3-Ethyl 5-methyl 2-hydr­oxy-6-methyl-4-(4-nitro­phen­yl)-2-trifluoro­methyl-1,2,3,4-tetra­hydro­pyridine-3,5-dicarboxyl­ate

Chen-Xia Yu; Pei-Li Qian; Jia-Jing Ping; Chang-Sheng Yao

doi:10.1107/S1600536808024835

. 2008 Aug 9;64(Pt 9):o1737. doi: 10.1107/S1600536808024835

3-Ethyl 5-methyl 2-hydroxy-6-methyl-4-(4-nitrophenyl)-2-trifluoromethyl-1,2,3,4-tetrahydropyridine-3,5-dicarboxylate

Chen-Xia Yu ^a,^b, Pei-Li Qian ^c, Jia-Jing Ping ^c, Chang-Sheng Yao ^a,^b,^*

PMCID: PMC2960706 PMID: 21201720

Abstract

In the title compound, C₁₈H₁₉F₃N₂O₇, the tetrahydropyridine ring adopts a half-chair conformation. The nitro group is disordered over two sites with occupancies of 0.780 (15) and 0.220 (15). An intramolecular N—H⋯F hydrogen bond is observed in the molecular structure. The molecules are linked into a two-dimensional network parallel to (100) by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Achiwa & Kato (1999 ▶); Dubur et al. (1989 ▶); Hermann et al. (2003 ▶); Ulrich (2004 ▶).

Experimental

Crystal data

C₁₈H₁₉F₃N₂O₇
M _r = 432.35
Monoclinic,
a = 28.678 (6) Å
b = 9.6678 (19) Å
c = 14.120 (3) Å
β = 95.72 (3)°
V = 3895.1 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 (2) K
0.16 × 0.16 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ▶) T _min = 0.979, T _max = 0.995
11673 measured reflections
3438 independent reflections
2572 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.150
S = 1.06
3438 reflections
284 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808024835/ci2642sup1.cif

e-64-o1737-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808024835/ci2642Isup2.hkl

e-64-o1737-Isup2.hkl^{(168.7KB, 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
O7—H7⋯O5ⁱ	0.82	1.98	2.783 (3)	166
N2—H2⋯O3ⁱⁱ	0.86	2.20	3.030 (3)	163
N2—H2⋯F2	0.86	2.42	2.735 (2)	102
C5—H5⋯O2ⁱⁱⁱ	0.93	2.51	3.432 (4)	171

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

Acknowledgments

The authors thank the Natural Science Foundation of Xuzhou Normal University (grant No. 06XLB07) and the Natural Science Foundation of Xuzhou City (grant No. XJ07065) for financial support.

supplementary crystallographic information

Comment

1,4-Dihydropyridines are well known compounds as a consequence of their pharmacological profile as the most important calcium channel modulators (Achiwa & Kato, 1999). 4-Aryl-2,6-dimethyl-1,4-dihydropyridine -3,5-dicarboxylate derivatives are widely used for the treatment of cardiovascular diseases such as hypertension, angina pectoris and infarction (Dubur et al., 1989). In addition, compounds that contain fluorine have special bioactivity, for example, flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich,2004). This led us to pay much attention to the synthesis and bioactivity of these fluoro-compounds. During the synthesis of trifluoromethylated 1,4-dihydropyridine derivatives, an intermediate, the title compound, was isolated. We report here the crystal structure of the title compound.

In the title molecule (Fig.1), the pyridine ring adopts a half-chair conformation, with atoms C10 and C11 deviating from the N2/C7/C8/C9 plane by 0.261 (4) Å and -0.544 (4)Å, respectively. The dihedral angle between the N2/C7/C8/C9 and C1-C6 planes is 72.30 (9)°. The N atom of the nitro group adopts a planar configuration in the major disorder component, while pyramidal configuration in the minor disorder component. An intramolecular N2—H2···F2 hydrogen bond is observed in the molecular structure.

The crystal packing is stabilized by O—H···O, N—H···O and C—H···O intermolecular hydrogen bonds (Table 1) which link the molecules into a two-dimensional network parallel to the (1 0 0) (Fig. 2).

Experimental

The title compound was synthesized by the reaction of 4-nitrobenzaldehyde (1 mmol), methyl 3-amino-but-2-enoate (1 mmol) and ethyl 4,4,4-trifluoro-3-oxobutanoate (1 mmol) catalyzed by triethylbenzylaminium chloride (0.02 g) in water (10 ml) at 363 K. After cooling, the reaction mixture was washed with water and recrystallized from ethanol, to obtain single crystals suitable for X-ray diffraction.