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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1424.
Published online 2010 May 22. doi:  10.1107/S1600536810018155
PMCID: PMC2979369

Diethyl 4-(4-cyano­phen­yl)-2,6-dimethyl-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Abstract

In the title compound, C20H22N2O4, the dihedral angle between the roughly planar dihydro­pyridine ring (r.m.s. deviation = 0.092 Å) and the benzene ring is 87.09 (6)°. One of the eth­oxy side chains is disordered over two orientations in a 0.669 (14):0.331 (14) ratio. In the crystal, mol­ecules are linked by N—H(...)N hydrogen bonds, generating chains.

Related literature

For general background to dihydro­pyridine derivatives, see: Gaudio et al. (1994 [triangle]).

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Object name is e-66-o1424-scheme1.jpg

Experimental

Crystal data

  • C20H22N2O4
  • M r = 354.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1424-efi1.jpg
  • a = 10.4596 (13) Å
  • b = 9.5117 (12) Å
  • c = 19.160 (2) Å
  • β = 91.493 (1)°
  • V = 1905.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.12 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.990, T max = 0.993
  • 10000 measured reflections
  • 3298 independent reflections
  • 2408 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.162
  • S = 1.02
  • 3298 reflections
  • 249 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018155/hb5444sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018155/hb5444Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The synthesis of 1,4-dihydropyridine derivatives has attracted continuous research interest due to various vasodilator, anti-hypertensive, bronchodilator, heptaprotective, anti-tumor, anti-mutagenic, geroprotective and anti-diabetic agents (Gaudio et al., 1994). Here, we describe the recystallization and structural characterization of the title compound.

The molecular structure is shown in Fig 1. The dihedral angle between the two rings is 87.09 (6) °. The mean devation of the dihydropyridine plane is 0.0824 Å. The intermolecular hydrogen bonding of N2—H2···N1 leads to a consolidation of the structure (Fig. 2; Table 1).

Experimental

Diethyl 2,6-dimethyl-4-(4-cyanophenyl)-1,4-dihydropyridine-3,5-dicarboxylate (1 mmol 0.39 g) was dissolved in 20 ml ethanol was evaporated in one open flask at room temperature. One week later, yellow blocks of (I) were obained. Anal. C20H22N2O4: C, 67.72; H, 5.64; N, 7.90 %. Found: C, 67.56; H, 5.46; N, 7.61 %.

Refinement

All hydrogen atoms bound to aromatic carbon atoms were refined in calculated positions using a riding model with a C—H distance of 0.93 Å and Uiso = 1.2Ueq(C). Hydrogen atoms attached to aromatic N atoms were refined with a N—H distance of 0.86 Å and Uiso = 1.2Ueq(N).

Figures

Fig. 1.
The molecular structure of (I) showing displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
The crystal packing of (I), displayed with N—H···N hydrogen bonds as dashed lines.

Crystal data

C20H22N2O4F(000) = 752
Mr = 354.40Dx = 1.235 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3532 reflections
a = 10.4596 (13) Åθ = 2.4–25.9°
b = 9.5117 (12) ŵ = 0.09 mm1
c = 19.160 (2) ÅT = 296 K
β = 91.493 (1)°Block, colorless
V = 1905.6 (4) Å30.12 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer3298 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
graphiteRint = 0.020
phi and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −12→10
Tmin = 0.990, Tmax = 0.993k = −9→11
10000 measured reflectionsl = −22→22

