Ethyl 2-(6-amino-5-cyano-3,4-dimethyl-2H,4H-pyrano[2,3-c]pyrazol-4-yl)acetate.

In he title compound, C(13)H(16)N(4)O(3), the pyrazole ring is planar (r.m.s. deviation = 0.054 Å). The pyran ring is not planar; the mean plane makes a dihedral angle of 1.9 (1)° with the pyrazole ring. In the crystal structure, inter-molecular N-H⋯N and N-H⋯O inter-actions lead to a linear chain motif.

Related literature

For biological applications of pyrazole and pyran­opyrazole derivatives, see: Wamhoff et al. (1993 ▶).; Velaparthi et al. (2008 ▶); Magedov et al. (2007 ▶); Rovnyak et al. (1982 ▶). For the synthesis, see: Vasuki & Kumaravel (2008 ▶).

Experimental

Crystal data

C13H16N4O3

M = 276.30

Triclinic,

a = 6.961 (5) Å

b = 7.373 (5) Å

c = 14.535 (5) Å

α = 86.405 (5)°

β = 85.183 (5)°

γ = 65.726 (5)°

V = 677.3 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2004 ▶) T min = 0.976, T max = 0.981

12811 measured reflections

2385 independent reflections

2130 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.117

S = 1.02

2378 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015540/ng2761sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015540/ng2761Isup2.hkl

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

C13H16N4O3	Z = 2
Mr = 276.30	F(000) = 292
Triclinic, P1	Dx = 1.355 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 6.961 (5) Å	Cell parameters from 7682 reflections
b = 7.373 (5) Å	θ = 2.8–32.8°
c = 14.535 (5) Å	µ = 0.10 mm−1
α = 86.405 (5)°	T = 293 K
β = 85.183 (5)°	Block, colourless
γ = 65.726 (5)°	0.25 × 0.20 × 0.20 mm
V = 677.3 (7) Å3

Bruker Kappa APEXII CCD diffractometer	2385 independent reflections
Radiation source: fine-focus sealed tube	2130 reflections with I > 2σ(I)
graphite	Rint = 0.020
Detector resolution: 0 pixels mm-1	θmax = 25.0°, θmin = 2.8°
ω and φ scan	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker 2004)	k = −8→8
Tmin = 0.976, Tmax = 0.981	l = −17→17
12811 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0655P)2 + 0.2561P] where P = (Fo2 + 2Fc2)/3
2378 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.26 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 > 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.Some "bad" relections were omitted in the refinement.

