Di­methyl 1-(3-chloro-4-methyl­phenyl)pyrazole-3,4-di­carboxyl­ate

The dihedral angle between the phenyl and pyrazole moieties of the title compound, C₁₄H₁₃ClN₂O₄, is 8.66 (8)°. In the solid state, the symmetry-related mol­ecules are linked by intermolecular C—H...O-type hydrogen bonds to form a continuous chain, which runs parallel to the c axis.

Key indicators

• Single-crystal X-ray study
• T = 160 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.116
• Data-to-parameter ratio = 21.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Version 1.07; Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).

Dimethyl 1-(3-chloro-4-methylphenyl)pyrazole-3,4-dicarboxylate

Crystal data

C14H13ClN2O4	F(000) = 640
Mr = 308.72	Dx = 1.475 Mg m^−3
Monoclinic, P21/c	Melting point: 381 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.2279 (1) Å	Cell parameters from 19230 reflections
b = 15.1992 (2) Å	θ = 2.0–30.0°
c = 11.6764 (2) Å	µ = 0.29 mm^−1
β = 107.7807 (7)°	T = 160 K
V = 1390.47 (3) Å^3	Tablet, colourless
Z = 4	0.30 × 0.28 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer	4068 independent reflections
Radiation source: Nonius FR591 sealed tube generator	3039 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.051
Detector resolution: 9 pixels mm^-1	θmax = 30.0°, θmin = 2.3°
φ and ω scans with κ offsets	h = −11→11
Absorption correction: multi-scan (Blessing, 1995)	k = −21→21
Tmin = 0.877, Tmax = 0.943	l = −16→16
35568 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 0.4477P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4068 reflections	Δρmax = 0.33 e Å^−3
194 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (3)

Special details

Experimental. Solvent used: ethanol Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.461 (1) Frames collected: 316 Seconds exposure per frame: 20 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 28.0

