organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxyl­ate

aFood Science and Pharmacy College, Zhejiang Ocean University, Zhoushan 316000, People's Republic of China, bPeople's Hospital of Jilin Province, Changchun 130021, People's Republic of China, and cDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China
*Correspondence e-mail: yunyuliu888@yahoo.com.cn

(Received 22 October 2009; accepted 22 October 2009; online 28 October 2009)

The pyran ring of the title compound, C13H18N2O3, is almost planar (r.m.s. deviation = 0.059 Å). The crystal packing is stabilized by N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carb­ox­yl­ate and its derivatives are widely utilized as organic inter­mediates, see: Liang et al. (2009[Liang, F., Cheng, X., Liu, J. & Liu, Q. (2009). Chem. Commun. pp. 3636-3538.]).

[Scheme 1]

Experimental

Crystal data
  • C13H18N2O3

  • Mr = 250.15

  • Triclinic, [P \overline 1]

  • a = 8.1172 (9) Å

  • b = 8.7956 (9) Å

  • c = 11.2877 (19) Å

  • α = 106.082 (12)°

  • β = 107.274 (12)°

  • γ = 103.315 (9)°

  • V = 695.20 (19) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 293 K

  • 0.25 × 0.23 × 0.20 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1998[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.65, Tmax = 0.87

  • 5049 measured reflections

  • 2826 independent reflections

  • 1577 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.129

  • S = 0.89

  • 2826 reflections

  • 172 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.13 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O1i 0.805 (18) 2.088 (19) 2.881 (2) 168.2 (17)
N2—H2B⋯N1ii 0.85 (2) 2.21 (2) 3.035 (3) 164.4 (17)
Symmetry codes: (i) x-1, y, z; (ii) -x-1, -y-1, -z+1.

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1998[Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates (Liang et al., 2009).

The pyran ring of the title compound, C13H18N2O3, is almost planar (r.m.s. deviation 0.059Å). The crystal packing is stabilized by N-H···O and N-H···N hydrogen bonds.

Related literature top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates, see: Liang et al. (2009).

Experimental top

A mixture of butyraldehyde (1.0 mmol), malononitrile (1.0 mmol) and acetyl acetate (1.0 mmol) was dissolved in 5 mL dimethylformamide and catalytic amount of piperidine (0.2 mmol) was added at room temperature under stirring. After 2h, the reaction mixture was poured into water and extracted with CH2Cl2. The combined organic phase was washed with water, dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by silica column chromatography. Yield: 87%. Pure product was dissolved in a mixture of petroleum ether. The single-crystals were obtained by slow evaporation of the solvents.

Refinement top

All H atoms on C atoms were positioned geometrically (C—H = 0.93-0.98Å) and refined as riding, with Uiso(H)=1.2Ueq(C) or Uiso(H)=1.5Ueq(Cmethyl). The H atoms bonded to N were freely refined.

Structure description top

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates (Liang et al., 2009).

The pyran ring of the title compound, C13H18N2O3, is almost planar (r.m.s. deviation 0.059Å). The crystal packing is stabilized by N-H···O and N-H···N hydrogen bonds.

Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate and its derivatives are widely utilized as organic intermediates, see: Liang et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxylate top
Crystal data top
C13H18N2O3Z = 2
Mr = 250.15F(000) = 268
Triclinic, P1Dx = 1.195 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1172 (9) ÅCell parameters from 2826 reflections
b = 8.7956 (9) Åθ = 3.0–26.4°
c = 11.2877 (19) ŵ = 0.09 mm1
α = 106.082 (12)°T = 293 K
β = 107.274 (12)°Block, colorless
γ = 103.315 (9)°0.25 × 0.23 × 0.20 mm
V = 695.20 (19) Å3
Data collection top
Bruker APEX CCD area-detector
diffractometer
2826 independent reflections
Radiation source: fine-focus sealed tube1577 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
φ and ω scansθmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1010
Tmin = 0.65, Tmax = 0.87k = 1010
5049 measured reflectionsl = 1314
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 0.89 w = 1/[σ2(Fo2) + (0.0757P)2]
where P = (Fo2 + 2Fc2)/3
2826 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C13H18N2O3γ = 103.315 (9)°
Mr = 250.15V = 695.20 (19) Å3
Triclinic, P1Z = 2
a = 8.1172 (9) ÅMo Kα radiation
b = 8.7956 (9) ŵ = 0.09 mm1
c = 11.2877 (19) ÅT = 293 K
α = 106.082 (12)°0.25 × 0.23 × 0.20 mm
β = 107.274 (12)°
Data collection top
Bruker APEX CCD area-detector
diffractometer
2826 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1577 reflections with I > 2σ(I)
Tmin = 0.65, Tmax = 0.87Rint = 0.023
5049 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 0.89Δρmax = 0.13 e Å3
2826 reflectionsΔρmin = 0.22 e Å3
172 parameters
Special details top

