Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055390/kj2071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055390/kj2071Isup2.hkl |
CCDC reference: 672876
A solution of 5-chloro-3-methyl-1-H-pyrazole-4-carbalhedyde (5 mmol) and aniline (6 mmol) in anhydrous ethanol (20 ml) were stirred under reflux until the reaction was completed (monitored by thin-layer chromatography). After removal of ethanol under reduced pressure, the residue was recrystallized from ethanol to give the target compound as a yellow solid (yield: 86%, m.p. 395–397 K). A crystal grown from anhydrous ethanol was selected for X-ray structure analysis.
H atoms bonded to C were placed at calculated positions, with C—H distances of 0.97 and 0.93 Å for H atoms bonded to sp3 and sp2 C atoms, respectively. They were refined using a riding model, with Uiso(H)=1.2Ueq(C),but the methyl H atoms with Uiso(H)=1.5Ueq(C).
Data collection: APEX2 (Bruker 2004); cell refinement: APEX2 (Bruker 2004); data reduction: SAINT (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2004); software used to prepare material for publication: SHELXTL (Bruker 2004).
Fig. 1. A view of the molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
C17H14ClN3 | F(000) = 616 |
Mr = 295.76 | Dx = 1.318 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7837 (9) Å | Cell parameters from 9958 reflections |
b = 11.0980 (12) Å | θ = 12–18° |
c = 15.6749 (16) Å | µ = 0.25 mm−1 |
β = 102.648 (1)° | T = 293 K |
V = 1490.9 (3) Å3 | Block, yellow |
Z = 4 | 0.40 × 0.19 × 0.18 mm |
Bruker APEXII CCD area-detector diffractometer | 2751 independent reflections |
Radiation source: fine-focus sealed tube | 2248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.816, Tmax = 0.955 | k = −13→13 |
9958 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0366P)2 + 0.4599P] where P = (Fo2 + 2Fc2)/3 |
2751 reflections | (Δ/σ)max = 0.002 |
191 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C17H14ClN3 | V = 1490.9 (3) Å3 |
Mr = 295.76 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.7837 (9) Å | µ = 0.25 mm−1 |
b = 11.0980 (12) Å | T = 293 K |
c = 15.6749 (16) Å | 0.40 × 0.19 × 0.18 mm |
β = 102.648 (1)° |
Bruker APEXII CCD area-detector diffractometer | 2751 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2248 reflections with I > 2σ(I) |
Tmin = 0.816, Tmax = 0.955 | Rint = 0.021 |
9958 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.17 e Å−3 |
2751 reflections | Δρmin = −0.21 e Å−3 |
191 parameters |
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 | ||
Cl1 | 0.63039 (5) | 0.64323 (4) | 1.01319 (3) | 0.05415 (16) | |
N1 | 0.74453 (16) | 0.43848 (11) | 1.09347 (8) | 0.0404 (3) | |
N2 | 0.82316 (17) | 0.33487 (12) | 1.08197 (9) | 0.0440 (3) | |
N3 | 0.86228 (18) | 0.43674 (13) | 0.82194 (9) | 0.0515 (4) | |
