organic compounds
2-Chloro-N-[1-(4-chlorophenyl)-3-cyano-1H-pyrazol-5-yl]acetamide
aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: rwan@njut.edu.cn
The title compound, C12H8Cl2N4O, was synthesized by the reaction of 5-amino-1-(4-chlorophenyl)-1H-pyrazole-3-carbonitrile and 2-chloroacetyl chloride. The dihedral angle between the pyrazole and benzene rings is 30.7 (3)°. In the strong N—H⋯O hydrogen bonds link the molecules 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
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Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell 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.
Supporting information
10.1107/S1600536812043966/rn2106sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043966/rn2106Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043966/rn2106Isup3.cml
To a stirred solution of 5-amino-1-(4-chlorophenyl)-1H-pyrazole-3-carbonitrile (5 mmol) in THF (20 ml) was added 2-chloroacetyl chloride (5 mmol) dropwise at 0–5°C. During the addition, the solution is cooled in an ice-salt bath. After the cooling bath had been removed, the reaction mixture was allowed to stand for 2 h at room temperature. The crude product (I) precipitated and was filtered. Pure compound (I) was obtained by crystallization from ethanol. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.
All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.97 Å and included in the
in riding motion approximation with Uiso(H) = 1.2 or 1.5Ueq of the carrier atom.Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell
CAD-4 EXPRESS (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: SHELXS97 (Sheldrick, 2008).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 | Absolute structure parameter: 0.09 (9) |
C12H8Cl2N4O | V = 1292.7 (4) Å3 |
Mr = 295.12 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 18.493 (4) Å | µ = 0.50 mm−1 |
b = 13.815 (3) Å | T = 293 K |
c = 5.060 (1) Å | 0.30 × 0.20 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 2255 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.865, Tmax = 0.952 | 3 standard reflections every 200 reflections |
2646 measured reflections | intensity decay: 1% |
2606 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 0.16 e Å−3 |
S = 1.01 | Δρmin = −0.24 e Å−3 |
2606 reflections | Absolute structure: Flack (1983), 1271 Friedel pairs |
173 parameters | Absolute structure parameter: 0.09 (9) |
1 restraint |
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 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H8Cl2N4O |
Mr | 295.12 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 293 |
a, b, c (Å) | 18.493 (4), 13.815 (3), 5.060 (1) |
V (Å3) | 1292.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.865, 0.952 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2646, 2606, 2255 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.604 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.01 |
No. of reflections | 2606 |
No. of parameters | 173 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.24 |
Absolute structure | Flack (1983), 1271 Friedel pairs |
Absolute structure parameter | 0.09 (9) |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···Oi | 0.8600 | 2.1600 | 2.858 (3) | 137.00 |
C12—H12C···N2ii | 0.9700 | 2.5200 | 3.445 (3) | 160.00 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y+1/2, z−1/2. |
Acknowledgements
The authors thank the Science and Technology Project of Jiangsu Province (No. BE2011352) for financial support and acknowledge the help of members of the laboratory.
References
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N-Pyrazole derivatives are of great interest because of their diverse biological activities such as insecticidal (Zhao et al., 2010) and antifungal activities (Liu et al., 2010). The title compound is an important intermediate in the synthesis of N-aromatic pyrazole derivatives. The molecular structure of (I) is shown in Fig.1. In this structure, bond length and angles are within the normal range (Allen et al., 1987) and the mean deviation from the plane(N1/N2/C9/C8/C7) is 0.0045 Å. The dihedral angle between the pyrazole and phenyl ring in compound (I) is 30.7 (3)°, which is smaller than the angle in the structure of 2-chloro-N- (3-cyano-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-1H-pyrazol-5-yl) acetamide (Zhang et al., 2012), which is 71.5 (3)°. While bond lengths of the two compounds are similar, the difference in the dihedral angle probably results from greater steric hindrance in the (trifluoromethyl)phenyl derivative. In the crystal structure, strong N—H···O hydrogen bonds link the molecules into infinite one-dimensional chains along the [001] direction. Intermolecular C—H···N and N—H···O hydrogen bonds (Table 1) may help to establish the molecular conformation of (I). (Fig. 2)