	x	y	z	Uiso*/Ueq
C1	0.4375 (2)	0.8266 (2)	0.84125 (10)	0.0288 (3)
C2	0.3125 (2)	0.7231 (2)	0.86328 (9)	0.0271 (3)
C3	0.2551 (2)	0.6151 (2)	0.79351 (9)	0.0271 (3)
C4	0.3682 (2)	0.6404 (2)	0.70213 (9)	0.0282 (3)
C5	0.4908 (2)	0.7439 (2)	0.68793 (10)	0.0306 (3)
C6	0.0126 (2)	0.7009 (2)	0.78369 (10)	0.0329 (3)
H6A	−0.0164	0.6276	0.7375	0.040*
H6B	−0.0563	0.6818	0.8420	0.040*
C7	−0.0780 (2)	0.9167 (2)	0.75667 (11)	0.0378 (4)
C8	−0.1525 (3)	1.1488 (3)	0.62848 (17)	0.0654 (6)
H8A	−0.2528	1.2402	0.6724	0.078*
H8B	−0.2217	1.1636	0.5715	0.078*
C9	0.0317 (5)	1.1990 (4)	0.6104 (3)	0.1088 (12)
H9A	0.0887	1.2023	0.6679	0.163*
H9B	−0.0109	1.3271	0.5794	0.163*
H9C	0.1375	1.1003	0.5722	0.163*
C10	0.2672 (2)	0.7477 (2)	0.95731 (10)	0.0320 (3)
C11	0.1408 (3)	0.6754 (3)	1.02539 (11)	0.0487 (5)
H11A	0.2177	0.5356	1.0380	0.073*
H11B	0.0091	0.6978	1.0006	0.073*
H11C	0.1140	0.7461	1.0816	0.073*
C12	0.3282 (3)	0.3931 (2)	0.82003 (11)	0.0385 (4)
H12A	0.4780	0.3351	0.8261	0.058*
H12B	0.2951	0.3270	0.7729	0.058*
H12C	0.2574	0.3782	0.8777	0.058*
C13	0.3419 (2)	0.5481 (2)	0.62484 (10)	0.0354 (4)
N1	0.4738 (2)	0.9108 (2)	0.91081 (8)	0.0351 (3)
N2	0.3649 (2)	0.8596 (2)	0.98199 (8)	0.0357 (3)
H2	0.3589	0.8954	1.0377	0.043*
N3	0.5923 (2)	0.7662 (2)	0.60839 (9)	0.0474 (4)
H3A	0.5831	0.7114	0.5594	0.057*
H3B	0.6667	0.8352	0.6064	0.057*
N4	0.3189 (3)	0.4715 (3)	0.56322 (10)	0.0555 (4)
O1	0.52556 (17)	0.84545 (17)	0.75515 (7)	0.0367 (3)
O2	−0.1338 (2)	1.0482 (2)	0.81014 (10)	0.0659 (4)
O3	−0.08990 (18)	0.94621 (17)	0.66504 (8)	0.0450 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0306 (7)	0.0354 (7)	0.0243 (7)	−0.0169 (6)	−0.0013 (5)	−0.0047 (6)
C2	0.0271 (7)	0.0322 (7)	0.0246 (7)	−0.0142 (6)	−0.0018 (5)	−0.0038 (5)
C3	0.0277 (7)	0.0322 (7)	0.0250 (7)	−0.0153 (6)	−0.0012 (5)	−0.0050 (5)
C4	0.0269 (7)	0.0353 (7)	0.0253 (7)	−0.0148 (6)	−0.0007 (5)	−0.0071 (6)
C5	0.0307 (7)	0.0399 (8)	0.0245 (7)	−0.0172 (6)	−0.0006 (6)	−0.0069 (6)
C6	0.0291 (7)	0.0450 (8)	0.0312 (8)	−0.0213 (6)	0.0005 (6)	−0.0068 (6)
C7	0.0250 (7)	0.0454 (9)	0.0434 (9)	−0.0128 (6)	−0.0036 (6)	−0.0124 (7)
C8	0.0592 (12)	0.0478 (11)	0.0810 (15)	−0.0144 (9)	−0.0116 (11)	0.0124 (10)
C9	0.096 (2)	0.0740 (17)	0.171 (3)	−0.0526 (16)	−0.029 (2)	0.0415 (19)
C10	0.0376 (8)	0.0365 (8)	0.0267 (7)	−0.0196 (6)	−0.0016 (6)	−0.0048 (6)
C11	0.0692 (12)	0.0637 (11)	0.0298 (8)	−0.0450 (10)	0.0083 (8)	−0.0090 (8)
C12	0.0481 (9)	0.0344 (8)	0.0364 (8)	−0.0197 (7)	−0.0038 (7)	−0.0028 (6)
C13	0.0362 (8)	0.0488 (9)	0.0289 (8)	−0.0255 (7)	0.0042 (6)	−0.0088 (7)
N1	0.0430 (7)	0.0457 (7)	0.0273 (6)	−0.0284 (6)	−0.0011 (5)	−0.0067 (5)
N2	0.0487 (8)	0.0459 (7)	0.0224 (6)	−0.0286 (6)	−0.0015 (5)	−0.0069 (5)
N3	0.0591 (9)	0.0738 (10)	0.0300 (7)	−0.0484 (8)	0.0114 (6)	−0.0162 (7)
N4	0.0675 (10)	0.0859 (12)	0.0357 (8)	−0.0534 (9)	0.0097 (7)	−0.0243 (8)
O1	0.0446 (6)	0.0537 (7)	0.0266 (6)	−0.0350 (5)	0.0047 (4)	−0.0106 (5)
O2	0.0652 (9)	0.0518 (8)	0.0677 (9)	−0.0048 (7)	−0.0160 (7)	−0.0270 (7)
O3	0.0440 (7)	0.0432 (6)	0.0457 (7)	−0.0163 (5)	−0.0008 (5)	−0.0005 (5)

