Ethyl 6-amino-5-cyano-2-methyl-4-propyl-4H-pyran-3-carboxyl-ate.

The pyran ring of the title compound, C(13)H(18)N(2)O(3), 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 ▶).

Experimental

Crystal data

C13H18N2O3

M = 250.15

Triclinic,

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 ▶) T min = 0.65, T max = 0.87

5049 measured reflections

2826 independent reflections

1577 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 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

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043748/bt5109sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043748/bt5109Isup2.hkl

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

C13H18N2O3	Z = 2
Mr = 250.15	F(000) = 268
Triclinic, P1	Dx = 1.195 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1172 (9) Å	Cell parameters from 2826 reflections
b = 8.7956 (9) Å	θ = 3.0–26.4°
c = 11.2877 (19) Å	µ = 0.09 mm−1
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

Bruker APEX CCD area-detector diffractometer	2826 independent reflections
Radiation source: fine-focus sealed tube	1577 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
Tmin = 0.65, Tmax = 0.87	k = −10→10
5049 measured reflections	l = −13→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H 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 parameters	Δρmax = 0.13 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	−0.2429 (2)	−0.09571 (19)	0.63342 (17)	0.0444 (4)
C2	−0.1346 (2)	−0.18666 (19)	0.61071 (16)	0.0428 (4)
C3	−0.2165 (2)	−0.3640 (2)	0.55184 (18)	0.0507 (5)
C4	0.0703 (2)	−0.10825 (19)	0.65363 (16)	0.0416 (4)
H4	0.1012	−0.1530	0.5765	0.050*
C5	0.1778 (2)	−0.1557 (2)	0.76684 (17)	0.0513 (5)
H5A	0.1418	−0.2774	0.7362	0.062*
H5B	0.3075	−0.1117	0.7850	0.062*
C6	0.1500 (3)	−0.0922 (3)	0.8948 (2)	0.0716 (6)
H6A	0.0195	−0.1271	0.8756	0.086*
H6B	0.1976	0.0298	0.9305	0.086*
C7	0.2423 (4)	−0.1545 (3)	1.0004 (2)	0.1038 (9)
H7A	0.2186	−0.1102	1.0791	0.156*
H7B	0.3723	−0.1175	1.0223	0.156*
H7C	0.1945	−0.2753	0.9666	0.156*
C8	0.0021 (2)	0.1608 (2)	0.70345 (17)	0.0446 (4)
C9	0.1207 (2)	0.08115 (19)	0.69043 (16)	0.0404 (4)
C10	0.0223 (3)	0.3431 (2)	0.7354 (2)	0.0670 (6)
H10A	−0.0868	0.3524	0.6792	0.101*
H10B	0.1258	0.3989	0.7199	0.101*
H10C	0.0409	0.3947	0.8274	0.101*
C11	0.3091 (2)	0.1666 (2)	0.70545 (18)	0.0466 (4)
C12	0.5617 (3)	0.4184 (3)	0.7863 (2)	0.0737 (6)
H12A	0.5646	0.4016	0.6984	0.088*
H12B	0.6491	0.3749	0.8326	0.088*
C13	0.6091 (4)	0.5982 (3)	0.8618 (3)	0.1117 (9)
H13A	0.7300	0.6584	0.8713	0.168*
H13B	0.6061	0.6135	0.9486	0.168*
H13C	0.5222	0.6403	0.8149	0.168*
N2	−0.4192 (2)	−0.1503 (2)	0.61418 (18)	0.0606 (5)
N1	−0.2822 (2)	−0.5075 (2)	0.50412 (19)	0.0763 (6)
O3	−0.17565 (15)	0.07590 (13)	0.68500 (12)	0.0530 (3)
O1	0.39733 (18)	0.09129 (16)	0.65942 (14)	0.0694 (4)
O2	0.37809 (16)	0.33123 (15)	0.77399 (14)	0.0612 (4)
H2A	−0.472 (2)	−0.083 (2)	0.6160 (17)	0.055 (5)*
H2B	−0.485 (3)	−0.253 (3)	0.585 (2)	0.062 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0435 (10)	0.0357 (9)	0.0503 (11)	0.0118 (8)	0.0178 (8)	0.0123 (8)
C2	0.0427 (10)	0.0356 (9)	0.0466 (10)	0.0149 (8)	0.0133 (8)	0.0131 (8)
C3	0.0410 (10)	0.0451 (11)	0.0606 (12)	0.0174 (9)	0.0140 (9)	0.0157 (9)
C4	0.0439 (10)	0.0366 (9)	0.0449 (10)	0.0182 (8)	0.0168 (8)	0.0129 (7)
C5	0.0490 (11)	0.0426 (10)	0.0593 (12)	0.0179 (8)	0.0138 (9)	0.0205 (9)
C6	0.0846 (16)	0.0705 (14)	0.0584 (13)	0.0299 (12)	0.0213 (11)	0.0261 (11)
C7	0.130 (2)	0.109 (2)	0.0662 (15)	0.0379 (18)	0.0184 (15)	0.0482 (16)
C8	0.0421 (10)	0.0380 (9)	0.0533 (11)	0.0135 (8)	0.0195 (8)	0.0152 (8)
C9	0.0412 (10)	0.0380 (9)	0.0441 (10)	0.0155 (8)	0.0161 (8)	0.0173 (8)
C10	0.0593 (13)	0.0393 (10)	0.1052 (17)	0.0212 (9)	0.0362 (12)	0.0222 (11)
C11	0.0453 (10)	0.0486 (11)	0.0552 (11)	0.0215 (9)	0.0197 (9)	0.0281 (9)
C12	0.0484 (12)	0.0710 (14)	0.0989 (17)	0.0079 (11)	0.0285 (12)	0.0374 (13)
C13	0.0887 (19)	0.0724 (17)	0.134 (3)	−0.0179 (14)	0.0439 (18)	0.0169 (17)
N2	0.0453 (10)	0.0414 (10)	0.0917 (13)	0.0153 (9)	0.0289 (9)	0.0167 (9)
N1	0.0583 (11)	0.0403 (10)	0.1089 (15)	0.0124 (9)	0.0212 (10)	0.0126 (10)
O3	0.0443 (7)	0.0348 (6)	0.0765 (9)	0.0148 (6)	0.0265 (6)	0.0115 (6)
O1	0.0578 (9)	0.0646 (9)	0.1057 (12)	0.0336 (7)	0.0447 (8)	0.0355 (8)
O2	0.0470 (7)	0.0474 (8)	0.0829 (10)	0.0073 (6)	0.0285 (7)	0.0184 (7)