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.162w = 1/[σ2(Fo2) + (0.0857P)2 + 0.6251P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3298 reflectionsΔρmax = 0.31 e Å3
249 parametersΔρmin = −0.28 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.012 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
C10.5366 (2)0.1062 (3)0.32734 (12)0.0574 (6)
C20.4507 (2)0.0690 (2)0.27004 (10)0.0483 (5)
C30.3890 (2)−0.0596 (3)0.26959 (12)0.0607 (6)
H30.4024−0.12220.30630.073*
C40.3078 (2)−0.0948 (2)0.21466 (12)0.0573 (6)
H40.2670−0.18170.21450.069*
C50.28599 (19)−0.0030 (2)0.15987 (10)0.0419 (5)
C60.3497 (2)0.1239 (2)0.16056 (12)0.0535 (6)
H60.33780.18540.12330.064*
C70.4306 (2)0.1614 (2)0.21529 (12)0.0552 (6)
H70.47130.24830.21540.066*
C80.19219 (19)−0.0393 (2)0.09975 (11)0.0444 (5)
H80.1533−0.13050.10980.053*
C90.2616 (2)−0.0512 (2)0.03111 (12)0.0507 (6)
C100.2559 (2)0.0529 (3)−0.01647 (11)0.0528 (6)
C110.08375 (19)0.1693 (2)0.04492 (10)0.0445 (5)
C120.08624 (18)0.0706 (2)0.09551 (10)0.0425 (5)
C13−0.0033 (2)0.0607 (2)0.15302 (12)0.0490 (5)
C14−0.1644 (3)0.1750 (3)0.21848 (15)0.0738 (8)
H14A−0.11520.17500.26210.089*
H14B−0.21900.09250.21750.089*
C15−0.2415 (3)0.3012 (3)0.2130 (2)0.0980 (11)
H15A−0.18710.38230.21680.147*
H15B−0.30190.30250.24980.147*
H15C−0.28640.30240.16870.147*
C16−0.0089 (2)0.2888 (3)0.03443 (13)0.0586 (6)
H16A−0.08830.26590.05570.088*
H16B−0.02350.3045−0.01460.088*
H16C0.02610.37240.05550.088*
C170.3287 (3)0.0650 (4)−0.08253 (13)0.0756 (8)
H17A0.40010.1272−0.07520.113*
H17B0.27350.1017−0.11900.113*
H17C0.3592−0.0261−0.09580.113*
C180.3377 (2)−0.1776 (3)0.01887 (15)0.0676 (7)
C190.3950 (6)−0.3990 (5)0.0605 (3)0.158 (2)
H19A0.3515−0.45560.02510.190*0.669 (14)
H19B0.4793−0.37650.04370.190*0.669 (14)
H19C0.4473−0.39090.01960.190*0.331 (14)
H19D0.4514−0.41470.10070.190*0.331 (14)
C20A0.4079 (13)−0.4759 (9)0.1207 (5)0.185 (6)0.669 (14)
H20A0.4549−0.56030.11160.278*0.669 (14)
H20B0.3248−0.49990.13710.278*0.669 (14)
H20C0.4530−0.42130.15560.278*0.669 (14)
C20B0.3114 (12)−0.5133 (12)0.0522 (12)0.141 (9)0.331 (14)
H20D0.3600−0.59800.04670.212*0.331 (14)
H20E0.2573−0.49880.01160.212*0.331 (14)
H20F0.2598−0.52130.09270.212*0.331 (14)
