2-Chloro-N-[3-cyano-1-(3,4-dichloro­phen­yl)-1H-pyrazol-5-yl]acetamide

Li, M.; Zhu, J.; Wei, H.; Wang, J.; Guo, C.

doi:10.1107/S1600536812008094

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1150

doi:10.1107/S1600536812008094

Open

access

2-Chloro-N-[3-cyano-1-(3,4-dichlorophenyl)-1H-pyrazol-5-yl]acetamide

Ming Li,^a Jing Zhu,^a Hong-xia Wei,^a Jian-qiang Wang ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 22 February 2012; accepted 23 February 2012; online 24 March 2012)

In the title compound, C₁₂H₇Cl₃N₄O, the dihedral angle between the pyrazole and benzene rings is 35.6 (3)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds generating C(4) chains propagating in [100].

Related literature

For background to the properties of N-pyrazoles, see: Liu et al. (2010 ); Zhao et al. (2010 ).

Experimental

Crystal data

C₁₂H₇Cl₃N₄O
M_r = 329.57
Monoclinic, P 2₁ /n
a = 4.6280 (9) Å
b = 17.245 (3) Å
c = 17.468 (4) Å
β = 94.04 (3)°
V = 1390.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.827, T_max = 0.937
5687 measured reflections
2564 independent reflections
1880 reflections with I > 2σ(I)
R_int = 0.040
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.139
S = 1.01
2564 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯Oⁱ	0.86	1.95	2.743 (3)	153
Symmetry code: (i) x-1, y, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008094/hb6649sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008094/hb6649Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008094/hb6649Isup3.cml

checkCIF report

Related literature top

For background to the properties of N-pyrazoles, see: Liu et al. (2010); Zhao et al. (2010).

Experimental top

To a stirred solution of 5-amino-1-(3,4-dichlorophenyl)-1H-pyrazole-3-carbonitrile (5 mmol) in THF (20 ml) was added 2-chloroacetyl chloride (5 mmol) dropwise at 0-5°C. After the addition, the reaction mixture was allowed to raise to room temperature and stirred for 2 h. The crude product (I) precipitated and was filterd. Pure compound (I) was obtained by crystallization from ethanol. Colourless blocks of (I) were obtained by slow evaporation of an acetone solution.

Structure description top

For background to the properties of N-pyrazoles, see: Liu et al. (2010); Zhao et al. (2010).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram for (I).

2-Chloro-N-[3-cyano-1-(3,4-dichlorophenyl)-1H-pyrazol-5-yl]acetamide top

Crystal data top

C₁₂H₇Cl₃N₄O	D_x = 1.574 Mg m⁻³
M_r = 329.57	Melting point: 473 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.6280 (9) Å	Cell parameters from 25 reflections
b = 17.245 (3) Å	θ = 9–13°
c = 17.468 (4) Å	µ = 0.66 mm⁻¹
β = 94.04 (3)°	T = 293 K
V = 1390.7 (5) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm
F(000) = 664

Data collection top

Enraf–Nonius CAD-4 diffractometer	1880 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = 0→5
Absorption correction: ψ scan (North et al., 1968)	k = −20→20
T_min = 0.827, T_max = 0.937	l = −21→21
5687 measured reflections	3 standard reflections every 200 reflections
2564 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.139	w = 1/[σ²(F_o²) + (0.090P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2564 reflections	Δρ_max = 0.31 e Å⁻³
182 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.019 (3)

