2-Chloro-N-[1-(4-chloro-phen-yl)-3-cyano-1H-pyrazol-5-yl]acetamide.

The title compound, C(12)H(8)Cl(2)N(4)O, was synthesized by the reaction of 5-amino-1-(4-chloro-phen-yl)-1H-pyrazole-3-carbonitrile and 2-chloro-acetyl chloride. The dihedral angle between the pyrazole and benzene rings is 30.7 (3)°. In the crystal structure, strong N-H⋯O hydrogen bonds link the mol-ecules into chains along [001]. C-H⋯N hydrogen bonds are also present.

Related literature

The title compound is important in the synthesis of derivatives of the insecticide Fipronil {systematic name: (RS)-5-amino-1-[2,6-dichloro-4-(trifluoro­meth­yl)phen­yl]-4-(trifluoro­methyl­sulfin­yl)-1H-pyrazole-3-carbonitrile}. For the biological activity of N-pyrazole derivatives, see: Zhao et al. (2010 ▶); Liu et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the structure of 2-chloro-N-(3-cyano-1-(2,6-dichloro-4-(tri­fluoro­meth­yl)phen­yl)-1H-pyrazol-5-yl)acetamide, see: Zhang et al. (2012 ▶).

Experimental

Crystal data

C12H8Cl2N4O

M = 295.12

Orthorhombic,

a = 18.493 (4) Å

b = 13.815 (3) Å

c = 5.060 (1) Å

V = 1292.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.50 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 = 0.865, T max = 0.952

2646 measured reflections

2606 independent reflections

2255 reflections with I > 2σ(I)

R int = 0.024

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 1.01

2606 reflections

173 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶), 1271 Friedel pairs

Flack parameter: 0.09 (9)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 EXPRESS; 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: SHELXS97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043966/rn2106sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043966/rn2106Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043966/rn2106Isup3.cml

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

C12H8Cl2N4O	Dx = 1.516 Mg m−3
Mr = 295.12	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 25 reflections
a = 18.493 (4) Å	θ = 9–13°
b = 13.815 (3) Å	µ = 0.50 mm−1
c = 5.060 (1) Å	T = 293 K
V = 1292.7 (4) Å3	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm
F(000) = 600

Enraf–Nonius CAD-4 diffractometer	2255 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.4°, θmin = 2.2°
ω/2θ scans	h = −22→22
Absorption correction: ψ scan (North et al., 1968)	k = 0→16
Tmin = 0.865, Tmax = 0.952	l = −6→0
2646 measured reflections	3 standard reflections every 200 reflections
2606 independent reflections	intensity decay: 1%

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.064P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.16 e Å−3
2606 reflections	Δρmin = −0.24 e Å−3
173 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.023 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1271 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.09 (9)

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.

	x	y	z	Uiso*/Ueq
O	0.20761 (11)	0.90238 (15)	−0.4786 (4)	0.0473 (5)
Cl1	0.07270 (4)	0.51152 (5)	0.76028 (19)	0.0634 (3)
N1	0.27787 (9)	0.73978 (13)	0.1128 (5)	0.0330 (5)
C1	0.25223 (13)	0.63629 (18)	0.4875 (6)	0.0385 (6)
H1A	0.3011	0.6381	0.5309	0.046*
Cl2	0.07546 (4)	0.99063 (6)	0.07496 (17)	0.0548 (2)
N2	0.34595 (10)	0.70361 (14)	0.0940 (6)	0.0397 (5)
C2	0.20505 (14)	0.58124 (18)	0.6366 (6)	0.0428 (7)
H2B	0.2220	0.5449	0.7785	0.051*
N3	0.20572 (11)	0.87436 (15)	−0.0382 (5)	0.0339 (5)
H3A	0.1824	0.8829	0.1070	0.041*
C3	0.13257 (15)	0.58071 (18)	0.5729 (6)	0.0432 (6)
C4	0.10698 (14)	0.63335 (19)	0.3602 (7)	0.0442 (7)
H4A	0.0579	0.6325	0.3198	0.053*
N4	0.51184 (12)	0.73394 (18)	−0.1943 (8)	0.0707 (9)
C5	0.15393 (13)	0.68719 (18)	0.2079 (6)	0.0407 (6)
H5A	0.1370	0.7220	0.0632	0.049*
C6	0.22697 (12)	0.68864 (16)	0.2739 (6)	0.0330 (6)
C7	0.27029 (12)	0.82144 (17)	−0.0352 (5)	0.0329 (6)
C8	0.33442 (12)	0.83866 (18)	−0.1594 (6)	0.0388 (6)
H8A	0.3457	0.8887	−0.2752	0.047*
C9	0.37887 (13)	0.76412 (17)	−0.0731 (6)	0.0390 (6)
C10	0.45341 (15)	0.74665 (18)	−0.1393 (8)	0.0492 (8)
C11	0.17925 (12)	0.91243 (17)	−0.2649 (5)	0.0314 (5)
C12	0.10972 (13)	0.96827 (18)	−0.2494 (6)	0.0357 (6)
H12B	0.0732	0.9332	−0.3483	0.043*
H12C	0.1168	1.0301	−0.3365	0.043*