C1—N1	1.3125 (19)	C8—H8A	0.9700
C1—O1	1.3714 (18)	C8—H8B	0.9700
C1—C2	1.383 (2)	C9—H9A	0.9600
C2—C10	1.383 (2)	C9—H9B	0.9600
C2—C3	1.5006 (19)	C9—H9C	0.9600
C3—C4	1.527 (2)	C10—N2	1.346 (2)
C3—C12	1.535 (2)	C10—C11	1.487 (2)
C3—C6	1.556 (2)	C11—H11A	0.9600
C4—C5	1.356 (2)	C11—H11B	0.9600
C4—C13	1.411 (2)	C11—H11C	0.9600
C5—N3	1.341 (2)	C12—H12A	0.9600
C5—O1	1.3616 (17)	C12—H12B	0.9600
C6—C7	1.490 (2)	C12—H12C	0.9600
C6—H6A	0.9700	C13—N4	1.144 (2)
C6—H6B	0.9700	N1—N2	1.3572 (18)
C7—O2	1.195 (2)	N2—H2	0.8600
C7—O3	1.340 (2)	N3—H3A	0.8600
C8—O3	1.452 (2)	N3—H3B	0.8600
C8—C9	1.474 (4)
N1—C1—O1	118.81 (13)	H8A—C8—H8B	108.0
N1—C1—C2	115.28 (13)	C8—C9—H9A	109.5
O1—C1—C2	125.90 (13)	C8—C9—H9B	109.5
C1—C2—C10	103.21 (13)	H9A—C9—H9B	109.5
C1—C2—C3	123.21 (13)	C8—C9—H9C	109.5
C10—C2—C3	133.58 (13)	H9A—C9—H9C	109.5
C2—C3—C4	105.90 (12)	H9B—C9—H9C	109.5
C2—C3—C12	111.39 (12)	N2—C10—C2	106.01 (13)
C4—C3—C12	109.91 (12)	N2—C10—C11	122.04 (14)
C2—C3—C6	112.12 (11)	C2—C10—C11	131.95 (14)
C4—C3—C6	110.22 (12)	C10—C11—H11A	109.5
C12—C3—C6	107.33 (12)	C10—C11—H11B	109.5
C5—C4—C13	116.78 (13)	H11A—C11—H11B	109.5
C5—C4—C3	126.29 (13)	C10—C11—H11C	109.5
C13—C4—C3	116.93 (13)	H11A—C11—H11C	109.5
N3—C5—C4	126.98 (14)	H11B—C11—H11C	109.5
N3—C5—O1	109.58 (13)	C3—C12—H12A	109.5
C4—C5—O1	123.44 (13)	C3—C12—H12B	109.5
C7—C6—C3	112.62 (12)	H12A—C12—H12B	109.5
C7—C6—H6A	109.1	C3—C12—H12C	109.5
C3—C6—H6A	109.1	H12A—C12—H12C	109.5
C7—C6—H6B	109.1	H12B—C12—H12C	109.5
C3—C6—H6B	109.1	N4—C13—C4	178.79 (17)
H6A—C6—H6B	107.8	C1—N1—N2	101.70 (12)
O2—C7—O3	123.82 (17)	C10—N2—N1	113.80 (12)
O2—C7—C6	124.23 (16)	C10—N2—H2	123.1
O3—C7—C6	111.94 (13)	N1—N2—H2	123.1
O3—C8—C9	111.08 (18)	C5—N3—H3A	120.0
O3—C8—H8A	109.4	C5—N3—H3B	120.0
C9—C8—H8A	109.4	H3A—N3—H3B	120.0
O3—C8—H8B	109.4	C5—O1—C1	115.14 (12)
C9—C8—H8B	109.4	C7—O3—C8	117.56 (15)
N1—C1—C2—C10	0.13 (17)	C12—C3—C6—C7	−179.24 (12)
O1—C1—C2—C10	179.38 (13)	C3—C6—C7—O2	−85.9 (2)
N1—C1—C2—C3	−179.36 (12)	C3—C6—C7—O3	94.18 (15)
O1—C1—C2—C3	−0.1 (2)	C1—C2—C10—N2	0.13 (16)
C1—C2—C3—C4	2.14 (18)	C3—C2—C10—N2	179.54 (14)
C10—C2—C3—C4	−177.17 (15)	C1—C2—C10—C11	−179.84 (17)
C1—C2—C3—C12	121.60 (15)	C3—C2—C10—C11	−0.4 (3)
C10—C2—C3—C12	−57.7 (2)	C5—C4—C13—N4	169 (9)
C1—C2—C3—C6	−118.10 (15)	C3—C4—C13—N4	−11 (9)
C10—C2—C3—C6	62.6 (2)	O1—C1—N1—N2	−179.63 (12)
C2—C3—C4—C5	−1.37 (19)	C2—C1—N1—N2	−0.32 (17)
C12—C3—C4—C5	−121.80 (16)	C2—C10—N2—N1	−0.35 (17)
C6—C3—C4—C5	120.10 (16)	C11—C10—N2—N1	179.63 (15)
C2—C3—C4—C13	178.97 (12)	C1—N1—N2—C10	0.41 (17)
C12—C3—C4—C13	58.54 (17)	N3—C5—O1—C1	−177.10 (12)
C6—C3—C4—C13	−59.56 (17)	C4—C5—O1—C1	3.8 (2)
C13—C4—C5—N3	−0.9 (2)	N1—C1—O1—C5	176.23 (12)
C3—C4—C5—N3	179.41 (14)	C2—C1—O1—C5	−3.0 (2)
C13—C4—C5—O1	178.03 (13)	O2—C7—O3—C8	7.0 (2)
C3—C4—C5—O1	−1.6 (2)	C6—C7—O3—C8	−173.07 (14)
C2—C3—C6—C7	58.13 (16)	C9—C8—O3—C7	87.2 (3)
C4—C3—C6—C7	−59.57 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2i	0.86	2.55	3.274 (2)	142
N2—H2···N1ii	0.86	2.37	2.956 (2)	126
N3—H3A···N4iii	0.86	2.19	3.012 (2)	160
N3—H3B···O3iv	0.86	2.40	3.192 (2)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2i	0.86	2.55	3.274 (2)	142
N2—H2⋯N1ii	0.86	2.37	2.956 (2)	126
N3—H3A⋯N4iii	0.86	2.19	3.012 (2)	160
N3—H3B⋯O3iv	0.86	2.40	3.192 (2)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .