Methyl [6-amino-5-cyano-4-(4-methoxyphen­yl)pyrano[2,3-c]pyrazol-3-yl]acetate

In the title compound, C₁₇H₁₆N₄O₄, the dihedral angle between the planar nine-membered bicyclic ring system and the benzene ring is 81.9 (1)°. Intra­molecular N—H...O and inter­molecular N—H...O, N—H...N and C—H...N hydrogen bonds are effective in stabilizing the mol­ecular and crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.055
• wR factor = 0.144
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.59 Ratio

Author Response: Crystal data was collected at room temperature. According to the other atoms of the molecule, the methyl groups behave most freely. Therefore, a large difference between Ueq will show up.

PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       5.58 Ratio

Author Response: See response above.

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.142
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.14
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.80 mm
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT213_ALERT_2_C Atom C17     has ADP max/min Ratio .............       3.30 prolat
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O4
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C4     -   C7     ...       1.42 Ang.

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Methyl [6-amino-5-cyano-4-(4-methoxyphenyl)pyrano[2,3-c]pyrazol-3-yl]acetate

Crystal data

C17H16N4O4	Z = 2
Mr = 340.34	F(000) = 356
Triclinic, P1	Dx = 1.407 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2806 (8) Å	Cell parameters from 2553 reflections
b = 9.9148 (12) Å	θ = 2.2–28.0°
c = 13.6958 (16) Å	µ = 0.10 mm^−1
α = 90.813 (10)°	T = 296 K
β = 97.042 (10)°	Rod, colourless
γ = 108.051 (9)°	0.80 × 0.45 × 0.06 mm
V = 803.53 (18) Å^3