	U11	U22	U33	U12	U13	U23
O	0.0494 (11)	0.0672 (14)	0.0253 (11)	0.0153 (10)	0.0035 (9)	0.0035 (9)
Cl1	0.0730 (5)	0.0656 (5)	0.0516 (5)	−0.0249 (4)	0.0147 (5)	0.0028 (5)
N1	0.0321 (10)	0.0332 (10)	0.0337 (13)	0.0041 (8)	−0.0021 (10)	−0.0001 (11)
C1	0.0422 (14)	0.0375 (14)	0.0358 (16)	0.0021 (11)	−0.0055 (13)	−0.0011 (12)
Cl2	0.0469 (4)	0.0817 (5)	0.0359 (4)	0.0234 (3)	0.0066 (4)	−0.0023 (4)
N2	0.0315 (10)	0.0376 (10)	0.0499 (15)	0.0067 (8)	−0.0030 (11)	0.0018 (13)
C2	0.0568 (16)	0.0392 (13)	0.0324 (16)	0.0039 (12)	−0.0011 (13)	0.0053 (13)
N3	0.0391 (11)	0.0391 (12)	0.0235 (11)	0.0119 (9)	0.0029 (10)	0.0032 (10)
C3	0.0561 (16)	0.0395 (13)	0.0341 (15)	−0.0064 (11)	0.0088 (15)	−0.0043 (14)
C4	0.0385 (14)	0.0512 (16)	0.0430 (17)	−0.0066 (12)	0.0014 (14)	−0.0034 (15)
N4	0.0401 (14)	0.0684 (16)	0.104 (3)	0.0034 (11)	0.0086 (17)	0.008 (2)
C5	0.0430 (14)	0.0443 (14)	0.0348 (16)	0.0042 (11)	−0.0031 (12)	0.0025 (13)
C6	0.0360 (12)	0.0303 (11)	0.0328 (14)	0.0022 (9)	0.0007 (11)	−0.0015 (12)
C7	0.0346 (12)	0.0344 (13)	0.0298 (13)	0.0039 (10)	−0.0011 (12)	−0.0003 (12)
C8	0.0409 (13)	0.0370 (13)	0.0384 (16)	0.0004 (11)	0.0043 (13)	0.0043 (13)
C9	0.0324 (12)	0.0382 (13)	0.0465 (17)	−0.0010 (11)	0.0011 (13)	−0.0002 (13)
C10	0.0397 (14)	0.0411 (15)	0.067 (2)	−0.0002 (11)	0.0052 (15)	0.0078 (16)
C11	0.0344 (12)	0.0338 (12)	0.0259 (13)	0.0009 (9)	−0.0002 (12)	0.0016 (12)
C12	0.0366 (12)	0.0425 (13)	0.0279 (13)	0.0059 (10)	−0.0019 (12)	0.0030 (13)