N10.6066 (2)0.1329 (3)0.37179 (12)0.0765 (7)
N20.17490 (18)0.1647 (2)−0.00618 (9)0.0534 (5)
H20.18130.2363−0.03330.064*
O10.4059 (2)−0.2026 (3)−0.02939 (13)0.1062 (8)
O20.3246 (2)−0.2705 (2)0.06982 (13)0.0967 (7)
O3−0.07949 (16)0.17231 (17)0.16008 (9)0.0641 (5)
O4−0.00600 (19)−0.0369 (2)0.19268 (11)0.0824 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0631 (14)0.0625 (15)0.0467 (13)0.0055 (12)−0.0004 (11)−0.0063 (11)
C20.0482 (12)0.0555 (13)0.0413 (11)0.0057 (10)−0.0013 (9)−0.0061 (9)
C30.0722 (15)0.0591 (15)0.0503 (13)−0.0007 (12)−0.0094 (12)0.0147 (11)
C40.0642 (14)0.0456 (13)0.0617 (14)−0.0084 (11)−0.0080 (11)0.0095 (10)
C50.0410 (10)0.0396 (11)0.0452 (11)0.0051 (9)0.0025 (8)−0.0017 (8)
C60.0648 (14)0.0462 (13)0.0489 (12)−0.0052 (11)−0.0103 (11)0.0075 (10)
C70.0603 (13)0.0466 (12)0.0582 (13)−0.0064 (11)−0.0068 (11)−0.0006 (10)
C80.0446 (11)0.0371 (11)0.0513 (12)−0.0006 (9)−0.0025 (9)−0.0032 (9)
C90.0453 (12)0.0539 (13)0.0525 (12)0.0024 (10)−0.0052 (10)−0.0144 (10)
C100.0461 (12)0.0658 (15)0.0464 (12)−0.0015 (11)−0.0022 (9)−0.0127 (11)
C110.0433 (11)0.0461 (12)0.0436 (11)0.0011 (9)−0.0056 (9)−0.0029 (9)
C120.0398 (11)0.0418 (11)0.0456 (11)−0.0011 (9)−0.0029 (9)−0.0042 (9)
C130.0465 (12)0.0448 (12)0.0557 (12)−0.0004 (10)0.0026 (10)0.0015 (10)
C140.0735 (17)0.0753 (18)0.0740 (17)0.0031 (14)0.0293 (14)−0.0027 (14)
C150.088 (2)0.074 (2)0.135 (3)0.0022 (16)0.058 (2)−0.0069 (19)
C160.0624 (14)0.0569 (14)0.0562 (13)0.0106 (11)−0.0044 (11)0.0070 (11)
C170.0687 (16)0.106 (2)0.0526 (14)0.0028 (15)0.0107 (12)−0.0091 (14)
C180.0628 (15)0.0681 (17)0.0715 (17)0.0159 (13)−0.0080 (13)−0.0218 (14)
C190.203 (5)0.090 (3)0.183 (5)0.084 (4)0.027 (4)−0.008 (3)
C20A0.279 (14)0.093 (5)0.186 (9)0.083 (7)0.039 (9)0.046 (6)
C20B0.128 (12)0.070 (9)0.23 (2)0.017 (7)0.035 (12)0.030 (10)
N10.0915 (16)0.0847 (16)0.0522 (12)−0.0014 (13)−0.0187 (12)−0.0122 (11)
N20.0585 (11)0.0569 (11)0.0450 (10)0.0036 (9)0.0028 (8)0.0062 (8)
O10.1042 (16)0.1076 (18)0.1084 (17)0.0390 (14)0.0303 (14)−0.0284 (14)
O20.1248 (18)0.0670 (13)0.0989 (16)0.0474 (13)0.0125 (13)−0.0023 (12)
O30.0684 (10)0.0557 (10)0.0694 (11)0.0101 (8)0.0264 (9)0.0053 (8)
O40.0811 (13)0.0715 (12)0.0963 (14)0.0160 (10)0.0341 (11)0.0318 (11)