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
Cl1	−0.03915 (5)	−0.20802 (3)	0.44906 (4)	0.03509 (13)
O16	0.45834 (17)	0.29552 (8)	0.21763 (11)	0.0442 (3)
O17	0.60007 (14)	0.28265 (6)	0.41463 (9)	0.0281 (2)
O13	0.41550 (16)	0.13046 (11)	0.06949 (11)	0.0518 (4)
O14	0.15087 (13)	0.08006 (7)	0.04167 (9)	0.0289 (2)
N1	0.29752 (14)	0.06468 (7)	0.40532 (10)	0.0214 (2)
N2	0.25129 (15)	0.04658 (8)	0.28565 (10)	0.0227 (2)
C5	0.38824 (17)	0.14038 (9)	0.43341 (12)	0.0225 (3)
H5	0.4326	0.1657	0.5112	0.027*
C4	0.40365 (17)	0.17344 (9)	0.32763 (13)	0.0233 (3)
C3	0.31518 (17)	0.11303 (9)	0.23845 (12)	0.0228 (3)
C6	0.25293 (17)	0.00422 (9)	0.48469 (12)	0.0207 (3)
C7	0.14298 (17)	−0.06481 (9)	0.43607 (12)	0.0226 (3)
H7	0.0977	−0.0719	0.3514	0.027*
C8	0.10072 (18)	−0.12325 (9)	0.51370 (13)	0.0239 (3)
C9	0.16436 (18)	−0.11610 (9)	0.63839 (13)	0.0241 (3)
C10	0.27483 (19)	−0.04585 (9)	0.68256 (12)	0.0252 (3)
H10	0.3214	−0.0389	0.7672	0.030*
C11	0.31958 (18)	0.01437 (9)	0.60790 (12)	0.0236 (3)
H11	0.3947	0.0617	0.6409	0.028*
C12	0.1206 (2)	−0.17992 (11)	0.72314 (15)	0.0343 (4)
H121	0.0046	−0.1682	0.7257	0.051*
H122	0.2016	−0.1729	0.8039	0.051*
H123	0.1270	−0.2402	0.6950	0.051*
C16	0.48717 (18)	0.25636 (9)	0.31168 (13)	0.0254 (3)
C18	0.6751 (2)	0.36832 (10)	0.41177 (16)	0.0355 (4)
H181	0.7116	0.3732	0.3396	0.053*
H182	0.7739	0.3758	0.4835	0.053*
H183	0.5904	0.4140	0.4102	0.053*
C13	0.30204 (19)	0.11015 (10)	0.10873 (13)	0.0267 (3)
C15	0.1299 (2)	0.07363 (12)	−0.08548 (13)	0.0370 (4)
H151	0.1260	0.1328	−0.1195	0.055*
H152	0.0232	0.0427	−0.1257	0.055*
H153	0.2261	0.0410	−0.0975	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0375 (2)	0.0295 (2)	0.0394 (2)	−0.01286 (15)	0.01335 (17)	−0.00357 (15)
O16	0.0466 (7)	0.0377 (7)	0.0385 (7)	−0.0090 (5)	−0.0014 (5)	0.0181 (5)
O17	0.0348 (6)	0.0220 (5)	0.0284 (5)	−0.0065 (4)	0.0111 (4)	−0.0009 (4)
O13	0.0383 (7)	0.0903 (11)	0.0304 (6)	−0.0172 (7)	0.0157 (5)	0.0040 (7)
O14	0.0299 (5)	0.0355 (6)	0.0215 (5)	−0.0021 (4)	0.0081 (4)	−0.0029 (4)
N1	0.0230 (6)	0.0213 (5)	0.0204 (5)	−0.0009 (4)	0.0072 (4)	−0.0008 (4)
N2	0.0238 (6)	0.0246 (6)	0.0201 (5)	−0.0005 (4)	0.0073 (4)	−0.0003 (4)
C5	0.0231 (7)	0.0197 (6)	0.0247 (6)	−0.0003 (5)	0.0074 (5)	−0.0013 (5)
C4	0.0215 (6)	0.0214 (6)	0.0275 (7)	0.0019 (5)	0.0084 (5)	0.0015 (5)
C3	0.0216 (6)	0.0241 (7)	0.0230 (6)	0.0015 (5)	0.0073 (5)	0.0026 (5)
C6	0.0215 (6)	0.0191 (6)	0.0226 (6)	0.0019 (5)	0.0087 (5)	−0.0003 (5)
C7	0.0233 (7)	0.0233 (7)	0.0211 (6)	−0.0010 (5)	0.0066 (5)	−0.0002 (5)
C8	0.0231 (6)	0.0203 (6)	0.0301 (7)	−0.0009 (5)	0.0108 (5)	−0.0017 (5)
C9	0.0261 (7)	0.0229 (7)	0.0268 (7)	0.0057 (5)	0.0133 (5)	0.0033 (5)
C10	0.0282 (7)	0.0271 (7)	0.0209 (6)	0.0056 (6)	0.0084 (5)	0.0004 (5)
C11	0.0251 (7)	0.0219 (6)	0.0233 (7)	0.0006 (5)	0.0069 (5)	−0.0018 (5)
C12	0.0409 (9)	0.0334 (8)	0.0337 (8)	0.0034 (7)	0.0190 (7)	0.0084 (7)
C16	0.0232 (7)	0.0217 (7)	0.0314 (7)	0.0023 (5)	0.0086 (6)	0.0045 (6)
C18	0.0398 (9)	0.0238 (7)	0.0453 (9)	−0.0096 (6)	0.0163 (7)	−0.0035 (7)
C13	0.0272 (7)	0.0281 (7)	0.0250 (7)	0.0013 (6)	0.0082 (6)	0.0042 (5)
C15	0.0429 (9)	0.0463 (10)	0.0207 (7)	−0.0006 (7)	0.0083 (7)	−0.0015 (7)

Geometric parameters (Å, º)