C1 | 0.7028 (2) | 0.55738 (16) | 1.21758 (12) | 0.0531 (5) | |
H1 | 0.7539 | 0.6225 | 1.1991 | 0.064* | |
C2 | 0.6436 (3) | 0.56587 (18) | 1.29239 (12) | 0.0633 (5) | |
H2 | 0.6532 | 0.6377 | 1.3237 | 0.076* | |
C3 | 0.5710 (3) | 0.46867 (18) | 1.32053 (13) | 0.0627 (5) | |
H3 | 0.5322 | 0.4749 | 1.3710 | 0.075* | |
C4 | 0.5553 (2) | 0.36212 (17) | 1.27452 (12) | 0.0558 (5) | |
H4 | 0.5069 | 0.2964 | 1.2941 | 0.067* | |
C5 | 0.6118 (2) | 0.35303 (15) | 1.19894 (11) | 0.0466 (4) | |
H5 | 0.6007 | 0.2815 | 1.1672 | 0.056* | |
C6 | 0.68477 (19) | 0.45104 (14) | 1.17102 (10) | 0.0406 (4) | |
C7 | 0.73015 (19) | 0.50980 (14) | 1.02245 (10) | 0.0402 (4) | |
C8 | 0.80029 (19) | 0.45418 (15) | 0.96253 (10) | 0.0409 (4) | |
C9 | 0.85765 (19) | 0.34494 (15) | 1.00415 (10) | 0.0418 (4) | |
C10 | 0.9500 (2) | 0.24798 (17) | 0.97332 (12) | 0.0559 (5) | |
H10A | 0.9787 | 0.1883 | 1.0183 | 0.084* | |
H10B | 1.0425 | 0.2820 | 0.9599 | 0.084* | |
H10C | 0.8883 | 0.2111 | 0.9218 | 0.084* | |
C11 | 0.8068 (2) | 0.49883 (16) | 0.87614 (11) | 0.0454 (4) | |
H11 | 0.7690 | 0.5757 | 0.8600 | 0.055* | |
C12 | 0.8679 (2) | 0.48835 (16) | 0.73967 (11) | 0.0470 (4) | |
C13 | 0.9156 (2) | 0.60538 (18) | 0.73050 (12) | 0.0540 (5) | |
H13 | 0.9405 | 0.6556 | 0.7790 | 0.065* | |
C14 | 0.9263 (3) | 0.6478 (2) | 0.64888 (13) | 0.0655 (6) | |
H14 | 0.9594 | 0.7264 | 0.6431 | 0.079* | |
C15 | 0.8887 (3) | 0.5751 (2) | 0.57643 (13) | 0.0687 (6) | |
H15 | 0.8960 | 0.6043 | 0.5219 | 0.082* | |
C16 | 0.8404 (3) | 0.4591 (2) | 0.58506 (13) | 0.0685 (6) | |
H16 | 0.8134 | 0.4100 | 0.5360 | 0.082* | |
C17 | 0.8315 (2) | 0.41479 (19) | 0.66612 (12) | 0.0604 (5) | |
H17 | 0.8010 | 0.3354 | 0.6716 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0622 (3) | 0.0463 (3) | 0.0581 (3) | 0.0086 (2) | 0.0222 (2) | 0.0086 (2) |
N1 | 0.0501 (8) | 0.0379 (7) | 0.0369 (7) | −0.0010 (6) | 0.0173 (6) | 0.0002 (6) |
N2 | 0.0564 (9) | 0.0391 (8) | 0.0394 (8) | 0.0010 (6) | 0.0168 (7) | 0.0005 (6) |
N3 | 0.0644 (10) | 0.0532 (9) | 0.0419 (8) | 0.0009 (7) | 0.0223 (7) | 0.0059 (7) |
C1 | 0.0696 (12) | 0.0448 (10) | 0.0489 (10) | −0.0097 (9) | 0.0220 (9) | −0.0056 (8) |
C2 | 0.0918 (16) | 0.0539 (12) | 0.0504 (11) | −0.0034 (11) | 0.0293 (11) | −0.0144 (9) |
C3 | 0.0837 (15) | 0.0666 (13) | 0.0474 (11) | 0.0015 (11) | 0.0351 (10) | −0.0037 (9) |
C4 | 0.0721 (13) | 0.0549 (11) | 0.0477 (10) | −0.0054 (9) | 0.0289 (9) | 0.0048 (9) |
C5 | 0.0605 (11) | 0.0423 (9) | 0.0411 (9) | −0.0021 (8) | 0.0196 (8) | −0.0001 (7) |
C6 | 0.0477 (10) | 0.0435 (9) | 0.0330 (8) | 0.0000 (7) | 0.0140 (7) | 0.0006 (7) |
C7 | 0.0437 (9) | 0.0381 (9) | 0.0406 (9) | −0.0039 (7) | 0.0134 (7) | 0.0032 (7) |
C8 | 0.0433 (9) | 0.0443 (9) | 0.0379 (8) | −0.0059 (7) | 0.0151 (7) | 0.0004 (7) |
C9 | 0.0474 (10) | 0.0422 (9) | 0.0387 (9) | −0.0036 (7) | 0.0156 (7) | −0.0012 (7) |