Crystal data top

C₁₂H₇Cl₃N₄O	V = 1390.7 (5) Å³
M_r = 329.57	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6280 (9) Å	µ = 0.66 mm⁻¹
b = 17.245 (3) Å	T = 293 K
c = 17.468 (4) Å	0.30 × 0.20 × 0.10 mm
β = 94.04 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1880 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.040
T_min = 0.827, T_max = 0.937	3 standard reflections every 200 reflections
5687 measured reflections	intensity decay: 1%
2564 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.01	Δρ_max = 0.31 e Å⁻³
2564 reflections	Δρ_min = −0.25 e Å⁻³
182 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O	0.8240 (5)	0.38138 (13)	0.35313 (18)	0.0813 (8)
Cl1	−0.40136 (18)	0.21696 (4)	−0.00295 (5)	0.0641 (3)
C1	−0.0120 (6)	0.23735 (15)	0.11596 (15)	0.0438 (6)
H1A	−0.0419	0.1852	0.1266	0.053*
Cl2	−0.3173 (2)	0.39579 (5)	−0.03563 (5)	0.0738 (3)
N1	0.3510 (5)	0.24173 (12)	0.22197 (12)	0.0426 (5)
N2	0.4349 (5)	0.16733 (12)	0.21185 (13)	0.0488 (6)
C2	−0.1647 (6)	0.27227 (15)	0.05502 (15)	0.0447 (6)
Cl3	0.69321 (17)	0.53185 (4)	0.41501 (5)	0.0602 (3)
C3	−0.1258 (7)	0.35054 (16)	0.04024 (15)	0.0496 (7)
N3	0.8375 (9)	0.01856 (18)	0.2981 (2)	0.0950 (11)
N4	0.3729 (4)	0.34308 (13)	0.31669 (13)	0.0456 (6)
H4A	0.1933	0.3562	0.3119	0.055*
C4	0.0724 (8)	0.39217 (16)	0.08606 (17)	0.0582 (8)
H4B	0.0990	0.4446	0.0762	0.070*
C5	0.2322 (7)	0.35752 (15)	0.14625 (16)	0.0521 (7)
H5A	0.3688	0.3857	0.1763	0.062*
C6	0.1850 (6)	0.27986 (14)	0.16112 (14)	0.0412 (6)
C7	0.4522 (5)	0.26933 (16)	0.29174 (15)	0.0425 (6)
C8	0.6121 (7)	0.21299 (17)	0.32747 (17)	0.0541 (7)
H8A	0.7116	0.2150	0.3756	0.065*
C9	0.5948 (7)	0.15113 (15)	0.27610 (16)	0.0489 (7)
C10	0.7278 (8)	0.07622 (19)	0.28682 (18)	0.0644 (9)
C11	0.5659 (6)	0.39367 (15)	0.34757 (15)	0.0426 (6)
C12	0.4304 (6)	0.46675 (15)	0.37652 (18)	0.0503 (7)
H12A	0.3004	0.4534	0.4157	0.060*
H12B	0.3171	0.4916	0.3346	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0337 (12)	0.0558 (13)	0.154 (3)	0.0049 (10)	0.0002 (13)	−0.0304 (15)
Cl1	0.0735 (6)	0.0549 (5)	0.0603 (5)	−0.0049 (4)	−0.0212 (4)	0.0010 (3)
C1	0.0494 (16)	0.0346 (13)	0.0471 (15)	−0.0013 (12)	0.0018 (12)	0.0003 (11)
Cl2	0.0949 (7)	0.0570 (5)	0.0673 (5)	0.0099 (4)	−0.0091 (5)	0.0194 (4)
N1	0.0480 (13)	0.0351 (11)	0.0440 (12)	−0.0008 (10)	−0.0004 (10)	−0.0051 (9)
N2	0.0626 (15)	0.0326 (11)	0.0507 (13)	0.0051 (10)	0.0013 (11)	−0.0040 (10)
C2	0.0482 (15)	0.0410 (14)	0.0448 (14)	0.0018 (12)	0.0021 (12)	−0.0013 (11)
Cl3	0.0585 (5)	0.0442 (4)	0.0767 (5)	−0.0064 (3)	−0.0043 (4)	−0.0129 (3)
C3	0.0626 (19)	0.0423 (15)	0.0440 (15)	0.0078 (13)	0.0044 (13)	0.0068 (11)
N3	0.138 (3)	0.0591 (19)	0.087 (2)	0.036 (2)	−0.001 (2)	0.0074 (16)
N4	0.0297 (11)	0.0483 (13)	0.0576 (13)	0.0067 (9)	−0.0046 (10)	−0.0182 (11)
C4	0.080 (2)	0.0360 (14)	0.0583 (18)	−0.0048 (14)	0.0049 (17)	0.0047 (12)
C5	0.067 (2)	0.0373 (14)	0.0515 (16)	−0.0100 (13)	0.0020 (14)	−0.0023 (12)
C6	0.0457 (14)	0.0339 (13)	0.0441 (14)	−0.0012 (11)	0.0040 (12)	−0.0037 (10)
C7	0.0361 (14)	0.0427 (14)	0.0485 (15)	0.0016 (11)	0.0005 (12)	−0.0111 (12)
C8	0.0557 (18)	0.0526 (17)	0.0526 (16)	0.0086 (14)	−0.0061 (14)	−0.0082 (13)
C9	0.0557 (17)	0.0393 (14)	0.0508 (16)	0.0054 (13)	−0.0012 (13)	−0.0021 (12)
C10	0.086 (2)	0.0515 (18)	0.0538 (17)	0.0120 (17)	−0.0060 (17)	−0.0009 (14)
C11	0.0333 (14)	0.0406 (14)	0.0535 (16)	0.0032 (11)	−0.0002 (12)	−0.0024 (11)
C12	0.0385 (15)	0.0445 (15)	0.0673 (18)	0.0007 (12)	−0.0006 (13)	−0.0132 (13)

Geometric parameters (Å, º) top

O—C11	1.210 (3)	N4—C11	1.335 (3)
Cl1—C2	1.726 (3)	N4—C7	1.402 (3)
C1—C2	1.374 (4)	N4—H4A	0.8600
C1—C6	1.375 (3)	C4—C5	1.378 (4)
C1—H1A	0.9300	C4—H4B	0.9300
Cl2—C3	1.728 (3)	C5—C6	1.384 (4)
N1—N2	1.356 (3)	C5—H5A	0.9300
N1—C7	1.360 (3)	C7—C8	1.348 (4)
N1—C6	1.427 (3)	C8—C9	1.393 (4)
N2—C9	1.330 (3)	C8—H8A	0.9300
C2—C3	1.388 (4)	C9—C10	1.438 (4)
Cl3—C12	1.754 (3)	C11—C12	1.511 (4)
C3—C4	1.376 (4)	C12—H12A	0.9700
N3—C10	1.127 (4)	C12—H12B	0.9700

