(4-Chloro­phen­yl)(3,8-dibromo-2-hydr­oxy-7-meth­oxy-1-naphth­yl)methanone

Ryosuke Mitsui; Shoji Watanabe; Atsushi Nagasawa; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S1600536810015527

. 2010 May 8;66(Pt 6):o1304. doi: 10.1107/S1600536810015527

(4-Chlorophenyl)(3,8-dibromo-2-hydroxy-7-methoxy-1-naphthyl)methanone

Ryosuke Mitsui ^a, Shoji Watanabe ^a, Atsushi Nagasawa ^a, Akiko Okamoto ^a, Noriyuki Yonezawa ^a,^*

PMCID: PMC2979364 PMID: 21579400

Abstract

In the title compound, C₁₈H₁₁Br₂ClO₃, an intramolecular O—H⋯O=C hydrogen bond occurs, forming a six-membered ring. The naphthalene ring system and the benzene ring make a dihedral angle of 57.36 (9)°. The central carbonyl C—(C=O)—C group is twisted away from the naphthalene ring system and the benzene ring by 18.61 (15) and 26.25 (16)°, respectively. In the crystal structure, two intermolecular Br⋯Cl close contacts [3.4927 (7) and 3.4325 (7) Å] are observed.

Related literature

For related structures, see: Mitsui et al. (2009 ▶); Mitsui, Nakaema, Nagasawa et al. (2010 ▶); Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008 ▶); Mitsui, Nakaema, Noguchi & Yonezawa (2008 ▶); Mitsui, Nagasawa, Watanabe et al. (2010 ▶). For information on halogen⋯halogen contacts, see: Moorthy et al. (2002 ▶); Pedireddi et al. (1994 ▶); Saruma & Desiraju (1986 ▶).

Experimental

Crystal data

C₁₈H₁₁Br₂ClO₃
M _r = 470.54
Monoclinic,
a = 12.1513 (2) Å
b = 10.06343 (18) Å
c = 13.8936 (3) Å
β = 103.675 (1)°
V = 1650.79 (5) Å³
Z = 4
Cu Kα radiation
μ = 7.85 mm⁻¹
T = 193 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.189, T _max = 0.308
29373 measured reflections
3022 independent reflections
2940 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.076
S = 1.11
3022 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.64 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 datablocks I, global. DOI: 10.1107/S1600536810015527/is2542sup1.cif

e-66-o1304-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015527/is2542Isup2.hkl

e-66-o1304-Isup2.hkl^{(145.3KB, hkl)}

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
O2—H2O⋯O1	0.83	1.85	2.585 (3)	146

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Acknowledgments

The authors would like to express their gratitude to Professor Keiichi Noguchi for technical advice. This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.

supplementary crystallographic information

Comment

Recently, we reported the crystal structures of 1-aroylated 2,7-dimethoxynaphthalenes, 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008), (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008), (4-chlorophenyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2009), 1-bromo-8-(4-chlorobenzoyl)-7-hydroxy-2-methoxynaphthalene (Mitsui, Nakaema, Nagasawa et al., 2010) and (8-bromo-2,7-dimethoxy-1-naphthyl)(4-chlorophenyl)methanone (Mitsui, Nagasawa, Watanabe et al., 2010). As a part of our ongoing studies on the synthesis and crystal structure analysis of aroylated naphthalene derivatives, we prepared and analysed the structure of crystal of 2,5-dibromo-4-(4-chlorobenzoyl)-3-hydroxy-6-methoxynaphthalene, (I). The title compound was prepared by electrophilic aromatic bromination reaction of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone with bromine.

An ORTEPIII (Burnett & Johnson, 1996) plot of (I) is shown in Fig. 1. In the molecule of (I), the intramolecular O—H···O═C hydrogen bond, which forms a six-membered ring including the C═O group and an edge of the naphthalene ring, is present (Table 1). The conformation of these groups resembles to that of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008). Intriguingly, the central C═O group is twisted away from the naphthalene ring and the benzene ring, and the bromo group at 8-position of naphthalene is out of the least-squares plane of the naphthalene ring. The angles of the C═O bond vector against the least-squares plane of the naphthalene ring and the benzene ring are 18.61 (15) and 26.25 (16)°, respectively. The angle of the C9—Br1 bond vector against the least-squares plane of the naphthalene ring is 14.93 (7)°. This is presumably caused by release of the large steric repulsion brought about by the benzene ring and the bromo group on the naphthalene ring of (I).

In the crystal structure, the contact distances Br1···Cl1 and Br2···Cl1 are 3.4927 (7) and 3.4325 (7) Å, respectively (Fig. 2). These contacts are shorter than the sum of their van der Waals radii (3.60 Å), and the five atoms are arranged nearly linear [C9—Br1···Cl1 = 154.14 (6)°, C3—Br2···Cl1 = 165.35 (7)°], suggesting that there is a possibility for halogen interaction (Saruma & Desiraju, 1986; Pedireddi et al., 1994; Moorthy et al., 2002).

Experimental

To a solution of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (313 mg, 1.00 mmol) in chloroform (5 ml) was added Br₂ (483 mg, 3.03 mmol) drop-wise. The reaction mixture was heated at reflux for 2 h, then poured into aqueous 2 M Na₂S₂O₃ (10 ml), and the aqueous layer was extracted with CHCl₃ (3 × 10 ml). The combined organic layers were washed with 2 M Na₂S₂O₃ (3 × 30 ml) and brine (3 × 30 ml), and dried over MgSO₄ overnight. The solvent was removed in vacuo and the crude material was purified by column chromatography (silica gel, CHCl₃) to give the title compound (yield 306 mg, 65%). Single crystals suitable for X-ray diffraction analysis were obtained from CHCl₃ as yellow blocks (m.p. 455.0–455.5 K).

Spectroscopic Data: ¹H NMR (300 MHz, CDCl₃) δ 8.10 (s, 1H), 8.04 (s, 1H), 7.75 (d, 1H), 7.58 (d, 2H), 7.31 (d, 2H), 7.17 (d, 1H), 3.95 (s, 3H); ¹³C NMR (75 MHz, CDCl₃) δ 195.6, 156.3, 152.6, 139.3, 138.3, 134.9, 132.4, 130.3, 129.1, 128.8, 125.8, 118.1, 112.2, 110.5, 105.9, 56.9; IR (KBr): 1670, 1607, 1587, 1495, 1276, 1215, 1096, 782; HRMS (m/z): [M + H]⁺ calcd for C₁₈H₁₂Br₂ClO₃, 468.8842 found, 468.8839. Anal. Calcd for C₁₈H₁₁Br₂ClO₃: C 45.95, H 2.36. Found: C 46.23, H 2.39.