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 > 2sigma(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) top
xyzUiso*/Ueq
C10.2429 (2)0.09571 (19)0.63342 (17)0.0444 (4)
C20.1346 (2)0.18666 (19)0.61071 (16)0.0428 (4)
C30.2165 (2)0.3640 (2)0.55184 (18)0.0507 (5)
C40.0703 (2)0.10825 (19)0.65363 (16)0.0416 (4)
H40.10120.15300.57650.050*
C50.1778 (2)0.1557 (2)0.76684 (17)0.0513 (5)
H5A0.14180.27740.73620.062*
H5B0.30750.11170.78500.062*
C60.1500 (3)0.0922 (3)0.8948 (2)0.0716 (6)
H6A0.01950.12710.87560.086*
H6B0.19760.02980.93050.086*
C70.2423 (4)0.1545 (3)1.0004 (2)0.1038 (9)
H7A0.21860.11021.07910.156*
H7B0.37230.11751.02230.156*
H7C0.19450.27530.96660.156*
C80.0021 (2)0.1608 (2)0.70345 (17)0.0446 (4)
C90.1207 (2)0.08115 (19)0.69043 (16)0.0404 (4)
C100.0223 (3)0.3431 (2)0.7354 (2)0.0670 (6)
H10A0.08680.35240.67920.101*
H10B0.12580.39890.71990.101*
H10C0.04090.39470.82740.101*
C110.3091 (2)0.1666 (2)0.70545 (18)0.0466 (4)
C120.5617 (3)0.4184 (3)0.7863 (2)0.0737 (6)
H12A0.56460.40160.69840.088*
H12B0.64910.37490.83260.088*
C130.6091 (4)0.5982 (3)0.8618 (3)0.1117 (9)
H13A0.73000.65840.87130.168*
H13B0.60610.61350.94860.168*
H13C0.52220.64030.81490.168*
N20.4192 (2)0.1503 (2)0.61418 (18)0.0606 (5)
N10.2822 (2)0.5075 (2)0.50412 (19)0.0763 (6)
O30.17565 (15)0.07590 (13)0.68500 (12)0.0530 (3)
O10.39733 (18)0.09129 (16)0.65942 (14)0.0694 (4)
O20.37809 (16)0.33123 (15)0.77399 (14)0.0612 (4)
H2A0.472 (2)0.083 (2)0.6160 (17)0.055 (5)*
H2B0.485 (3)0.253 (3)0.585 (2)0.062 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0435 (10)0.0357 (9)0.0503 (11)0.0118 (8)0.0178 (8)0.0123 (8)
C20.0427 (10)0.0356 (9)0.0466 (10)0.0149 (8)0.0133 (8)0.0131 (8)
C30.0410 (10)0.0451 (11)0.0606 (12)0.0174 (9)0.0140 (9)0.0157 (9)
C40.0439 (10)0.0366 (9)0.0449 (10)0.0182 (8)0.0168 (8)0.0129 (7)
C50.0490 (11)0.0426 (10)0.0593 (12)0.0179 (8)0.0138 (9)0.0205 (9)
C60.0846 (16)0.0705 (14)0.0584 (13)0.0299 (12)0.0213 (11)0.0261 (11)
C70.130 (2)0.109 (2)0.0662 (15)0.0379 (18)0.0184 (15)0.0482 (16)
C80.0421 (10)0.0380 (9)0.0533 (11)0.0135 (8)0.0195 (8)0.0152 (8)
C90.0412 (10)0.0380 (9)0.0441 (10)0.0155 (8)0.0161 (8)0.0173 (8)
C100.0593 (13)0.0393 (10)0.1052 (17)0.0212 (9)0.0362 (12)0.0222 (11)
C110.0453 (10)0.0486 (11)0.0552 (11)0.0215 (9)0.0197 (9)0.0281 (9)
C120.0484 (12)0.0710 (14)0.0989 (17)0.0079 (11)0.0285 (12)0.0374 (13)
C130.0887 (19)0.0724 (17)0.134 (3)0.0179 (14)0.0439 (18)0.0169 (17)
N20.0453 (10)0.0414 (10)0.0917 (13)0.0153 (9)0.0289 (9)0.0167 (9)
N10.0583 (11)0.0403 (10)0.1089 (15)0.0124 (9)0.0212 (10)0.0126 (10)
O30.0443 (7)0.0348 (6)0.0765 (9)0.0148 (6)0.0265 (6)0.0115 (6)
O10.0578 (9)0.0646 (9)0.1057 (12)0.0336 (7)0.0447 (8)0.0355 (8)
O20.0470 (7)0.0474 (8)0.0829 (10)0.0073 (6)0.0285 (7)0.0184 (7)
Geometric parameters (Å, º) top
C1—N21.329 (2)C8—C91.333 (2)
C1—C21.350 (2)C8—O31.3862 (19)
C1—O31.3638 (19)C8—C101.501 (2)
C2—C31.415 (2)C9—C111.476 (2)
C2—C41.512 (2)C10—H10A0.9600
C3—N11.145 (2)C10—H10B0.9600
C4—C91.522 (2)C10—H10C0.9600