C2—C1—C6	119.7 (2)	C1—C6—C5	121.0 (3)
C2—C1—H1A	120.2	C1—C6—N1	118.8 (2)
C6—C1—H1A	120.2	C5—C6—N1	120.1 (2)
N2—N1—C7	111.4 (2)	C8—C7—N1	107.8 (2)
N2—N1—C6	118.88 (19)	C8—C7—N4	131.1 (2)
C7—N1—C6	129.7 (2)	N1—C7—N4	121.0 (2)
C9—N2—N1	103.7 (2)	C7—C8—C9	104.4 (3)
C1—C2—C3	120.3 (3)	C7—C8—H8A	127.8
C1—C2—Cl1	118.9 (2)	C9—C8—H8A	127.8
C3—C2—Cl1	120.9 (2)	N2—C9—C8	112.7 (2)
C4—C3—C2	119.3 (3)	N2—C9—C10	120.4 (2)
C4—C3—Cl2	119.7 (2)	C8—C9—C10	126.8 (3)
C2—C3—Cl2	121.0 (2)	N3—C10—C9	177.1 (4)
C11—N4—C7	122.4 (2)	O—C11—N4	123.1 (2)
C11—N4—H4A	118.8	O—C11—C12	123.3 (2)
C7—N4—H4A	118.8	N4—C11—C12	113.5 (2)
C3—C4—C5	121.2 (3)	C11—C12—Cl3	111.68 (19)
C3—C4—H4B	119.4	C11—C12—H12A	109.3
C5—C4—H4B	119.4	Cl3—C12—H12A	109.3
C4—C5—C6	118.6 (3)	C11—C12—H12B	109.3
C4—C5—H5A	120.7	Cl3—C12—H12B	109.3
C6—C5—H5A	120.7	H12A—C12—H12B	107.9

C7—N1—N2—C9	−1.5 (3)	N2—N1—C7—C8	1.7 (3)
C6—N1—N2—C9	176.8 (2)	C6—N1—C7—C8	−176.4 (3)
C6—C1—C2—C3	−1.6 (4)	N2—N1—C7—N4	−175.1 (2)
C6—C1—C2—Cl1	177.7 (2)	C6—N1—C7—N4	6.9 (4)
C1—C2—C3—C4	1.6 (4)	C11—N4—C7—C8	51.2 (5)
Cl1—C2—C3—C4	−177.7 (2)	C11—N4—C7—N1	−132.9 (3)
C1—C2—C3—Cl2	−179.5 (2)	N1—C7—C8—C9	−1.1 (3)
Cl1—C2—C3—Cl2	1.1 (4)	N4—C7—C8—C9	175.2 (3)
C2—C3—C4—C5	−0.1 (5)	N1—N2—C9—C8	0.8 (3)
Cl2—C3—C4—C5	−178.9 (2)	N1—N2—C9—C10	−179.3 (3)
C3—C4—C5—C6	−1.5 (5)	C7—C8—C9—N2	0.2 (4)
C2—C1—C6—C5	0.1 (4)	C7—C8—C9—C10	−179.7 (3)
C2—C1—C6—N1	−177.2 (2)	N2—C9—C10—N3	176 (8)
C4—C5—C6—C1	1.5 (4)	C8—C9—C10—N3	−4 (9)
C4—C5—C6—N1	178.7 (3)	C7—N4—C11—O	3.5 (5)
N2—N1—C6—C1	35.1 (3)	C7—N4—C11—C12	−175.1 (2)
C7—N1—C6—C1	−147.0 (3)	O—C11—C12—Cl3	2.4 (4)
N2—N1—C6—C5	−142.2 (3)	N4—C11—C12—Cl3	−179.0 (2)
C7—N1—C6—C5	35.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Oⁱ	0.86	1.95	2.743 (3)	153

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₇Cl₃N₄O
M_r	329.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.6280 (9), 17.245 (3), 17.468 (4)
β (°)	94.04 (3)
V (Å³)	1390.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.827, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	5687, 2564, 1880
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.139, 1.01
No. of reflections	2564
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Oⁱ	0.86	1.95	2.743 (3)	153

Symmetry code: (i) x−1, y, z.

References

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Liu, Y. Y., Shi, H., Li, Y. F. & Zhu, H. J. (2010). J. Heterocycl. Chem. 47, 897–902. Web of Science CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, Q. Q., Li, Y. Q., Xiong, L. X. & Wang, Q. M. (2010). J. Agric. Food Chem. 58, 4992–4998. Web of Science CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1150

doi:10.1107/S1600536812008094

Open

access