Diethyl 2,6-dimethyl-4-phenyl-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Ming-Sheng Bai; Yan-Yun Chen; Dong-Ling Niu; Li Peng

doi:10.1107/S1600536809009118

. 2009 Mar 19;65(Pt 4):o799. doi: 10.1107/S1600536809009118

Diethyl 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate

Ming-Sheng Bai ^a,^*, Yan-Yun Chen ^a, Dong-Ling Niu ^a, Li Peng ^a

PMCID: PMC2969073 PMID: 21582523

Abstract

The title molecule, C₁₉H₂₃NO₄, was synthesized by the reaction of benzaldehyde, ethyl acetoacetate and NH₄HCO₃. The dihydropyridine ring adopts a flattened boat conformation and the plane of the base of the boat forms a dihedral angle of 88.78 (9)° with the phenyl ring. The packing is stabilized by strong intermolecular N—H⋯O and weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background, see: Cutshall et al. (2002 ▶); Henry (2004 ▶). For the crystal structure of the related compound diethyl 2,6-dimethyl-4-styryl-1,4-dihydropyridine-3,5-dicarboxylate, see: Wang et al., (2007 ▶). For hydrogen bond definitions, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C₁₉H₂₃NO₄
M _r = 329.38
Monoclinic,
a = 9.7502 (12) Å
b = 7.3854 (9) Å
c = 24.326 (2) Å
β = 92.567 (1)°
V = 1749.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.50 × 0.46 × 0.32 mm

Data collection

Siemens SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.958, T _max = 0.973
8718 measured reflections
3084 independent reflections
1989 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.131
S = 1.01
3084 reflections
225 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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 datablocks I, global. DOI: 10.1107/S1600536809009118/fb2141sup1.cif

e-65-0o799-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009118/fb2141Isup2.hkl

e-65-0o799-Isup2.hkl^{(151.3KB, 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
N1—H1⋯O4ⁱ	0.81 (3)	2.19 (3)	2.986 (3)	168 (3)
C3—H3⋯O1	0.98	2.35	2.733 (3)	103
C3—H3⋯O4	0.98	2.43	2.816 (3)	103
C7—H7⋯O1	0.93	2.55	3.169 (3)	124
C12—H12C⋯O2	0.96	2.27	2.841 (3)	116
C15—H15A⋯O3	0.96	2.42	2.762 (3)	101
C8—H8⋯O2ⁱⁱ	0.93	2.51	3.387 (3)	157

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

Acknowledgments

The authors acknowledge the support of the Natural Science Foundation of the College of Life Science, Ningxia University (grant No. 081040).

supplementary crystallographic information

Comment

The development of new methods for the synthesis of substituted pyridines is a motive for the current study. Substituted pyridines attract the interest because of their presence in numerous natural products along with a wide spectrum of their physiological activities (Cutshall et al., 2002). Pyridine derivatives and their complexes have been studied for their fungicidal and antibacterial effects, as well as antiviral drugs (Henry, 2004).

In this paper, we present the structure of diethyl 2,6-dimethyl-4-phenyl-1,4-dihydropyridine-3,5-dicarboxylate (Fig. 1).

The bond lengths and angles are normal and comparable to those observed in the reported diethyl 2,6-dimethyl-4-styryl-1,4-dihydropyridine-3,5-dicarboxylate (Wang et al., 2007).

In the crystal structure, the dihydropyridine ring adopts a flattened boat conformation and the plane of the base of the boat (C1/C2/C4/C5) contains 88.78 (9)° with the phenyl ring. There are present strong (Desiraju & Steiner, 1999) intermolecular N—H···O hydrogen bonds (Tab. 1) that link the molecules into chains propagated in the direction [010].

Experimental

Fresh benzaldehyde (6 mmol), ethyl acetoacetate (6 mmol) and NH₄HCO₃ (6 mmol) were mixed in a 50 ml flask. After the mixture had been stirred for 3 h at 293 K, the crude product was obtained. The title crystals were obtained by recrystallization from ethanol, affording the title compound as a yellow block crystalline solid. Elemental analysis: calculated for C₁₉H₂₃NO₄: C 69.28, H 7.04, N 4.25 weight%; found: C 69.29, H 7.85, N 4.29 weight%.