Ethyl 3-methyl-1-(2,4-di­nitro­phenyl)-1H-pyrazole-4-carboxyl­ate

The title compound, C₁₃H₁₂N₄O₆, containing a di­nitro­phenyl ring substituted on the pyrazole ring, was obtained by a reaction of ethyl aceto­acetate (2,4-di­nitro­phenyl)­hydrazone with Vilsmeier reagent. The benzene and pyrazole rings are oriented at an angle of 35.49 (6)° with respect to each other. The packing of the mol­ecules is controlled by intermolecular C—H...O hydrogen bonds, in addition to van der Waals forces.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.128
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT432_ALERT_2_B Short Inter X...Y Contact  O6     ..  C4       =       2.89 Ang.

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT430_ALERT_2_C Short Inter D...A Contact  O6     ..  O6       =       2.87 Ang.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   2 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
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Ethyl 3-methyl-1-(2,4-dinitrophenyl)-1H-pyrazole-4-carboxylate

Crystal data

C13H12N4O6	Z = 2
Mr = 320.27	F(000) = 332
Triclinic, P1	Dx = 1.464 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7531 (8) Å	Cell parameters from 1829 reflections
b = 9.7146 (10) Å	θ = 2.0–28.0°
c = 11.4051 (12) Å	µ = 0.12 mm^−1
α = 113.649 (2)°	T = 293 K
β = 92.989 (2)°	Block, pale yellow
γ = 109.089 (2)°	0.21 × 0.19 × 0.18 mm
V = 726.74 (13) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3210 independent reflections
Radiation source: fine-focus sealed tube	2600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ω scans	θmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.976, Tmax = 0.979	k = −9→12
4623 measured reflections	l = −15→13