Geometric parameters (Å, °)

C1—N11.137 (3)C14—H14A0.9700
C1—C21.444 (3)C14—H14B0.9700
C2—C71.380 (3)C15—H15A0.9600
C2—C31.383 (3)C15—H15B0.9600
C3—C41.377 (3)C15—H15C0.9600
C3—H30.9300C16—H16A0.9600
C4—C51.380 (3)C16—H16B0.9600
C4—H40.9300C16—H16C0.9600
C5—C61.378 (3)C17—H17A0.9600
C5—C81.533 (3)C17—H17B0.9600
C6—C71.377 (3)C17—H17C0.9600
C6—H60.9300C18—O11.206 (3)
C7—H70.9300C18—O21.326 (4)
C8—C91.523 (3)C19—C20A1.370 (8)
C8—C121.524 (3)C19—C20B1.401 (9)
C8—H80.9800C19—O21.440 (4)
C9—C101.346 (3)C19—H19A0.9700
C9—C181.464 (3)C19—H19B0.9700
C10—N21.377 (3)C19—H19C0.9700
C10—C171.499 (3)C19—H19D0.9700
C11—C121.349 (3)C20A—H20A0.9600
C11—N21.385 (3)C20A—H20B0.9600
C11—C161.504 (3)C20A—H20C0.9600
C12—C131.467 (3)C20B—H20D0.9600
C13—O41.201 (3)C20B—H20E0.9600
C13—O31.336 (3)C20B—H20F0.9600
C14—O31.447 (3)N2—H20.8600
C14—C151.448 (4)
N1—C1—C2178.1 (3)H15B—C15—H15C109.5
C7—C2—C3119.8 (2)C11—C16—H16A109.5
C7—C2—C1120.1 (2)C11—C16—H16B109.5
C3—C2—C1120.1 (2)H16A—C16—H16B109.5
C4—C3—C2119.9 (2)C11—C16—H16C109.5
C4—C3—H3120.0H16A—C16—H16C109.5
C2—C3—H3120.0H16B—C16—H16C109.5
C3—C4—C5120.9 (2)C10—C17—H17A109.5
C3—C4—H4119.5C10—C17—H17B109.5
C5—C4—H4119.5H17A—C17—H17B109.5
C6—C5—C4118.5 (2)C10—C17—H17C109.5
C6—C5—C8120.27 (18)H17A—C17—H17C109.5
C4—C5—C8121.25 (19)H17B—C17—H17C109.5
C7—C6—C5121.4 (2)O1—C18—O2120.5 (3)
C7—C6—H6119.3O1—C18—C9128.2 (3)
C5—C6—H6119.3O2—C18—C9111.2 (2)
C6—C7—C2119.5 (2)C20A—C19—C20B74.2 (9)
C6—C7—H7120.3C20A—C19—O2112.8 (5)
C2—C7—H7120.3C20B—C19—O2110.7 (7)
C9—C8—C12111.57 (17)C20A—C19—H19A109.0
C9—C8—C5110.82 (16)O2—C19—H19A109.0
C12—C8—C5109.63 (16)C20A—C19—H19B109.0
C9—C8—H8108.2C20B—C19—H19B134.7
C12—C8—H8108.2O2—C19—H19B109.0
C5—C8—H8108.2H19A—C19—H19B107.8
C10—C9—C18120.7 (2)C20A—C19—H19C132.7
C10—C9—C8121.06 (19)C20B—C19—H19C109.5
C18—C9—C8118.2 (2)O2—C19—H19C109.5
C9—C10—N2119.2 (2)H19A—C19—H19C75.2
C9—C10—C17127.9 (2)C20B—C19—H19D109.5
N2—C10—C17112.9 (2)O2—C19—H19D109.5
C12—C11—N2119.03 (18)H19A—C19—H19D137.2
C12—C11—C16128.49 (19)H19B—C19—H19D76.0
N2—C11—C16112.47 (18)H19C—C19—H19D108.1
C11—C12—C13125.70 (19)C19—C20A—H20A109.5
C11—C12—C8121.06 (18)C19—C20A—H20B109.5
C13—C12—C8113.16 (18)H20A—C20A—H20B109.5
O4—C13—O3121.7 (2)C19—C20A—H20C109.5
O4—C13—C12123.4 (2)H20A—C20A—H20C109.5
O3—C13—C12114.78 (19)H20B—C20A—H20C109.5
O3—C14—C15108.1 (2)C19—C20B—H20D109.5
O3—C14—H14A110.1C19—C20B—H20E109.5
C15—C14—H14A110.1H20D—C20B—H20E109.5
O3—C14—H14B110.1C19—C20B—H20F109.5
C15—C14—H14B110.1H20D—C20B—H20F109.5
H14A—C14—H14B108.4H20E—C20B—H20F109.5
C14—C15—H15A109.5C10—N2—C11124.26 (19)
C14—C15—H15B109.5C10—N2—H2117.9
H15A—C15—H15B109.5C11—N2—H2117.9
C14—C15—H15C109.5C18—O2—C19114.2 (3)
H15A—C15—H15C109.5C13—O3—C14118.16 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.862.323.098 (3)150

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5444).

References

  • Bruker (2001). SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gaudio, A. C., Korolkovas, A. & Takahata, Y. (1994). J. Pharm. Sci.A, 83, 1110–1115. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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