C10 | 0.0671 (12) | 0.0535 (11) | 0.0542 (11) | 0.0063 (9) | 0.0285 (9) | 0.0004 (9) |
C11 | 0.0483 (10) | 0.0474 (10) | 0.0434 (9) | −0.0016 (8) | 0.0161 (8) | 0.0069 (8) |
C12 | 0.0489 (10) | 0.0554 (11) | 0.0406 (9) | 0.0078 (8) | 0.0185 (8) | 0.0078 (8) |
C13 | 0.0572 (11) | 0.0635 (12) | 0.0431 (10) | −0.0049 (9) | 0.0149 (8) | 0.0047 (9) |
C14 | 0.0731 (14) | 0.0708 (14) | 0.0569 (12) | −0.0066 (11) | 0.0240 (10) | 0.0171 (10) |
C15 | 0.0809 (15) | 0.0877 (16) | 0.0448 (11) | 0.0160 (13) | 0.0295 (10) | 0.0163 (11) |
C16 | 0.0896 (16) | 0.0768 (15) | 0.0441 (11) | 0.0179 (12) | 0.0257 (10) | −0.0026 (10) |
C17 | 0.0789 (14) | 0.0554 (11) | 0.0529 (11) | 0.0069 (10) | 0.0279 (10) | 0.0002 (9) |
Cl1—C7 | 1.7106 (17) | C8—C9 | 1.416 (2) |
N1—C7 | 1.349 (2) | C8—C11 | 1.455 (2) |
N1—N2 | 1.3734 (18) | C9—C10 | 1.490 (2) |
N1—C6 | 1.4324 (19) | C10—H10A | 0.9600 |
N2—C9 | 1.324 (2) | C10—H10B | 0.9600 |
N3—C11 | 1.271 (2) | C10—H10C | 0.9600 |
N3—C12 | 1.422 (2) | C11—H11 | 0.9300 |
C1—C6 | 1.378 (2) | C12—C13 | 1.382 (3) |
C1—C2 | 1.386 (2) | C12—C17 | 1.392 (3) |
C1—H1 | 0.9300 | C13—C14 | 1.386 (2) |
C2—C3 | 1.374 (3) | C13—H13 | 0.9300 |
C2—H2 | 0.9300 | C14—C15 | 1.373 (3) |
C3—C4 | 1.376 (3) | C14—H14 | 0.9300 |
C3—H3 | 0.9300 | C15—C16 | 1.371 (3) |
C4—C5 | 1.384 (2) | C15—H15 | 0.9300 |
C4—H4 | 0.9300 | C16—C17 | 1.381 (3) |
C5—C6 | 1.382 (2) | C16—H16 | 0.9300 |
C5—H5 | 0.9300 | C17—H17 | 0.9300 |
C7—C8 | 1.377 (2) | ||
C7—N1—N2 | 109.99 (13) | N2—C9—C10 | 119.23 (15) |
C7—N1—C6 | 131.12 (14) | C8—C9—C10 | 129.25 (15) |
N2—N1—C6 | 118.76 (12) | C9—C10—H10A | 109.5 |
C9—N2—N1 | 105.86 (13) | C9—C10—H10B | 109.5 |
C11—N3—C12 | 118.84 (15) | H10A—C10—H10B | 109.5 |
C6—C1—C2 | 119.03 (17) | C9—C10—H10C | 109.5 |
C6—C1—H1 | 120.5 | H10A—C10—H10C | 109.5 |
C2—C1—H1 | 120.5 | H10B—C10—H10C | 109.5 |
C3—C2—C1 | 120.31 (18) | N3—C11—C8 | 122.45 (16) |
C3—C2—H2 | 119.8 | N3—C11—H11 | 118.8 |
C1—C2—H2 | 119.8 | C8—C11—H11 | 118.8 |
C2—C3—C4 | 120.43 (17) | C13—C12—C17 | 119.01 (16) |
C2—C3—H3 | 119.8 | C13—C12—N3 | 123.00 (16) |
C4—C3—H3 | 119.8 | C17—C12—N3 | 117.90 (17) |
C3—C4—C5 | 119.84 (17) | C12—C13—C14 | 119.93 (18) |
C3—C4—H4 | 120.1 | C12—C13—H13 | 120.0 |
C5—C4—H4 | 120.1 | C14—C13—H13 | 120.0 |
C6—C5—C4 | 119.45 (16) | C15—C14—C13 | 120.7 (2) |
C6—C5—H5 | 120.3 | C15—C14—H14 | 119.6 |
C4—C5—H5 | 120.3 | C13—C14—H14 | 119.6 |
C1—C6—C5 | 120.92 (15) | C16—C15—C14 | 119.58 (18) |
C1—C6—N1 | 120.77 (15) | C16—C15—H15 | 120.2 |
C5—C6—N1 | 118.29 (14) | C14—C15—H15 | 120.2 |
N1—C7—C8 | 108.96 (14) | C15—C16—C17 | 120.4 (2) |
N1—C7—Cl1 | 122.11 (12) | C15—C16—H16 | 119.8 |
C8—C7—Cl1 | 128.87 (13) | C17—C16—H16 | 119.8 |
C7—C8—C9 | 103.69 (14) | C16—C17—C12 | 120.3 (2) |
C7—C8—C11 | 126.65 (16) | C16—C17—H17 | 119.9 |
C9—C8—C11 | 129.64 (15) | C12—C17—H17 | 119.9 |