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0737P)^2 + 0.0853P] where P = (Fo^2 + 2Fc^2)/3
3210 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.33971 (16)	0.45890 (16)	0.63006 (13)	0.0591 (3)
O2	0.37071 (14)	0.37774 (14)	0.78603 (10)	0.0470 (3)
O3	1.1906 (2)	0.89878 (18)	0.97845 (13)	0.0784 (5)
O4	1.4153 (2)	0.8115 (2)	0.96059 (14)	0.0792 (5)
O5	1.72140 (19)	0.9461 (2)	0.63105 (16)	0.0941 (6)
O6	1.55237 (18)	0.86268 (15)	0.44242 (12)	0.0570 (3)
N1	0.92725 (17)	0.64369 (15)	0.73161 (12)	0.0412 (3)
N2	0.94311 (17)	0.56952 (16)	0.80975 (12)	0.0434 (3)
N3	1.2894 (2)	0.83692 (18)	0.91575 (14)	0.0563 (4)
N4	1.5707 (2)	0.88453 (17)	0.55618 (15)	0.0516 (3)
C1	0.7702 (2)	0.49489 (17)	0.81583 (14)	0.0394 (3)
C2	0.6410 (2)	0.52023 (17)	0.74120 (14)	0.0390 (3)
C3	0.7471 (2)	0.61362 (19)	0.68814 (16)	0.0428 (3)
C4	0.4361 (2)	0.45189 (18)	0.71271 (15)	0.0416 (3)
C5	0.1724 (2)	0.2805 (3)	0.7542 (2)	0.0565 (4)
C6	0.1462 (3)	0.1804 (3)	0.8273 (3)	0.0745 (6)
C7	0.7330 (3)	0.3934 (3)	0.8881 (2)	0.0536 (4)
C8	1.0868 (2)	0.71899 (17)	0.69331 (14)	0.0392 (3)
C9	1.2630 (2)	0.79859 (17)	0.77585 (14)	0.0415 (3)
C10	1.4224 (2)	0.85295 (18)	0.73264 (16)	0.0442 (4)
C11	1.4026 (2)	0.83283 (17)	0.60573 (15)	0.0429 (3)
C12	1.2299 (2)	0.76324 (19)	0.52269 (15)	0.0441 (3)
C13	1.0726 (2)	0.70505 (19)	0.56639 (15)	0.0439 (4)
H3	0.712 (3)	0.655 (2)	0.6306 (18)	0.056 (5)*
H5A	0.109 (3)	0.355 (3)	0.782 (2)	0.070 (6)*
H5B	0.129 (3)	0.209 (3)	0.655 (2)	0.082 (7)*
H6A	0.011 (4)	0.108 (4)	0.807 (3)	0.106 (8)*
H6B	0.213 (5)	0.103 (4)	0.794 (3)	0.132 (11)*
H6C	0.193 (5)	0.240 (5)	0.922 (4)	0.145 (13)*
H7A	0.853 (3)	0.402 (3)	0.931 (2)	0.079 (6)*
H7B	0.652 (3)	0.282 (3)	0.831 (2)	0.071 (6)*
H7C	0.665 (3)	0.425 (3)	0.947 (2)	0.084 (7)*
H10	1.544 (3)	0.906 (2)	0.7896 (18)	0.059 (5)*
H12	1.219 (3)	0.749 (2)	0.4315 (19)	0.056 (5)*
H13	0.953 (3)	0.649 (2)	0.5087 (18)	0.052 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0407 (6)	0.0803 (8)	0.0676 (8)	0.0182 (6)	0.0042 (5)	0.0480 (7)
O2	0.0343 (5)	0.0596 (7)	0.0495 (6)	0.0124 (5)	0.0102 (4)	0.0305 (5)
O3	0.0721 (9)	0.0825 (10)	0.0481 (7)	0.0038 (8)	0.0166 (7)	0.0181 (7)
O4	0.0639 (8)	0.1020 (11)	0.0701 (9)	0.0035 (8)	−0.0101 (7)	0.0616 (9)
O5	0.0410 (7)	0.1447 (16)	0.0879 (11)	0.0050 (9)	0.0095 (7)	0.0677 (11)
O6	0.0661 (8)	0.0559 (7)	0.0536 (7)	0.0216 (6)	0.0282 (6)	0.0280 (6)
N1	0.0357 (6)	0.0441 (7)	0.0456 (7)	0.0085 (5)	0.0045 (5)	0.0274 (5)
N2	0.0384 (7)	0.0485 (7)	0.0435 (7)	0.0074 (5)	0.0025 (5)	0.0286 (6)
N3	0.0485 (8)	0.0581 (8)	0.0457 (8)	−0.0067 (7)	0.0010 (6)	0.0296 (7)
N4	0.0458 (8)	0.0522 (8)	0.0588 (9)	0.0130 (6)	0.0159 (6)	0.0305 (7)
C1	0.0374 (7)	0.0418 (7)	0.0360 (7)	0.0084 (6)	0.0039 (6)	0.0201 (6)
C2	0.0369 (7)	0.0418 (7)	0.0381 (7)	0.0116 (6)	0.0061 (6)	0.0203 (6)
C3	0.0381 (8)	0.0483 (8)	0.0479 (8)	0.0148 (6)	0.0073 (6)	0.0285 (7)
C4	0.0371 (7)	0.0466 (8)	0.0433 (8)	0.0148 (6)	0.0087 (6)	0.0228 (6)
C5	0.0344 (8)	0.0670 (11)	0.0694 (12)	0.0135 (8)	0.0151 (8)	0.0356 (10)
C6	0.0595 (13)	0.0737 (14)	0.0867 (16)	0.0059 (11)	0.0161 (11)	0.0474 (13)
C7	0.0425 (9)	0.0670 (12)	0.0588 (11)	0.0103 (8)	0.0049 (8)	0.0440 (9)
C8	0.0365 (7)	0.0376 (7)	0.0436 (8)	0.0091 (6)	0.0060 (6)	0.0225 (6)
C9	0.0409 (8)	0.0414 (7)	0.0393 (7)	0.0063 (6)	0.0035 (6)	0.0232 (6)
C10	0.0377 (8)	0.0437 (8)	0.0474 (8)	0.0055 (6)	0.0031 (6)	0.0250 (7)
C11	0.0401 (8)	0.0409 (8)	0.0490 (8)	0.0103 (6)	0.0110 (6)	0.0248 (6)
C12	0.0467 (8)	0.0459 (8)	0.0395 (8)	0.0118 (7)	0.0070 (6)	0.0236 (6)
C13	0.0394 (8)	0.0457 (8)	0.0433 (8)	0.0078 (7)	0.0013 (6)	0.0240 (7)

Geometric parameters (Å, º)