Data collection

Stoe IPDS-II diffractometer	3149 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2297 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.142
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.2°
ω scans	h = −7→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −12→12
Tmin = 0.922, Tmax = 0.994	l = −16→16
13193 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0699P)^2 + 0.1859P] where P = (Fo^2 + 2Fc^2)/3
3149 reflections	(Δ/σ)max < 0.001
240 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1230 (2)	0.42683 (15)	0.93760 (12)	0.0359 (5)
O2	0.7757 (4)	0.9557 (2)	0.78964 (18)	0.0686 (8)
O3	0.9691 (3)	0.88300 (19)	0.68592 (15)	0.0575 (7)
O4	0.5226 (4)	0.2797 (3)	0.43249 (14)	0.0754 (9)
N1	0.4633 (3)	0.7447 (2)	0.87454 (14)	0.0330 (6)
N2	0.2795 (3)	0.66796 (19)	0.91585 (14)	0.0339 (6)
N3	−0.0219 (4)	0.1965 (2)	0.95871 (17)	0.0437 (7)
N4	0.3564 (4)	0.0221 (2)	0.8839 (2)	0.0580 (9)
C1	0.5793 (3)	0.6642 (2)	0.84069 (16)	0.0305 (6)
C2	0.4668 (3)	0.5254 (2)	0.86065 (16)	0.0293 (6)
C3	0.5077 (3)	0.3866 (2)	0.84052 (16)	0.0298 (6)
C4	0.3204 (4)	0.2730 (2)	0.88276 (16)	0.0316 (6)
C5	0.1470 (4)	0.2953 (2)	0.92380 (16)	0.0320 (6)
C6	0.2881 (3)	0.5372 (2)	0.90557 (16)	0.0292 (6)
C7	0.3371 (4)	0.1331 (2)	0.88372 (18)	0.0380 (7)
C8	0.7844 (4)	0.7162 (2)	0.78970 (18)	0.0381 (7)
C9	0.8377 (4)	0.8644 (2)	0.75619 (19)	0.0398 (7)
C10	1.0367 (7)	1.0239 (3)	0.6486 (3)	0.0845 (13)
C11	0.5133 (3)	0.3561 (2)	0.73150 (16)	0.0317 (6)
C12	0.6810 (5)	0.3103 (4)	0.7018 (2)	0.0618 (13)
C13	0.6907 (6)	0.2843 (4)	0.6024 (2)	0.0758 (13)
C14	0.5291 (5)	0.3025 (3)	0.53229 (19)	0.0510 (9)
C15	0.3591 (4)	0.3473 (3)	0.56057 (19)	0.0450 (8)
C16	0.3530 (4)	0.3747 (3)	0.65909 (18)	0.0404 (8)
C17	0.7041 (8)	0.2448 (8)	0.3998 (3)	0.134 (3)
H1	0.493 (5)	0.837 (4)	0.872 (2)	0.062 (9)*
H3	0.65340	0.38980	0.87720	0.0360*
H3A	−0.129 (4)	0.225 (3)	0.986 (2)	0.044 (7)*
H3B	−0.061 (5)	0.114 (4)	0.938 (2)	0.061 (9)*
H8A	0.76590	0.65250	0.73270	0.0460*
H8B	0.91360	0.71000	0.83400	0.0460*
H10A	0.92000	1.03250	0.59920	0.1260*
H10B	1.17410	1.03900	0.62020	0.1260*
H10C	1.06090	1.09360	0.70160	0.1260*
H12	0.79070	0.29620	0.74900	0.0740*
H13	0.80740	0.25470	0.58390	0.0910*
H15	0.24770	0.35920	0.51330	0.0540*
H16	0.23800	0.40660	0.67720	0.0490*
H17A	0.84330	0.31740	0.42350	0.2010*
H17B	0.68440	0.23780	0.32910	0.2010*
H17C	0.70830	0.15540	0.42460	0.2010*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0379 (8)	0.0237 (8)	0.0497 (10)	0.0104 (6)	0.0173 (7)	0.0036 (6)
O2	0.0825 (14)	0.0318 (10)	0.1019 (18)	0.0179 (10)	0.0514 (13)	0.0094 (10)
O3	0.0737 (12)	0.0378 (10)	0.0587 (13)	0.0047 (9)	0.0332 (10)	0.0067 (8)
O4	0.0729 (13)	0.132 (2)	0.0337 (11)	0.0518 (14)	0.0046 (10)	−0.0078 (12)
N1	0.0390 (10)	0.0227 (9)	0.0392 (11)	0.0099 (8)	0.0122 (8)	0.0042 (7)
N2	0.0372 (9)	0.0268 (9)	0.0409 (11)	0.0121 (8)	0.0117 (8)	0.0023 (8)
N3	0.0495 (12)	0.0249 (11)	0.0577 (14)	0.0061 (9)	0.0255 (11)	0.0004 (9)
N4	0.0740 (15)	0.0322 (12)	0.0780 (18)	0.0266 (11)	0.0221 (13)	0.0099 (11)
C1	0.0347 (10)	0.0273 (11)	0.0306 (11)	0.0108 (9)	0.0055 (9)	0.0010 (8)
C2	0.0327 (10)	0.0253 (10)	0.0305 (11)	0.0099 (8)	0.0045 (8)	0.0019 (8)
C3	0.0331 (10)	0.0263 (11)	0.0335 (12)	0.0129 (8)	0.0081 (9)	0.0026 (8)
C4	0.0405 (11)	0.0226 (10)	0.0344 (12)	0.0127 (9)	0.0074 (9)	0.0042 (8)
C5	0.0396 (11)	0.0244 (10)	0.0327 (12)	0.0103 (9)	0.0072 (9)	0.0010 (8)
C6	0.0330 (10)	0.0239 (10)	0.0326 (12)	0.0105 (8)	0.0072 (9)	0.0015 (8)
C7	0.0461 (12)	0.0301 (12)	0.0431 (14)	0.0157 (10)	0.0162 (10)	0.0062 (9)
C8	0.0407 (12)	0.0318 (12)	0.0448 (14)	0.0125 (10)	0.0135 (10)	0.0050 (10)
C9	0.0395 (11)	0.0289 (12)	0.0483 (15)	0.0049 (10)	0.0117 (10)	−0.0009 (10)
C10	0.125 (3)	0.0469 (18)	0.079 (2)	0.0083 (19)	0.051 (2)	0.0258 (17)
C11	0.0374 (11)	0.0253 (10)	0.0334 (12)	0.0099 (9)	0.0083 (9)	0.0042 (8)
C12	0.0684 (18)	0.104 (3)	0.0350 (15)	0.0608 (19)	0.0023 (13)	−0.0025 (14)
C13	0.075 (2)	0.138 (3)	0.0422 (17)	0.074 (2)	0.0083 (15)	−0.0064 (18)
C14	0.0560 (15)	0.0693 (19)	0.0307 (14)	0.0241 (14)	0.0063 (11)	−0.0017 (12)
C15	0.0416 (12)	0.0562 (16)	0.0366 (14)	0.0163 (11)	0.0007 (10)	0.0045 (11)
C16	0.0377 (11)	0.0471 (14)	0.0419 (14)	0.0199 (11)	0.0085 (10)	0.0038 (10)
C17	0.125 (3)	0.286 (8)	0.036 (2)	0.131 (5)	0.009 (2)	−0.020 (3)