N2—C9—C8 | 111.50 (14) | ||
C7—N1—N2—C9 | 0.75 (18) | Cl1—C7—C8—C11 | 0.9 (3) |
C6—N1—N2—C9 | 176.95 (14) | N1—N2—C9—C8 | −0.95 (18) |
C6—C1—C2—C3 | 1.3 (3) | N1—N2—C9—C10 | 177.53 (15) |
C1—C2—C3—C4 | −0.4 (3) | C7—C8—C9—N2 | 0.79 (19) |
C2—C3—C4—C5 | −0.6 (3) | C11—C8—C9—N2 | −177.42 (16) |
C3—C4—C5—C6 | 0.6 (3) | C7—C8—C9—C10 | −177.49 (18) |
C2—C1—C6—C5 | −1.3 (3) | C11—C8—C9—C10 | 4.3 (3) |
C2—C1—C6—N1 | −179.85 (17) | C12—N3—C11—C8 | −178.45 (16) |
C4—C5—C6—C1 | 0.3 (3) | C7—C8—C11—N3 | −173.72 (17) |
C4—C5—C6—N1 | 178.91 (16) | C9—C8—C11—N3 | 4.1 (3) |
C7—N1—C6—C1 | −49.2 (3) | C11—N3—C12—C13 | 43.5 (3) |
N2—N1—C6—C1 | 135.51 (17) | C11—N3—C12—C17 | −140.12 (18) |
C7—N1—C6—C5 | 132.20 (18) | C17—C12—C13—C14 | 0.1 (3) |
N2—N1—C6—C5 | −43.1 (2) | N3—C12—C13—C14 | 176.48 (18) |
N2—N1—C7—C8 | −0.27 (19) | C12—C13—C14—C15 | 0.5 (3) |
C6—N1—C7—C8 | −175.84 (15) | C13—C14—C15—C16 | −0.2 (3) |
N2—N1—C7—Cl1 | 177.06 (11) | C14—C15—C16—C17 | −0.9 (3) |
C6—N1—C7—Cl1 | 1.5 (2) | C15—C16—C17—C12 | 1.6 (3) |
N1—C7—C8—C9 | −0.30 (18) | C13—C12—C17—C16 | −1.2 (3) |
Cl1—C7—C8—C9 | −177.38 (13) | N3—C12—C17—C16 | −177.71 (18) |
N1—C7—C8—C11 | 177.98 (15) |
Experimental details
Crystal data | |
Chemical formula | C17H14ClN3 |
Mr | 295.76 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.7837 (9), 11.0980 (12), 15.6749 (16) |
β (°) | 102.648 (1) |
V (Å3) | 1490.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.40 × 0.19 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.816, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9958, 2751, 2248 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 1.05 |
No. of reflections | 2751 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.21 |
Computer programs: APEX2 (Bruker 2004), SAINT (Bruker 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2004).
Pyrazole derivatives are attracting the increasing attention of the synthetic community for decades (Wang, 2004), owing to their wide range of biological activities in pesticide and medicine science (Liang & Bai, 2006; He, 2005). In recent years, we have been engaged in the preparation of derivatives of pyrazole compounds, and expected to find low toxicity and high activity lead compounds for the pesticide field.
Herein, we report the crystal structure of the title compound (Fig. 1), which was synthesized by the condensation reaction of aldehyde with aniline.
The title compound adopts the more stable E-configuration. In the pyrazole ring of the title molecule, bond lengths and angles are similar to those observed in closely related structures (Trilleras et al., 2005). The pyrazole ring and the adjacent benzene ring (C1–C6) are inclined at 45.54 (7)°. The imine group (N3—C11—H11) is twisted by 5.41 (12)° away from the pyrazole ring, and 42.59 (11)° away from the adjacent benzene ring (C12–C17).