(4-Chloro­phen­yl)(2,7-dimeth­oxy-8-nitro­naphthalen-1-yl)methanone

Takahiro Nishijima; Atsushi Nagasawa; Teruhisa Takada; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S1600536810051998

. 2010 Dec 18;67(Pt 1):o155. doi: 10.1107/S1600536810051998

(4-Chlorophenyl)(2,7-dimethoxy-8-nitronaphthalen-1-yl)methanone

Takahiro Nishijima ^a, Atsushi Nagasawa ^a, Teruhisa Takada ^a, Akiko Okamoto ^a,^*, Noriyuki Yonezawa ^a

PMCID: PMC3050249 PMID: 21522662

Abstract

In the title compound, C₁₉H₁₄ClNO₅, the aroyl group is attached to the naphthalene ring system with a non-coplanar configuration. The dihedral angle between naphthalene ring system and benzene ring is 70.62 (6)°. The nitro group is oriented in parallel with the adjacent carbonyl plane. The torsion angle of the carbonyl group and naphthalene ring is 54.68 (19)° (C—C—C—O), and that of nitro group and naphthalene ring is 54.26 (18)° (O—N—C—C). In the crystal, π–π interactions between naphthalene systems [centroid–centroid distances = 3.5633 (9), 3,5634 (9), and 3.9758(9) Å], C—H⋯O hydrogen bonds, intermolecular N—O⋯Cl interactions [2.9937 (12) Å] and C—H⋯π contacts are observed.

Related literature

For electrophilic aromatic substitution of naphthalene derivatives giving aryl naphthyl ketone compounds, see: Okamoto & Yonezawa (2009 ▶). For related structures, see: Kato et al. (2010 ▶); Mitsui et al. (2008 ▶, 2010 ▶); Nishijima et al. (2010 ▶); Watanabe et al. (2010 ▶).

Experimental

Crystal data

C₁₉H₁₄ClNO₅
M _r = 371.76
Monoclinic,
a = 8.57511 (16) Å
b = 14.0424 (3) Å
c = 14.0842 (3) Å
β = 100.206 (1)°
V = 1669.12 (5) Å³
Z = 4
Cu Kα radiation
μ = 2.31 mm⁻¹
T = 193 K
0.60 × 0.40 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.294, T _max = 0.544
29408 measured reflections
3058 independent reflections
2793 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.093
S = 1.03
3058 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 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: ORTEP (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051998/om2387sup1.cif

e-67-0o155-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051998/om2387Isup2.hkl

e-67-0o155-Isup2.hkl^{(147KB, hkl)}

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

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

Cg1 is the centroid of the C1–C4/C9/C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O5ⁱ	0.93	2.44	3.137 (2)	132
C18—H18C⋯O3ⁱ	0.96	2.51	3.449 (2)	167
C19—H19B⋯Cg1ⁱⁱ	0.96	2.81	3.5845 (19)	139

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

Acknowledgments

The authors express their gratitude to Professor Keiichi Noguchi, Instumentation Analysis Center, Tokyo University of Agriculture & Technology, for technical advice. This work was partially supported by a Sasakawa 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, peri-aroylnaphthalene compounds have proven to be formed regioselectively with 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-aminobenzoyl)-2,7-dimethoxynaphthalene (Nishijima et al., 2010). The aromatic rings in these molecules are arranged in a non-coplanar alignment to each other. Furthermore, we have also clarified the crystal structures of 1-monoaroylated naphthalene compounds. They have essentially the same non-coplanar structure with the 1,8-diaroylated naphthalene, e.g., 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui et al., 2008), 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010) and (2,7-dimethoxynaphthalen-1-yl)(phenyl)methanone (Kato, et al., 2010). In the course of this work, we have revealed the crystal structure of 1-monoaroylnaphthalene compounds having a substituent, other than aroyl group, at the 8-position such as (8-bromo-2,7-dimethoxy-1-naphthyl)(4-chlorophenyl)methanone (Mitsui, Nagasawa, Watanabe et al. 2010). The aroyl group and naphthalene ring in these molecules have similar configuration to 1,8-diaroylated naphthalene. As a part of our continuous study on the molecular structures of these kinds of homologous molecules, the crystal structure of title compound, a 1-chlorobenzoylated naphthalene bearing nitro group at the 8-position, is discussed in this report.