Geometric parameters (Å, º)

O1—C5	1.372 (2)	C4—C7	1.423 (3)
O1—C6	1.374 (2)	C8—C9	1.495 (3)
O2—C9	1.196 (3)	C11—C16	1.381 (3)
O3—C9	1.322 (3)	C11—C12	1.370 (4)
O3—C10	1.449 (4)	C12—C13	1.394 (4)
O4—C14	1.376 (3)	C13—C14	1.365 (5)
O4—C17	1.409 (6)	C14—C15	1.370 (4)
N1—N2	1.364 (3)	C15—C16	1.380 (4)
N1—C1	1.347 (3)	C3—H3	0.9800
N2—C6	1.321 (3)	C8—H8A	0.9700
N3—C5	1.344 (3)	C8—H8B	0.9700
N4—C7	1.144 (3)	C10—H10A	0.9600
N1—H1	0.88 (4)	C10—H10B	0.9600
N3—H3A	0.92 (3)	C10—H10C	0.9600
N3—H3B	0.81 (4)	C12—H12	0.9300
C1—C8	1.494 (3)	C13—H13	0.9300
C1—C2	1.387 (3)	C15—H15	0.9300
C2—C3	1.504 (3)	C16—H16	0.9300
C2—C6	1.379 (3)	C17—H17A	0.9600
C3—C4	1.533 (3)	C17—H17B	0.9600
C3—C11	1.526 (3)	C17—H17C	0.9600
C4—C5	1.359 (4)
O1···O1^i	3.063 (2)	C4···H10C^viii	3.0100
O2···N3^ii	3.149 (3)	C5···H12^v	3.0700
O2···N1	2.768 (3)	C6···H3^vii	3.0000
O3···C17^iii	3.059 (6)	C7···H3B	2.65 (3)
O3···O4^iv	3.222 (3)	C7···H10C^viii	2.8100
O4···C9^iv	3.209 (3)	C9···H1	2.79 (3)
O4···O3^iv	3.222 (3)	C10···H17C^iii	2.9700
O4···C8^iv	3.405 (3)	C11···H8A	2.8700
O1···H3^v	2.8700	C13···H17C	2.7600
O2···H1	2.25 (3)	C13···H17A	2.7300
O2···H10A	2.9000	C15···H10B^viii	3.0800
O2···H10C	2.3600	C16···H10C^viii	2.9300
O2···H3B^ii	2.46 (3)	C17···H13	2.5200
O3···H17B^iii	2.8200	H1···O2	2.25 (3)
O3···H17C^iii	2.7800	H1···N4^vi	2.27 (4)
N1···O2	2.768 (3)	H1···C9	2.79 (3)
N1···N4^vi	3.031 (3)	H3···O1^x	2.8700
N2···C4^vii	3.407 (3)	H3···H12	2.3500
N2···N3^i	3.056 (3)	H3···N2^vii	2.9100
N3···N2^i	3.056 (3)	H3···C6^vii	3.0000
N3···O2^viii	3.149 (3)	H3A···N2^i	2.17 (3)
N4···C9^viii	3.389 (4)	H3B···O2^viii	2.46 (3)
N4···N1^ix	3.031 (3)	H3B···C7	2.65 (3)
N1···H17B^iv	2.8500	H8A···C11	2.8700
N2···H3A^i	2.17 (3)	H8B···N2^x	2.5900
N2···H8B^v	2.5900	H8B···N3^vii	2.9100
N2···H3^vii	2.9100	H10A···O2	2.9000
N3···H8B^vii	2.9100	H10A···H13^vi	2.5200
N4···H1^ix	2.27 (4)	H10B···C15^ii	3.0800
C1···C16	3.584 (3)	H10B···H17C^iii	2.3700
C1···C5^vii	3.420 (3)	H10C···O2	2.3600
C2···C6^vii	3.528 (3)	H10C···C4^ii	3.0100
