Ethyl 4-[(E)-(2-hy­droxy­benzyl­idene)amino]­piperidine-1-carboxyl­ate

Rui-Qin Fang; Zhi-Li Shan; Xing Guo

doi:10.1107/S1600536811049750

. 2011 Nov 25;67(Pt 12):o3448. doi: 10.1107/S1600536811049750

Ethyl 4-[(E)-(2-hydroxybenzylidene)amino]piperidine-1-carboxylate

Rui-Qin Fang ^a,^b,^*, Zhi-Li Shan ^a, Xing Guo ^a

PMCID: PMC3239079 PMID: 22199927

Abstract

In the title compound, C₁₅H₂₀N₂O₃, the piperidine ring adopts a chair conformation, although the amide N atom is almost planar (bond angle sum = 359.7°). The molecule adopts an E conformation about the C=N bond, which allows for the formation of an intramolecular O—H⋯N hydrogen bond. In the crystal, molecules are linked by C—H⋯O interations, resulting in C(6) chains propagating in [010].

Related literature

For a related structure, see: Tas et al. (2007 ▶). For standard bond lengths, see: Allen et al. 1987) ▶.

Experimental

Crystal data

C₁₅H₂₀N₂O₃
M _r = 276.33
Monoclinic,
a = 15.732 (3) Å
b = 9.1890 (18) Å
c = 10.414 (2) Å
β = 97.24 (3)°
V = 1493.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.28 × 0.23 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968) ▶ T _min = 0.976, T _max = 0.981
3098 measured reflections
2922 independent reflections
1750 reflections with I > 2σ(I)
R _int = 0.032
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.174
S = 1.09
2922 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811049750/hb6521sup1.cif

e-67-o3448-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049750/hb6521Isup2.hkl

e-67-o3448-Isup2.hkl^{(143.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049750/hb6521Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811049750/hb6521Isup4.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—H1⋯N1	0.82	1.87	2.592 (3)	146
C15—H15B⋯O2ⁱ	0.96	2.56	3.475 (5)	160

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the Fundamental Research Funds for the Central Universities (ZYGX2009J085) and the China Postdoctoral Science Foundation (20110491380) for support.

supplementary crystallographic information

Comment

The cystal structure of the Schiff base N-(1-ethoxycarbonyl)piperidine-4-yl)-3,5-di-t-butylsalicylaldimine, derived from ethyl 4-aminopiperidine-1-carboxylate and 3,5-di-tert-butylsalicylaldehyde, has been reported before (Tas et al., 2007). There are two tert butyl subsitituents on the 3- and 5- positons, as compared with the title compound. The molecular structure of title compound (I), Fig. 1, possesses an E configuration about C7=N1 double bond, and the bond length 1.268 (3) Å is in the normal range. (Allen et al. 1987). The C13=O2 double bond 1.208 (4) Å. The C2—O1, N2—C13 and C13—O3 single bond lengths are 1.352 (3), 1.343 (4) and 1.347 (4) Å, respectively. All these bond lengths is comparable to that observed in the reference compound. (Tas et al., 2007) The torsion angle of C9—C8—N1—C7 and C12—C8—N1—C7 is -108.8 (3) ° and 131.3 (3) °. The Rms deviation of phenyl ring is 0.0072 Å, and the Rms of six-member piperidine ring of chair conformation is 0.2282 Å. The The dihedral angle between phenyl plane and piperidine ring in title compound is 77.58 (10) °. There is an intramolecular hydrogen bond, O1—H1···N1, together with one kind of intermolecular hydrogen bond C15—H15B···O2 in the crystal structure of title compound. All these hydrogen bonds the molecule to form an extended network along b axis, Fig. 2.

Experimental

The title compound was prepared by stirring a mixture of salicylaldehyde (122 mg, 1 mmol) and ethyl 4-aminopiperidine-1-carboxylate (172 mg, 1 mmol) in methanol (15 ml) for 3 h at room temperature. After keeping the solution in air for 4 d, yellow block-shaped crystals of (I) were formed. The crystals were isolated, washed three times with methanol and dried in a vacuum desiccator containing anhydrous CaCl₂.