An ORTEP (Burnett & Johnson, 1996) plot of the title compound is displayed in Fig. 1. In the molecule, the dihedral angle between the benzene ring (C11—C16) and the naphthalene ring (C1—C10) is 70.62 (6)°. The nitro group are also twisted away from the naphthalene ring system, then the nitro group and the carbonyl group are arranged almost in parallel. The dihedral angle between the ketonic C=O plane (O3/C1/C11/C17) and naphthalene ring (C1—C10) is 60.33 (7)° [C9—C1—C17—O3 torsion angle is 54.68 (19)°] and between the nitro plane (O4/O5/N1/C8) and naphthalene ring (C1—C10) is 57.34 (8)° [O4—N1—C8—O9 torsion angle is 54.26 (18)°]. On the other hand, the carbonyl group and the 4-chlorophenyl one have almost coplanar configuration [C16—C11—C17—O3 torsion angle is 10.5 (2)°], but the torsion angle is larger than those of another homologous compounds, i.e., the torsion angles of 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene and (8-bromo-2,7-dimethoxy-1-naphthyl)(4-chlorophenyl)methanone are -4.4 (2)° and -3.6 (4)°, respectively.

The molecular packing of the title compound is mainly stabilized by weak intermolecular hydrogen bonds and van der Waals interactions. The 4-chlorophenyl groups interact with the nitro groups [C13—H13···O5 is 2.44 Å; (i) x, 3/2 - y, 1/2 + z] of adjacent molecules along the c axis (Fig. 2). Interaction between the methoxy groups and the carbonyl groups [C18—H18C···O3 = 2.51 Å; (i) x, 3/2 - y, 1/2 + z] form naphthalene ring systems into zigzag arrangement (Fig. 2). On the other hand, C—H···π interaction and π–π interactions deposit layer upon layer of naphthalene rings [C1/C2/C3/C4/C9/C10 ring with centroid Cg1 and C5-C10 ring with centroid Cg2 (Fig. 3). Furthermore, O4 and C11 interact with each other [O4···Cl1 = 2.9937 (12) Å; (iii) 2 - x, -y, 1-z] (Fig. 4).

Experimental

To a solution of 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (653.4 mg, 2.0 mmol) in methylene chloride (10 ml), aqueous 61% nitric acid (2.0 ml) was dropped by portions at 273 K. After the reaction mixture was stirred at 273 K for 2 h, it was poured into ice-cold water (25 ml). The aqueous solution was extracted with CHCl₃(15 ml × 3). The combined extracts were washed with water 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 reprecipitation (good solvent:CHCl₃, poor solvent:hexane) and column chromatography (silica gel, CHCl₃) (isolated yield 448.8 mg, 60%). Single crystals suitable for X-ray diffraction analysis were obtained by crystallization from acetone as yellow plates.

Spectral data: ¹H NMR δ (300 MHz, CDCl₃); 3.73 (3H, s), 3.97 (3H, s), 7.22 (1H, d, J = 9.3 Hz), 7.24 (1H, d, J = 8.6 Hz), 7.38 (2H, d, J = 8.9 Hz), 7.82 (2H, d, J = 8.6 Hz), 7.95 (1H, d, J = 9.3 Hz), 7.96 (1H, d, J = 8.9 Hz). ¹³C NMR δ (75 MHz, CDCl₃); 56.48, 57.22, 111.26, 111.86, 118.02, 124.16, 124.59, 128.64, 130.51, 132.59, 133.24, 134.39, 136.79, 139.17, 151.61, 157.76, 193.23. IR (KBr); 1655 (C=O), 1623 (Ar), 1527 (Ar), 1372 (NO₂), 1275 (O—Me) cm^-1. HRMS (m/z); [M + H]⁺ Calcd for C₁₉H₁₅ClNO₅, 272.0639; found, 272.0601. m.p. = 483.1–486.4 K.