C3···C6^vii	3.541 (3)	H10C···C7^ii	2.8100
C4···N2^vii	3.407 (3)	H10C···C16^ii	2.9300
C5···C1^vii	3.420 (3)	H12···C5^x	3.0700
C6···C2^vii	3.528 (3)	H12···H3	2.3500
C6···C3^vii	3.541 (3)	H13···C17	2.5200
C7···C10^viii	3.500 (5)	H13···H10A^ix	2.5200
C8···O4^iv	3.405 (3)	H13···H17A	2.3100
C8···C11	3.479 (3)	H13···H17C	2.3100
C9···N4^ii	3.389 (4)	H15···H17A^v	2.5900
C9···O4^iv	3.209 (3)	H16···C2	2.7800
C10···C16^ii	3.420 (4)	H17A···C13	2.7300
C10···C15^ii	3.538 (4)	H17A···H13	2.3100
C10···C7^ii	3.500 (5)	H17A···H15^x	2.5900
C11···C8	3.479 (3)	H17B···O3^iii	2.8200
C15···C10^viii	3.538 (4)	H17B···N1^iv	2.8500
C15···C15^iv	3.549 (4)	H17B···C1^iv	3.0400
C16···C10^viii	3.420 (4)	H17C···C13	2.7600
C16···C1	3.584 (3)	H17C···H13	2.3100
C17···O3^iii	3.059 (6)	H17C···O3^iii	2.7800
C1···H17B^iv	3.0400	H17C···C10^iii	2.9700
C2···H16	2.7800	H17C···H10B^iii	2.3700
C5—O1—C6	114.89 (16)	C11—C12—C13	121.4 (3)
C9—O3—C10	116.0 (2)	C12—C13—C14	120.0 (3)
C14—O4—C17	117.7 (3)	O4—C14—C13	124.7 (3)
N2—N1—C1	113.22 (18)	C13—C14—C15	119.4 (3)
N1—N2—C6	102.14 (18)	O4—C14—C15	115.9 (3)
C1—N1—H1	128 (2)	C14—C15—C16	120.1 (2)
N2—N1—H1	119 (2)	C11—C16—C15	121.7 (2)
C5—N3—H3A	118.7 (18)	C2—C3—H3	108.00
H3A—N3—H3B	116 (3)	C4—C3—H3	108.00
C5—N3—H3B	121 (2)	C11—C3—H3	108.00
N1—C1—C8	126.03 (18)	C1—C8—H8A	108.00
N1—C1—C2	106.23 (18)	C1—C8—H8B	108.00
C2—C1—C8	127.72 (18)	C9—C8—H8A	108.00
C3—C2—C6	123.75 (17)	C9—C8—H8B	108.00
C1—C2—C3	132.64 (19)	H8A—C8—H8B	107.00
C1—C2—C6	103.60 (17)	O3—C10—H10A	109.00
C4—C3—C11	112.67 (16)	O3—C10—H10B	109.00
C2—C3—C4	105.73 (17)	O3—C10—H10C	110.00
C2—C3—C11	112.92 (17)	H10A—C10—H10B	109.00
C3—C4—C7	116.8 (2)	H10A—C10—H10C	109.00
C3—C4—C5	125.95 (18)	H10B—C10—H10C	109.00
C5—C4—C7	117.2 (2)	C11—C12—H12	119.00
O1—C5—N3	109.6 (2)	C13—C12—H12	119.00
O1—C5—C4	123.69 (19)	C12—C13—H13	120.00
N3—C5—C4	126.7 (2)	C14—C13—H13	120.00
O1—C6—C2	125.89 (17)	C14—C15—H15	120.00
N2—C6—C2	114.80 (18)	C16—C15—H15	120.00
O1—C6—N2	119.30 (18)	C11—C16—H16	119.00
N4—C7—C4	178.1 (3)	C15—C16—H16	119.00