C1—N2	1.329 (2)	C8—C9	1.333 (2)
C1—C2	1.350 (2)	C8—O3	1.3862 (19)
C1—O3	1.3638 (19)	C8—C10	1.501 (2)
C2—C3	1.415 (2)	C9—C11	1.476 (2)
C2—C4	1.512 (2)	C10—H10A	0.9600
C3—N1	1.145 (2)	C10—H10B	0.9600
C4—C9	1.522 (2)	C10—H10C	0.9600
C4—C5	1.540 (2)	C11—O1	1.2122 (18)
C4—H4	0.9800	C11—O2	1.326 (2)
C5—C6	1.502 (3)	C12—O2	1.456 (2)
C5—H5A	0.9700	C12—C13	1.467 (3)
C5—H5B	0.9700	C12—H12A	0.9700
C6—C7	1.517 (3)	C12—H12B	0.9700
C6—H6A	0.9700	C13—H13A	0.9600
C6—H6B	0.9700	C13—H13B	0.9600
C7—H7A	0.9600	C13—H13C	0.9600
C7—H7B	0.9600	N2—H2A	0.805 (18)
C7—H7C	0.9600	N2—H2B	0.85 (2)
N2—C1—C2	128.59 (16)	C9—C8—C10	130.81 (16)
N2—C1—O3	110.12 (13)	O3—C8—C10	107.27 (12)
C2—C1—O3	121.28 (15)	C8—C9—C11	123.41 (14)
C1—C2—C3	117.85 (15)	C8—C9—C4	122.47 (15)
C1—C2—C4	122.94 (14)	C11—C9—C4	114.08 (12)
C3—C2—C4	119.09 (12)	C8—C10—H10A	109.5
N1—C3—C2	179.8 (2)	C8—C10—H10B	109.5
C2—C4—C9	109.31 (11)	H10A—C10—H10B	109.5
C2—C4—C5	111.67 (13)	C8—C10—H10C	109.5
C9—C4—C5	112.78 (13)	H10A—C10—H10C	109.5
C2—C4—H4	107.6	H10B—C10—H10C	109.5
C9—C4—H4	107.6	O1—C11—O2	121.58 (16)
C5—C4—H4	107.6	O1—C11—C9	122.36 (16)
C6—C5—C4	114.61 (13)	O2—C11—C9	116.06 (13)
C6—C5—H5A	108.6	O2—C12—C13	107.97 (17)
C4—C5—H5A	108.6	O2—C12—H12A	110.1
C6—C5—H5B	108.6	C13—C12—H12A	110.1
C4—C5—H5B	108.6	O2—C12—H12B	110.1
H5A—C5—H5B	107.6	C13—C12—H12B	110.1
C5—C6—C7	113.67 (18)	H12A—C12—H12B	108.4
C5—C6—H6A	108.8	C12—C13—H13A	109.5
C7—C6—H6A	108.8	C12—C13—H13B	109.5
C5—C6—H6B	108.8	H13A—C13—H13B	109.5
C7—C6—H6B	108.8	C12—C13—H13C	109.5
H6A—C6—H6B	107.7	H13A—C13—H13C	109.5
C6—C7—H7A	109.5	H13B—C13—H13C	109.5
C6—C7—H7B	109.5	C1—N2—H2A	117.1 (13)
H7A—C7—H7B	109.5	C1—N2—H2B	124.7 (13)
C6—C7—H7C	109.5	H2A—N2—H2B	117.0 (18)
H7A—C7—H7C	109.5	C1—O3—C8	120.17 (11)
H7B—C7—H7C	109.5	C11—O2—C12	116.81 (13)
C9—C8—O3	121.91 (14)

D—H···A	D—H	H···A	D···A	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)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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) ; (ii) .