O—C11	1.210 (3)	N3—H3A	0.8600
Cl1—C3	1.743 (3)	C3—C4	1.382 (4)
N1—N2	1.358 (2)	C4—C5	1.379 (4)
N1—C7	1.361 (3)	C4—H4A	0.9300
N1—C6	1.431 (3)	N4—C10	1.129 (3)
C1—C6	1.382 (4)	C5—C6	1.391 (3)
C1—C2	1.382 (4)	C5—H5A	0.9300
C1—H1A	0.9300	C7—C8	1.363 (3)
Cl2—C12	1.786 (3)	C8—C9	1.388 (3)
N2—C9	1.336 (4)	C8—H8A	0.9300
C2—C3	1.379 (4)	C9—C10	1.439 (4)
C2—H2B	0.9300	C11—C12	1.502 (3)
N3—C11	1.354 (3)	C12—H12B	0.9700
N3—C7	1.400 (3)	C12—H12C	0.9700
N2—N1—C7	111.21 (19)	C1—C6—C5	120.6 (2)
N2—N1—C6	117.91 (19)	C1—C6—N1	118.8 (2)
C7—N1—C6	130.88 (18)	C5—C6—N1	120.6 (2)
C6—C1—C2	120.1 (2)	N1—C7—C8	108.0 (2)
C6—C1—H1A	119.9	N1—C7—N3	121.8 (2)
C2—C1—H1A	119.9	C8—C7—N3	130.2 (2)
C9—N2—N1	103.70 (19)	C7—C8—C9	103.9 (2)
C3—C2—C1	119.3 (3)	C7—C8—H8A	128.0
C3—C2—H2B	120.4	C9—C8—H8A	128.0
C1—C2—H2B	120.4	N2—C9—C8	113.2 (2)
C11—N3—C7	121.4 (2)	N2—C9—C10	118.6 (2)
C11—N3—H3A	119.3	C8—C9—C10	128.2 (3)
C7—N3—H3A	119.3	N4—C10—C9	179.0 (4)
C2—C3—C4	120.8 (3)	O—C11—N3	123.8 (2)
C2—C3—Cl1	119.6 (2)	O—C11—C12	118.5 (2)
C4—C3—Cl1	119.6 (2)	N3—C11—C12	117.7 (2)
C5—C4—C3	120.2 (2)	C11—C12—Cl2	116.15 (19)
C5—C4—H4A	119.9	C11—C12—H12B	108.2
C3—C4—H4A	119.9	Cl2—C12—H12B	108.2
C4—C5—C6	119.0 (3)	C11—C12—H12C	108.2
C4—C5—H5A	120.5	Cl2—C12—H12C	108.2
C6—C5—H5A	120.5	H12B—C12—H12C	107.4
C7—N1—N2—C9	−1.3 (3)	C6—N1—C7—C8	−177.8 (3)
C6—N1—N2—C9	178.0 (2)	N2—N1—C7—N3	−177.1 (2)
C6—C1—C2—C3	−1.2 (4)	C6—N1—C7—N3	3.8 (4)
C1—C2—C3—C4	0.9 (4)	C11—N3—C7—N1	−139.4 (3)
C1—C2—C3—Cl1	−179.9 (2)	C11—N3—C7—C8	42.6 (4)
C2—C3—C4—C5	0.2 (4)	N1—C7—C8—C9	−0.7 (3)
Cl1—C3—C4—C5	−179.0 (2)	N3—C7—C8—C9	177.5 (3)
C3—C4—C5—C6	−0.9 (4)	N1—N2—C9—C8	0.8 (3)
C2—C1—C6—C5	0.5 (4)	N1—N2—C9—C10	−179.9 (3)
C2—C1—C6—N1	−175.9 (2)	C7—C8—C9—N2	−0.1 (3)
C4—C5—C6—C1	0.5 (4)	C7—C8—C9—C10	−179.3 (3)
C4—C5—C6—N1	176.9 (2)	N2—C9—C10—N4	169 (22)
N2—N1—C6—C1	29.2 (3)	C8—C9—C10—N4	−12 (22)
C7—N1—C6—C1	−151.8 (3)	C7—N3—C11—O	1.6 (4)
N2—N1—C6—C5	−147.2 (2)	C7—N3—C11—C12	−179.9 (2)
C7—N1—C6—C5	31.8 (4)	O—C11—C12—Cl2	−174.0 (2)
N2—N1—C7—C8	1.3 (3)	N3—C11—C12—Cl2	7.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Oi	0.86	2.16	2.858 (3)	137
C12—H12C···N2ii	0.97	2.52	3.445 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Oi	0.86	2.16	2.858 (3)	137
C12—H12C⋯N2ii	0.97	2.52	3.445 (3)	160

Symmetry codes: (i) ; (ii) .