O1—C4	1.2097 (18)	C5—C6	1.490 (3)
O2—C4	1.3282 (18)	C5—H5A	0.96 (2)
O2—C5	1.451 (2)	C5—H5B	1.03 (2)
O3—N3	1.213 (2)	C6—H6A	1.01 (3)
O4—N3	1.218 (2)	C6—H6B	1.01 (4)
O5—N4	1.2172 (19)	C6—H6C	0.97 (4)
O6—N4	1.2202 (18)	C7—H7A	0.99 (2)
N1—C3	1.3514 (19)	C7—H7B	0.97 (2)
N1—N2	1.3749 (16)	C7—H7C	0.90 (3)
N1—C8	1.4061 (19)	C8—C9	1.393 (2)
N2—C1	1.3195 (19)	C8—C13	1.394 (2)
N3—C9	1.472 (2)	C9—C10	1.377 (2)
N4—C11	1.465 (2)	C10—C11	1.374 (2)
C1—C2	1.424 (2)	C10—H10	0.96 (2)
C1—C7	1.492 (2)	C11—C12	1.381 (2)
C2—C3	1.367 (2)	C12—C13	1.376 (2)
C2—C4	1.467 (2)	C12—H12	0.988 (19)
C3—H3	0.965 (19)	C13—H13	0.956 (19)
C4—O2—C5	118.11 (13)	C5—C6—H6B	109.2 (19)
C3—N1—N2	111.83 (12)	H6A—C6—H6B	105 (2)
C3—N1—C8	128.32 (12)	C5—C6—H6C	116 (2)
N2—N1—C8	119.25 (11)	H6A—C6—H6C	110 (3)
C1—N2—N1	105.14 (11)	H6B—C6—H6C	106 (3)
O3—N3—O4	125.24 (17)	C1—C7—H7A	109.7 (14)
O3—N3—C9	117.54 (15)	C1—C7—H7B	111.4 (13)
O4—N3—C9	117.11 (17)	H7A—C7—H7B	112.4 (18)
O5—N4—O6	123.61 (15)	C1—C7—H7C	110.3 (16)
O5—N4—C11	117.90 (14)	H7A—C7—H7C	111 (2)
O6—N4—C11	118.50 (14)	H7B—C7—H7C	102 (2)
N2—C1—C2	110.73 (12)	C9—C8—C13	118.31 (14)
N2—C1—C7	120.00 (13)	C9—C8—N1	121.87 (13)
C2—C1—C7	129.18 (14)	C13—C8—N1	119.67 (13)
C3—C2—C1	105.48 (13)	C10—C9—C8	121.85 (14)
C3—C2—C4	124.67 (13)	C10—C9—N3	115.88 (13)
C1—C2—C4	129.62 (13)	C8—C9—N3	122.20 (13)
N1—C3—C2	106.80 (13)	C11—C10—C9	117.83 (14)
N1—C3—H3	122.1 (11)	C11—C10—H10	120.7 (12)
C2—C3—H3	131.1 (11)	C9—C10—H10	121.5 (11)
O1—C4—O2	124.51 (14)	C10—C11—C12	122.30 (14)
O1—C4—C2	123.86 (14)	C10—C11—N4	118.78 (14)
O2—C4—C2	111.60 (12)	C12—C11—N4	118.91 (14)
O2—C5—C6	106.50 (16)	C13—C12—C11	118.95 (14)
O2—C5—H5A	107.0 (13)	C13—C12—H12	119.9 (11)
C6—C5—H5A	111.9 (13)	C11—C12—H12	121.0 (11)
O2—C5—H5B	109.9 (14)	C12—C13—C8	120.58 (14)
C6—C5—H5B	111.4 (13)	C12—C13—H13	120.6 (11)
H5A—C5—H5B	110.0 (18)	C8—C13—H13	118.7 (11)
C5—C6—H6A	109.9 (16)
C3—N1—N2—C1	−0.92 (17)	N2—N1—C8—C13	140.36 (14)
C8—N1—N2—C1	−172.80 (13)	C13—C8—C9—C10	−4.5 (2)
N1—N2—C1—C2	0.09 (16)	N1—C8—C9—C10	171.00 (14)
N1—N2—C1—C7	176.91 (15)	C13—C8—C9—N3	172.35 (14)
N2—C1—C2—C3	0.73 (18)	N1—C8—C9—N3	−12.1 (2)
C7—C1—C2—C3	−175.72 (17)	O3—N3—C9—C10	129.84 (16)
N2—C1—C2—C4	175.27 (14)	O4—N3—C9—C10	−46.5 (2)
C7—C1—C2—C4	−1.2 (3)	O3—N3—C9—C8	−47.2 (2)
N2—N1—C3—C2	1.39 (18)	O4—N3—C9—C8	136.41 (16)
C8—N1—C3—C2	172.35 (14)	C8—C9—C10—C11	2.8 (2)
C1—C2—C3—N1	−1.24 (17)	N3—C9—C10—C11	−174.25 (14)
C4—C2—C3—N1	−176.13 (14)	C9—C10—C11—C12	1.1 (2)
C5—O2—C4—O1	8.4 (2)	C9—C10—C11—N4	−177.87 (13)
C5—O2—C4—C2	−169.71 (14)	O5—N4—C11—C10	−1.3 (2)
C3—C2—C4—O1	7.0 (3)	O6—N4—C11—C10	178.21 (14)
C1—C2—C4—O1	−166.59 (16)	O5—N4—C11—C12	179.72 (17)
C3—C2—C4—O2	−174.84 (14)	O6—N4—C11—C12	−0.8 (2)
C1—C2—C4—O2	11.6 (2)	C10—C11—C12—C13	−3.1 (2)
C4—O2—C5—C6	166.06 (17)	N4—C11—C12—C13	175.83 (14)
C3—N1—C8—C9	154.49 (15)	C11—C12—C13—C8	1.3 (2)
N2—N1—C8—C9	−35.1 (2)	C9—C8—C13—C12	2.4 (2)
C3—N1—C8—C13	−30.0 (2)	N1—C8—C13—C12	−173.25 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O5^i	1.00 (4)	2.50 (3)	3.358 (3)	144 (2)
C13—H13···O1^ii	0.95 (2)	2.34 (2)	3.292 (2)	173 (2)

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