4-[(2-Hydr­oxy-1-naphth­yl)(piperidin-1-yl)meth­yl]benzonitrile

Yuan Zhang; Yong Hua Li

doi:10.1107/S1600536809033728

. 2009 Aug 29;65(Pt 9):o2257. doi: 10.1107/S1600536809033728

4-[(2-Hydroxy-1-naphthyl)(piperidin-1-yl)methyl]benzonitrile

Yuan Zhang ^a, Yong Hua Li ^a,^*

PMCID: PMC2970085 PMID: 21577653

Abstract

In the title compound, C₂₃H₂₂N₂O, obtained from the condensation reaction of 4-formylbenzonitrile, 2-naphthol and piperidine, the dihedral angle between the naphthalene ring system and the benzene ring is 75.31 (4)°. The piperidine ring adopts a chair conformation. The crystal structure is stabilized by intermolecular C—H⋯N hydrogen bonds, which link the molecules into centrosymmetric dimers. An intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For applications of Betti-type reactions, see: Zhao & Li et al. (2004 ▶); Lu et al. (2002 ▶); Xu et al. (2004 ▶); Wang et al. (2005 ▶)

Experimental

Crystal data

C₂₃H₂₂N₂O
M _r = 342.43
Monoclinic,
a = 6.9989 (6) Å
b = 15.588 (1) Å
c = 17.211 (1) Å
β = 101.207 (2)°
V = 1841.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.2 × 0.1 × 0.1 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005 ▶) T _min = 0.98, T _max = 0.98
10945 measured reflections
3245 independent reflections
2661 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.108
S = 1.05
3245 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.13 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/PC (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033728/lx2110sup1.cif

e-65-o2257-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033728/lx2110Isup2.hkl

e-65-o2257-Isup2.hkl^{(159.2KB, 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
O1—H1⋯N2	0.99	1.70	2.614	151
C14—H14⋯N1ⁱ	0.93	2.55	3.395 (2)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by a start-up grant (4007041028) and a science technology grant (KJ2009375) from Southeast University to Professor Yong-Hua Li.

supplementary crystallographic information

Comment

Over one hundred years ago, Betti developed a straightforward synthesis involving the condensation of 2-naphthol, ammonia and equivalents of benzaldehyde, followed by the addition of HCl and KOH to yield 1-(a-aminobenzyl)-2-naphthol. This product which possesses an asymmetric carbon center is known as a Betti base (Zhao & Li et al. 2004). Betti-type reaction is an important method to synthesize chiral ligands and by this method many unnatural homochiral amino-phenol compounds have been obtained (Lu et al. 2002; Xu et al. 2004; Wang et al. 2005). Here we report the synthesis and crystal structure of the title compound, 4-[(2-hydroxy-1-naphthyl)(1-piperidinyl)methyl]benzonitrile (Fig. 1).

The naphthalene (A; C1-C10), benzene (B; C12-C17) and piperidine (C; N2/C19-C23) rings are planar and the dihedral angles between A/B, A/C, and B/C are 75.31 (4)°, 67.24 (5)°, and 88.80 (5)°, respectively. The crystal structure (Fig. 2) is stabilized by intermolecular C–H···N hydrogen bonds between an H atom of benzene ring and the N atom of the nitrile group, with a C14–H14···N1i (Table 1 and Fig. 2), which link the molecules into centrosymmetric dimers. In addition, the crystal structure exhibits an intramolecular O–H···N hydrogen bond, with a O1–H1···N2 (Table 1 and Fig. 2).

Experimental

4-Formylbenzonitrile (1.97 g, 0.015 mol) and piperidine (1.275 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 10 h. The system was treated with 20 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-4:1). 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.