Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039310/jh6027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039310/jh6027Isup2.hkl |
CCDC reference: 296721
To a suspension of 1-phenyl-3-methyl-1H-pyrazol-5-one (Liu & Li, 2004; 0.36 g, 2 mmol), anhydrous sodium carbonate (0.11 g, 1 mmol), and a catalytic amount of tetrabutylammonium bromide in benzene (20 ml) and water (2 ml) was added dropwise 2,4-dichlorobenzoyl chloride (0.44 g, 2.1 mmol) in benzene (5 ml) over a period of half an hour at 283 K, and the reaction mixture was stirred at ambient temperature for an additional 1 h. The reaction was quenched by aqueous saturated sodium carbonate (10 ml), and the benzene layer was collected and evaporated under reduced pressure to yield 0.65 g of (I) as an colorless solid in 94% yield (m.p. 364.0–365.5 K). 1H NMR (CDCl3, 500 MHz, p.p.m.): δ 7.85 (d, 1H, J = 8.5 Hz), 7.56–7.53 (m, 3H), 7.43 (t, 2H, J = 7.5 Hz), 7.34–7.31 (m, 2H), 6.28 (s, 1H), 2.36 (s, 3H); 13C NMR (CDCl3, 500 MHz, p.p.m.): δ 159.5, 149.1, 144.0, 140.0, 137.9, 136.3, 133.0,131.7, 129.1 (2 C), 127.5, 127.4, 125.6, 123.5 (2 C), 95.9, 14.5. Suitable crystals were grown by evaporation from a mixture of ethyl acetate and n-hexane (2:1 v/v).
All H atoms were included in the riding-model approximation, with C—H distances of 0.93 (aromatic) and 0.96 Å (methyl), and with Uiso(H) = 1.2Ueq(Carom) and 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. Displacement ellipsoid plot of the molecular structure of (I). H atoms are shown as small spheres of arbitrary radii. |
C17H12Cl2N2O2 | F(000) = 712 |
Mr = 347.19 | Dx = 1.403 Mg m−3 |
Monoclinic, P21/n | Melting point = 364.0–365.5 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 10.799 (3) Å | Cell parameters from 2156 reflections |
b = 10.385 (3) Å | θ = 2.4–21.7° |
c = 14.656 (4) Å | µ = 0.41 mm−1 |
β = 91.292 (4)° | T = 294 K |
V = 1643.3 (7) Å3 | Prism, colorless |
Z = 4 | 0.24 × 0.20 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 3354 independent reflections |
Radiation source: fine-focus sealed tube | 1837 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.892, Tmax = 0.930 | k = −6→12 |
9043 measured reflections | l = −17→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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0805P)2 + 0.7399P] where P = (Fo2 + 2Fc2)/3 |
3354 reflections | (Δ/σ)max = 0.002 |
209 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C17H12Cl2N2O2 | V = 1643.3 (7) Å3 |
Mr = 347.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.799 (3) Å | µ = 0.41 mm−1 |
b = 10.385 (3) Å | T = 294 K |
c = 14.656 (4) Å | 0.24 × 0.20 × 0.18 mm |
β = 91.292 (4)° |
