1-[(4-Bromo­phen­yl)(morpholin-4-yl)­meth­yl]naphthalen-2-ol

Qun Zhao

doi:10.1107/S160053681200459X

. 2012 Feb 24;68(Pt 3):o812. doi: 10.1107/S160053681200459X

1-[(4-Bromophenyl)(morpholin-4-yl)methyl]naphthalen-2-ol

Qun Zhao ^a,^*

PMCID: PMC3297874 PMID: 22412677

Abstract

The title compound, C₂₁H₂₀BrNO₂, was obtained via a one-pot synthesis from the reaction of 4-bromobenzaldehyde, 2-naphthol and morpholine. In the asymmetric unit, there are four molecules with similar structures. The morpholine ring adopts a chair conformation, and the hydroxy group links with the morpholine via an intramolecular O—H⋯N hydrogen bond. The bromophenyl ring is approximately perpendicular to the mean pane of the naphthalene system at dihedral angles of 76.7 (3), 81.4 (3), 79.7 (3) and 84.5 (3)° in the four independent molecules. Weak C—H⋯O hydrogen bonds are observed in the crystal.

Related literature

For the application of the Betti-type reaction, see: Gardiner & Raston (1997 ▶); Gutsche & Nam (1998 ▶).

Experimental

Crystal data

C₂₁H₂₀BrNO₂
M _r = 398.28
Triclinic,
a = 10.514 (2) Å
b = 10.700 (2) Å
c = 34.002 (7) Å
α = 82.32 (3)°
β = 89.43 (3)°
γ = 88.67 (3)°
V = 3789.8 (13) Å³
Z = 8
Mo Kα radiation
μ = 2.18 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 (2 × 2 bin mode) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.822, T _max = 1.000
26170 measured reflections
13194 independent reflections
5620 reflections with I > 2σ(I)
R _int = 0.094

Refinement

R[F ² > 2σ(F ²)] = 0.083
wR(F ²) = 0.192
S = 1.03
13194 reflections
901 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200459X/xu5461sup1.cif

e-68-0o812-sup1.cif^{(41.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200459X/xu5461Isup2.hkl

e-68-0o812-Isup2.hkl^{(645KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681200459X/xu5461Isup3.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
O1—H1A⋯N1	0.82	1.92	2.600 (7)	139
O3—H3B⋯N2	0.82	1.92	2.601 (7)	140
O5—H5A⋯N3	0.82	1.91	2.612 (7)	142
O7—H7B⋯N4	0.82	1.93	2.620 (7)	142
C25—H25A⋯O4ⁱ	0.93	2.58	3.473 (10)	162
C46—H46A⋯O6ⁱⁱ	0.93	2.57	3.371 (10)	144
C55—H55A⋯O5	0.93	2.59	3.305 (9)	134
C67—H67A⋯O8ⁱⁱⁱ	0.93	2.41	3.208 (9)	143

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

Acknowledgments

The author is grateful to the Starter Fund of Nanjing University of Chinese Medicine.

supplementary crystallographic information

Comment

The reaction of substituted phenols and aldehydes under controlled conditions has been used to build up supramolecular compounds, the most important ones being calixarenes (Gardiner & Raston, 1997; Gutsche & Nam, 1998). 2-Naphthol reacts with aromatic aldehydes to produce 14-aryl-14H-dibenzo[a,j]xanthenes, which could be used as anti-inflamatory agents. Herein we report the synthesis and crystal structure of the title compound (Fig. 1).

In the title compound, bond lengths and angles have normal values. There are four molecules in the asymmetric unit, all having similar conformations. The morpholine rings adopt chair conformation. The dihedral angles between rings A (C1–C10) and B (C12–C17), and between rings C(C22–C31) and D(C33–C38), and between rings E(C43–C52) and F (C54–C59), and between rings G(C64–C73) and H(C75–C80), are 76.7 (3), 81.4 (3), 79.7 (3) and 84.5 (3)°, respectively. The crystal structure is stabilized by intermolecular C–H···O hydrogen bonds, which link the molecules into a three-dimensional network(Fig. 2). The intramolecular O–H···N hydrogen bonds are also present, Table 1.

Experimental

4-Bromobenzaldehyde (2.76 g, 0.015 mol) and morpholine (1.305 g, 0.015 mol) was added to 2-naphthol (2.16 g, 0.015 mol) without solvent under nitrogen. The temperature was raised to 120°C in one hour gradually and the mixture was stirred at this temperature for 12 h. The system was treated with 30 ml of ethanol 95% and cooled. The precipitate was filtered and washed with a small amount of ethanol 95%. The title compound was isolated using column chromatography (Petroleum ether: ethyl acetate-5:1). Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of a solution of the title compound in ethyl acetate at room temperature.