) Å³
Z = 2
Cu Kα radiation
μ = 0.95 mm⁻¹
T = 193 K
0.60 × 0.20 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.599, T _max = 0.911
19272 measured reflections
3818 independent reflections
2769 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.124
S = 1.09
3818 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (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/S1600536811027619/is2749sup1.cif

e-67-o2040-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027619/is2749Isup2.hkl

e-67-o2040-Isup2.hkl^{(183.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811027619/is2749Isup3.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
C6—H6⋯O7ⁱ	0.95	2.58	3.211 (3)	124
C23—H23⋯O4ⁱⁱ	0.95	2.55	3.435 (2)	154

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

Acknowledgments

The authors express their gratitude to Masters Yuichi Kato and Atsushi Nagasawa, Department of Organic and Polymer Materials Chemistry, Graduate School, Tokyo University of Agriculture & Technology, and Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for technical advice.

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proven to be formed regioselectively with the aid of suitable acidic mediators (Okamoto & Yonezawa, 2009). Recently, we have reported the crystal structures of several 1,8-diaroylated naphthalene homologues exemplified by 1,8-bis(4-methylbenzoyl)-2,7-dimethoxynaphthalene (Muto et al., 2010). The aroyl groups at the 1,8-positions of the naphthalene rings in these compounds are twistedly connected in an almost perpendicular fashion, but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. The crystal structures of 1-monoaroylated naphthalene compounds such as 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010) also exhibit essentially the same non-coplanar structure as the 1,8-diaroylated naphthalenes. Furthermore, the crystal structures of several 1-monoaroylated naphthalene derivatives have revealed. For example, (2-hydroxy-7-methoxynaphthalen-1-yl)(4-methylphenyl)methanone (Nagasawa et al., 2010) and (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008) prepared by regioselective demethylation form intramolecular hydrogen bond between the carbonyl group and the adjacent hydroxy one. Besides, (4-chlorobenzoyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2009) has similar non-coplanar configuration to 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008). As a part of our continuous studies on the molecular structures of this kind of homologous molecules, the crystal structure of the title compound, 1-monoaroylated naphthalene bearing 4-nitrobenzoyloxy group at 2-position is discussed in this report.

The molecular structure of the title compound is displayed in Fig. 1. The benzene ring of nitrophenyl ketone moiety (C12–C17) is out of the plane of the naphthalene ring. The dihedral angle between the best planes of the benzene ring (C12–C17) and the naphthalene ring system (C1–C10) is 82.64 (7)° [C2–C1–C11–O1 torsion angle = -79.8 (2)°]. However, the carbonyl group (C11═O1) and the benzene ring (C12–C17) have almost coplanar configuration [O1–C11–C12–C17 torsion angle = 5.0 (2)°]. Besides, the dihedral angle between the benzene ring (C12–C17) and the nitro group plane (O4/N1/O5) is 29.35 (9)°. On the other hand, the benzene ring of nitrophenyl ester moiety (C19–C24) makes a rather small dihedral angle with naphthalene ring system (C1–C10) than that with the benzene ring of nitrophenyl ketone moiety (C12–C17), i.e., 31.38 (7)°. Moreover, the dihedral angles of the benzene ring (C19–C24) and the naphthalene ring system (C1–C10) with the ester plane (O2—C18(═ O6)—C19) are 11.47 (9)° and 42.12 (8)°, respectively. The nitro group plane (O7/N2/O8) makes a small dihedral angle of 6.47 (10)° with the benzene ring (C19–C24). In the crystal structure, the molecular packing of the title compound is stabilized mainly by van der Waals interactions. The crystal packing is additionally stabilized by intermolecular C—H···O interaction between the oxygen atom (O7) of the nitro group in nitrophenyl ester and one hydrogen atom (H6) of the naphthalene ring of the adjacent molecule (C6—H6···O7ⁱ; Fig. 2 and Table 1). Moreover, there is also intermolecular C—H···O interaction between the oxygen atom (O4) of the nitro group in nitrophenyl ketone and one hydrogen atom (H23) of the nitrophenyl ester of the adjacent molecule (C23—H23···O4ⁱⁱ; Fig. 3 and Table 1).

Experimental

To a 100 ml flask, 4-nitrobenzoyl chloride (17 mmol, 3.173 g), aluminium chloride (18.7 mmol, 2.495 g) and methylene chloride (21 ml) were placed and stirred at 273 K. To the reaction mixture thus obtained, 2,7-dimethoxynaphthalene (8.5 mmol, 1.599 g) was added. After the reaction mixture was stirred at 273 K for 60 h, it was poured into ice-cold water (10 ml). The aqueous layer was extracted with CHCl₃ (10 ml × 3). The combined extracts were washed with 2 M aqueous NaOH followed by washing 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 silica-gel chromatography from CHCl₃. Yellow platelet single crystals suitable for X-ray diffraction were obtained by crystallization from ethanol (10 mg, 0.2% yield).

¹H NMR δ (300 MHz, CDCl₃); 3.75 (3H, s), 6.91 (1H, d, J = 2.4 Hz), 7.24 (1H, dd, J = 2.4, 9.0 Hz), 7.34 (1H, d, J = 8.4 Hz), 7.89 (1H, d, J = 9.0 Hz), 7.98 (2H, d, J = 9.0 Hz), 8.00 (2H, d, J = 8.4 Hz), 8.04 (1H, d, J = 9.0 Hz), 8.21 (2H, d, J = 8.4 Hz), 8.22 (2H, d, J = 9.3 Hz) p.p.m..

¹³C NMR δ (75 MHz, CDCl₃); 55.32, 103.27, 118.37, 119.57, 123.65, 123.93, 125.45, 127.27, 130.14, 130.39, 131.00, 132.03, 132.54, 133.55, 141.98, 146.62, 150.55, 150.96, 159.37, 162.57, 194.18 p.p.m..

IR (KBr); 1746, 1679, 1619, 1525, 1349, 1234, 1208 cm^-1

HRMS (m/z); [M + H]+ Calcd for C₂₅H₁₇N₂O₈, 473.0985; found, 473.0977.

m.p. = 452.0–454.0 K