C1—C8—C9	116.3 (2)	O4—C17—H17A	109.00
O2—C9—O3	124.1 (2)	O4—C17—H17B	109.00
O3—C9—C8	110.8 (2)	O4—C17—H17C	109.00
O2—C9—C8	125.1 (2)	H17A—C17—H17B	109.00
C3—C11—C16	121.88 (19)	H17A—C17—H17C	109.00
C12—C11—C16	117.4 (2)	H17B—C17—H17C	109.00
C3—C11—C12	120.7 (2)
C5—O1—C6—N2	−179.9 (2)	C6—C2—C3—C4	−1.9 (3)
C5—O1—C6—C2	1.2 (3)	C2—C3—C4—C7	−172.6 (2)
C6—O1—C5—C4	0.7 (3)	C4—C3—C11—C16	73.9 (3)
C6—O1—C5—N3	179.34 (19)	C2—C3—C11—C16	−45.8 (3)
C10—O3—C9—O2	−0.6 (4)	C2—C3—C4—C5	3.8 (3)
C10—O3—C9—C8	−178.8 (3)	C4—C3—C11—C12	−106.9 (3)
C17—O4—C14—C13	−4.7 (6)	C2—C3—C11—C12	133.4 (2)
C17—O4—C14—C15	174.9 (4)	C11—C3—C4—C5	−120.0 (2)
C1—N1—N2—C6	−0.1 (2)	C11—C3—C4—C7	63.6 (3)
N2—N1—C1—C2	−0.1 (2)	C7—C4—C5—O1	172.9 (2)
N2—N1—C1—C8	178.5 (2)	C3—C4—C5—O1	−3.5 (4)
N1—N2—C6—C2	0.3 (2)	C7—C4—C5—N3	−5.6 (4)
N1—N2—C6—O1	−178.65 (18)	C3—C4—C5—N3	178.0 (2)
C2—C1—C8—C9	165.6 (2)	C1—C8—C9—O3	−159.1 (2)
C8—C1—C2—C3	0.5 (4)	C1—C8—C9—O2	22.8 (4)
C8—C1—C2—C6	−178.3 (2)	C3—C11—C16—C15	179.8 (2)
N1—C1—C2—C6	0.3 (2)	C3—C11—C12—C13	−178.9 (3)
N1—C1—C8—C9	−12.7 (3)	C16—C11—C12—C13	0.4 (5)
N1—C1—C2—C3	179.0 (2)	C12—C11—C16—C15	0.6 (4)
C3—C2—C6—N2	−179.3 (2)	C11—C12—C13—C14	−0.9 (5)
C3—C2—C6—O1	−0.4 (3)	C12—C13—C14—O4	−179.9 (3)
C6—C2—C3—C11	121.8 (2)	C12—C13—C14—C15	0.4 (5)
C1—C2—C6—O1	178.5 (2)	O4—C14—C15—C16	−179.2 (3)
C1—C2—C3—C11	−56.8 (3)	C13—C14—C15—C16	0.5 (4)
C1—C2—C6—N2	−0.4 (3)	C14—C15—C16—C11	−1.0 (4)
C1—C2—C3—C4	179.6 (2)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x+1, y+1, z; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x−1, y, z; (vi) x, y+1, z; (vii) −x+1, −y+1, −z+2; (viii) x−1, y−1, z; (ix) x, y−1, z; (x) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88 (4)	2.25 (3)	2.768 (3)	118 (3)
N1—H1···N4^vi	0.88 (4)	2.27 (4)	3.031 (3)	146 (3)
N3—H3A···N2^i	0.92 (3)	2.17 (3)	3.056 (3)	160 (2)
N3—H3B···O2^viii	0.81 (4)	2.46 (3)	3.149 (3)	143 (3)
C8—H8B···N2^x	0.97	2.59	3.537 (3)	167

Symmetry codes: (i) −x, −y+1, −z+2; (vi) x, y+1, z; (viii) x−1, y−1, z; (x) x+1, y, z.