(4-Chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone

Ryosuke Mitsui; Kosuke Nakaema; Keiichi Noguchi; Noriyuki Yonezawa

doi:10.1107/S1600536808039603

. 2008 Nov 29;64(Pt 12):o2497. doi: 10.1107/S1600536808039603

(4-Chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone

Ryosuke Mitsui ^a, Kosuke Nakaema ^a, Keiichi Noguchi ^b, Noriyuki Yonezawa ^a,^*

PMCID: PMC2959982 PMID: 21581458

Abstract

The title compound, C₁₈H₁₃ClO₃, has an intramolecular O—H⋯O=C hydrogen bond between the carbonyl group and the hydroxy substituent on the naphthalene ring system. The angle between the C=O bond plane and the naphthalene ring system is relatively small [20.96 (8)°]. The angle between the benzene ring and the carbonyl group is rather large [35.65 (9)°] compared to that in an analogous compound [3.43 (11)°] having a methoxy group instead of a hydroxy substituent.

Related literature

For the structures of closely related compounds, see: Nakaema et al. (2007 ▶, 2008 ▶); Mitsui et al. (2008 ▶).

Experimental

Crystal data

C₁₈H₁₃ClO₃
M _r = 312.73
Orthorhombic,
a = 17.8030 (3) Å
b = 8.68121 (10) Å
c = 18.8683 (3) Å
V = 2916.14 (8) Å³
Z = 8
Cu Kα radiation
μ = 2.41 mm⁻¹
T = 123 K
0.60 × 0.15 × 0.05 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.485, T _max = 0.886
49864 measured reflections
2669 independent reflections
2347 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.096
S = 1.08
2669 reflections
205 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 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 global, I. DOI: 10.1107/S1600536808039603/su2069sup1.cif

e-64-o2497-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039603/su2069Isup2.hkl

e-64-o2497-Isup2.hkl^{(128.5KB, 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—H2⋯O1	0.94 (2)	1.71 (2)	2.5573 (16)	148 (2)

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Acknowledgments

This work was financially supported by SEIKI KOGYO CO., Ltd, Tokorozawa, Saitama, Japan.

supplementary crystallographic information

Comment

Recently, we have reported on the crystal structure of 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene, (I) [Mitsui et al., 2008]. As a part of our ongoing studies on the synthesis and crystal structure analyses of aroylated naphthalene derivatives, we prepared and analysed the crystal structure of the title compound, (II). Compound (II) was prepared by regioselective demethylation reaction of compound (I) with aluminium trichloride.

The molecular structure of compound (II) is illustrated in Fig. 1. In analogous aroylated naphthalenes, for example compound (I) shown in Fig. 2, the C═O bond plane is almost perpendicular to the mean plane of the naphthalene ring (Nakaema et al., 2007, 2008; Mitsui et al., 2008). In contrast, the angle between the C═O bond and the naphthalene ring in compound (II) is considerably smaller, i.e. 20.96 (8)°. This is apparently caused by the intramolecular O—H···O═C hydrogen bond, which forms a six-membered ring including the carbonyl group and an edge of the naphthalene ring (Fig. 1 and Table 1).

In compound (I) the C═O bond and the benzene ring are almost coplanar with a dihedral angle of 3.43 (11)°. In compound (II) the mean plane of the benzene ring is twisted away from the C═O bond by 35.65 (9)°. This is presumably caused by the release of the rather large steric repulsion between the benzene ring and the naphthalene ring brought about by the small angle of the C═O bond plane and the naphthalene ring. The dihedral angle between the naphthalene ring (C1—C10) and the benzene ring (C12—C17) is 58.10 (6)°.

In the crystal structure the molecular packing of (II) is mainly stabilized by van der Waals interactions. The naphthalene rings interact with the phenyl rings [C5···C13 = 3.363 (2) Å] and the carbonyl groups [H6···O1 = 2.70 Å] along the a-axis. They also interact with the methyl groups [H3···C18 = 2.79 Å] and aroyl groups [H6···Cl1 = 2.88 Å] along the c-axis (Fig. 3). On the other hand, the naphthalene rings also interact with the methyl groups [C6···H18B = 2.81 Å, C7···H18B = 2.70 Å] and the phenyl rings [C6···H17 = 2.88 Å, C7···H17 = 2.79 Å] along the b-axis. The naphthalene rings are almost perpendicular to the phenyl rings of the adjacent molecules along the b-axis. In addition, the hydroxy groups interact with the phenyl rings [O2···H14 = 2.71 Å] along the b-axis (Fig. 4).

Experimental

To a solution of 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (33 mg, 0.10 mmol) in CH₂Cl₂ (1.0 ml) was added AlCl₃ (67 mg, 0.50 mmol). The reaction mixture was refluxed for 30 min giving a dark red solution, which was then poured into H₂O (5 ml) and CHCl₃ (3 ml). The aqueous layer was extracted with CHCl₃ (3 × 5 ml). The combined organic layers were washed with brine (3 × 10 ml), and dried over MgSO₄ overnight. The solvent was removed in vacuo and the crude material was purified by recrystallization from hexane to give compound (II) as yellow platelets (m.p. 391–391.5 K, yield 23 mg, 75%).

Spectroscopic Data: ¹H NMR (300 MHz, CDCl₃) δ 11.35 (s, 1H), 7.85 (d, 1H), 7.63 (d, 1H), 7.58 (d, 2H), 7.40 (d, 2H), 7.07 (d, 1H), 6.91 (dd, 1H), 6.58 (d, 1H), 3.37 (s, 3H); ¹³C NMR (75 MHz, CDCl₃) δ 199.1, 162.6, 158.2, 138.8, 138.7, 136.5, 133.8, 130.7, 130.2, 128.9, 123.7, 116.4, 115.8, 113.4, 106.5, 54.5; IR (KBr): 3434, 1623, 1583, 1513, 1214, 843.

Anal. Calcd for C₁₈H₁₃ClO₃: C 69.13, H 4.19. Found: C 69.11, H 4.09.