Cl1—C8	1.7389 (14)	C7—C8	1.3871 (19)
O16—C16	1.2072 (18)	C7—H7	0.9500
O17—C16	1.3362 (18)	C8—C9	1.393 (2)
O17—C18	1.4456 (18)	C9—C10	1.395 (2)
O13—C13	1.1992 (19)	C9—C12	1.506 (2)
O14—C13	1.3321 (18)	C10—C11	1.389 (2)
O14—C15	1.4446 (17)	C10—H10	0.9500
N1—C5	1.3561 (17)	C11—H11	0.9500
N1—N2	1.3594 (16)	C12—H121	0.9800
N1—C6	1.4304 (17)	C12—H122	0.9800
N2—C3	1.3332 (18)	C12—H123	0.9800
C5—C4	1.3747 (19)	C18—H181	0.9800
C5—H5	0.9500	C18—H182	0.9800
C4—C3	1.412 (2)	C18—H183	0.9800
C4—C16	1.4743 (19)	C15—H151	0.9800
C3—C13	1.4858 (19)	C15—H152	0.9800
C6—C11	1.3829 (19)	C15—H153	0.9800
C6—C7	1.3885 (19)
C16—O17—C18	115.65 (12)	C9—C10—H10	118.7
C13—O14—C15	115.12 (12)	C6—C11—C10	118.85 (13)
C5—N1—N2	112.39 (11)	C6—C11—H11	120.6
C5—N1—C6	128.28 (12)	C10—C11—H11	120.6
N2—N1—C6	119.30 (11)	C9—C12—H121	109.5
C3—N2—N1	104.46 (11)	C9—C12—H122	109.5
N1—C5—C4	106.72 (12)	H121—C12—H122	109.5
N1—C5—H5	126.6	C9—C12—H123	109.5
C4—C5—H5	126.6	H121—C12—H123	109.5
C5—C4—C3	104.87 (12)	H122—C12—H123	109.5
C5—C4—C16	126.90 (13)	O16—C16—O17	124.09 (13)
C3—C4—C16	128.16 (13)	O16—C16—C4	124.52 (14)
N2—C3—C4	111.55 (12)	O17—C16—C4	111.39 (12)
N2—C3—C13	118.94 (12)	O17—C18—H181	109.5
C4—C3—C13	129.16 (13)	O17—C18—H182	109.5
C11—C6—C7	120.77 (12)	H181—C18—H182	109.5
C11—C6—N1	120.25 (12)	O17—C18—H183	109.5
C7—C6—N1	118.99 (12)	H181—C18—H183	109.5
C8—C7—C6	118.61 (13)	H182—C18—H183	109.5
C8—C7—H7	120.7	O13—C13—O14	124.05 (14)
C6—C7—H7	120.7	O13—C13—C3	123.99 (14)
C7—C8—C9	122.95 (13)	O14—C13—C3	111.94 (12)
C7—C8—Cl1	117.11 (11)	O14—C15—H151	109.5
C9—C8—Cl1	119.95 (11)	O14—C15—H152	109.5
C8—C9—C10	116.15 (12)	H151—C15—H152	109.5
C8—C9—C12	123.20 (14)	O14—C15—H153	109.5
C10—C9—C12	120.64 (13)	H151—C15—H153	109.5
C11—C10—C9	122.69 (13)	H152—C15—H153	109.5
C11—C10—H10	118.7
C5—N1—N2—C3	−0.04 (15)	Cl1—C8—C9—C10	−179.58 (10)
C6—N1—N2—C3	−178.20 (11)	C7—C8—C9—C12	−179.27 (14)
N2—N1—C5—C4	−0.44 (15)	Cl1—C8—C9—C12	1.06 (19)
C6—N1—C5—C4	177.52 (12)	C8—C9—C10—C11	0.3 (2)
N1—C5—C4—C3	0.70 (15)	C12—C9—C10—C11	179.66 (13)
N1—C5—C4—C16	177.88 (13)	C7—C6—C11—C10	0.1 (2)
N1—N2—C3—C4	0.51 (15)	N1—C6—C11—C10	−179.51 (12)
N1—N2—C3—C13	174.37 (12)	C9—C10—C11—C6	−0.4 (2)
C5—C4—C3—N2	−0.77 (16)	C18—O17—C16—O16	7.0 (2)
C16—C4—C3—N2	−177.90 (13)	C18—O17—C16—C4	−173.36 (12)
C5—C4—C3—C13	−173.84 (14)	C5—C4—C16—O16	−157.99 (16)
C16—C4—C3—C13	9.0 (2)	C3—C4—C16—O16	18.5 (2)
C5—N1—C6—C11	−7.4 (2)	C5—C4—C16—O17	22.4 (2)
N2—N1—C6—C11	170.45 (12)	C3—C4—C16—O17	−161.08 (13)
C5—N1—C6—C7	173.03 (13)	C15—O14—C13—O13	−0.5 (2)
N2—N1—C6—C7	−9.14 (18)	C15—O14—C13—C3	−178.76 (13)
C11—C6—C7—C8	0.3 (2)	N2—C3—C13—O13	−137.36 (17)
N1—C6—C7—C8	179.86 (12)	C4—C3—C13—O13	35.3 (2)
C6—C7—C8—C9	−0.4 (2)	N2—C3—C13—O14	40.94 (18)
C6—C7—C8—Cl1	179.32 (10)	C4—C3—C13—O14	−146.43 (14)
C7—C8—C9—C10	0.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O16^i	0.95	2.43	3.336 (2)	160
C11—H11···O16^i	0.95	2.35	3.225 (2)	154

Symmetry code: (i) x, −y+1/2, z+1/2.