C4—C51.540 (2)C11—O11.2122 (18)
C4—H40.9800C11—O21.326 (2)
C5—C61.502 (3)C12—O21.456 (2)
C5—H5A0.9700C12—C131.467 (3)
C5—H5B0.9700C12—H12A0.9700
C6—C71.517 (3)C12—H12B0.9700
C6—H6A0.9700C13—H13A0.9600
C6—H6B0.9700C13—H13B0.9600
C7—H7A0.9600C13—H13C0.9600
C7—H7B0.9600N2—H2A0.805 (18)
C7—H7C0.9600N2—H2B0.85 (2)
N2—C1—C2128.59 (16)C9—C8—C10130.81 (16)
N2—C1—O3110.12 (13)O3—C8—C10107.27 (12)
C2—C1—O3121.28 (15)C8—C9—C11123.41 (14)
C1—C2—C3117.85 (15)C8—C9—C4122.47 (15)
C1—C2—C4122.94 (14)C11—C9—C4114.08 (12)
C3—C2—C4119.09 (12)C8—C10—H10A109.5
N1—C3—C2179.8 (2)C8—C10—H10B109.5
C2—C4—C9109.31 (11)H10A—C10—H10B109.5
C2—C4—C5111.67 (13)C8—C10—H10C109.5
C9—C4—C5112.78 (13)H10A—C10—H10C109.5
C2—C4—H4107.6H10B—C10—H10C109.5
C9—C4—H4107.6O1—C11—O2121.58 (16)
C5—C4—H4107.6O1—C11—C9122.36 (16)
C6—C5—C4114.61 (13)O2—C11—C9116.06 (13)
C6—C5—H5A108.6O2—C12—C13107.97 (17)
C4—C5—H5A108.6O2—C12—H12A110.1
C6—C5—H5B108.6C13—C12—H12A110.1
C4—C5—H5B108.6O2—C12—H12B110.1
H5A—C5—H5B107.6C13—C12—H12B110.1
C5—C6—C7113.67 (18)H12A—C12—H12B108.4
C5—C6—H6A108.8C12—C13—H13A109.5
C7—C6—H6A108.8C12—C13—H13B109.5
C5—C6—H6B108.8H13A—C13—H13B109.5
C7—C6—H6B108.8C12—C13—H13C109.5
H6A—C6—H6B107.7H13A—C13—H13C109.5
C6—C7—H7A109.5H13B—C13—H13C109.5
C6—C7—H7B109.5C1—N2—H2A117.1 (13)
H7A—C7—H7B109.5C1—N2—H2B124.7 (13)
C6—C7—H7C109.5H2A—N2—H2B117.0 (18)
H7A—C7—H7C109.5C1—O3—C8120.17 (11)
H7B—C7—H7C109.5C11—O2—C12116.81 (13)
C9—C8—O3121.91 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.805 (18)2.088 (19)2.881 (2)168.2 (17)
N2—H2B···N1ii0.85 (2)2.21 (2)3.035 (3)164.4 (17)
Symmetry codes: (i) x1, y, z; (ii) x1, y1, z+1.

Experimental details

Crystal data
Chemical formulaC13H18N2O3
Mr250.15
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)8.1172 (9), 8.7956 (9), 11.2877 (19)
α, β, γ (°)106.082 (12), 107.274 (12), 103.315 (9)
V3)695.20 (19)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.25 × 0.23 × 0.20
Data collection
DiffractometerBruker APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.65, 0.87
No. of measured, independent and
observed [I > 2σ(I)] reflections
5049, 2826, 1577
Rint0.023
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.129, 0.89
No. of reflections2826
No. of parameters172
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.22

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.805 (18)2.088 (19)2.881 (2)168.2 (17)
N2—H2B···N1ii0.85 (2)2.21 (2)3.035 (3)164.4 (17)
Symmetry codes: (i) x1, y, z; (ii) x1, y1, z+1.
 

Acknowledgements

We thank Zhejiang Ocean University, the People's Hospital of Jilin Province and the Science Foundation for Young Teachers of Northeast Normal University (No. 20080305) for support.

References

First citationBruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationLiang, F., Cheng, X., Liu, J. & Liu, Q. (2009). Chem. Commun. pp. 3636–3538.  Web of Science CSD CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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