Bruker SMART CCD area-detector diffractometer | 3354 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1837 reflections with I > 2σ(I) |
Tmin = 0.892, Tmax = 0.930 | Rint = 0.044 |
9043 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.66 e Å−3 |
3354 reflections | Δρmin = −0.48 e Å−3 |
209 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 | 0.20027 (10) | 1.12808 (11) | 0.35699 (7) | 0.0857 (4) | |
Cl2 | −0.13994 (12) | 1.35954 (12) | 0.55581 (9) | 0.1083 (5) | |
O1 | 0.25881 (19) | 0.8814 (2) | 0.59991 (15) | 0.0554 (6) | |
O2 | 0.3494 (3) | 0.9738 (4) | 0.4829 (2) | 0.1290 (15) | |
N2 | 0.4013 (3) | 0.5871 (3) | 0.65368 (19) | 0.0589 (7) | |
N1 | 0.3093 (2) | 0.6785 (2) | 0.65378 (17) | 0.0491 (7) | |
C1 | 0.1989 (3) | 0.6556 (3) | 0.7009 (2) | 0.0476 (8) | |
C2 | 0.1527 (3) | 0.7477 (3) | 0.7588 (2) | 0.0575 (9) | |
H2 | 0.1929 | 0.8263 | 0.7662 | 0.069* | |
C3 | 0.0460 (4) | 0.7218 (4) | 0.8059 (3) | 0.0762 (11) | |
H3 | 0.0136 | 0.7840 | 0.8443 | 0.091* | |
C4 | −0.0123 (4) | 0.6053 (5) | 0.7963 (3) | 0.0855 (13) | |
H4 | −0.0835 | 0.5880 | 0.8288 | 0.103* | |
C5 | 0.0343 (4) | 0.5143 (4) | 0.7388 (3) | 0.0777 (12) | |
H5 | −0.0053 | 0.4352 | 0.7327 | 0.093* | |
C6 | 0.1391 (3) | 0.5385 (3) | 0.6898 (2) | 0.0605 (9) | |
H6 | 0.1693 | 0.4771 | 0.6498 | 0.073* | |
C7 | 0.6100 (3) | 0.5674 (4) | 0.5924 (3) | 0.0850 (13) | |
H7A | 0.6724 | 0.5968 | 0.6352 | 0.127* | |
H7B | 0.6374 | 0.5816 | 0.5314 | 0.127* | |
H7C | 0.5957 | 0.4771 | 0.6015 | 0.127* | |
C8 | 0.4916 (3) | 0.6405 (3) | 0.6068 (2) | 0.0606 (9) | |
C9 | 0.4598 (3) | 0.7642 (3) | 0.5752 (2) | 0.0594 (9) | |
H9 | 0.5072 | 0.8198 | 0.5406 | 0.071* | |
C10 | 0.3444 (3) | 0.7839 (3) | 0.6065 (2) | 0.0490 (8) | |
C11 | 0.2647 (3) | 0.9701 (3) | 0.5326 (2) | 0.0605 (9) | |
C12 | 0.1628 (3) | 1.0635 (3) | 0.5363 (2) | 0.0494 (8) | |
C13 | 0.1318 (3) | 1.1427 (3) | 0.4620 (2) | 0.0562 (8) | |
C14 | 0.0395 (3) | 1.2335 (3) | 0.4685 (3) | 0.0662 (10) | |
H14 | 0.0192 | 1.2859 | 0.4189 | 0.079* | |
C15 | −0.0220 (3) | 1.2459 (3) | 0.5484 (3) | 0.0676 (10) | |
C16 | 0.0050 (3) | 1.1684 (4) | 0.6232 (3) | 0.0666 (10) | |
H16 | −0.0383 | 1.1774 | 0.6770 | 0.080* | |
C17 | 0.0965 (3) | 1.0786 (3) | 0.6161 (2) | 0.0541 (8) | |
H17 | 0.1151 | 1.0259 | 0.6659 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0896 (8) | 0.1028 (9) | 0.0649 (6) | 0.0134 (6) | 0.0052 (5) | 0.0277 (6) |
Cl2 | 0.1170 (10) | 0.1039 (9) | 0.1021 (9) | 0.0644 (7) | −0.0385 (7) | −0.0316 (7) |
O1 | 0.0539 (13) | 0.0516 (13) | 0.0609 (14) | 0.0134 (11) | 0.0085 (11) | 0.0156 (11) |
O2 | 0.114 (2) | 0.161 (3) | 0.115 (3) | 0.072 (2) | 0.061 (2) | 0.079 (2) |
N2 | 0.0577 (17) | 0.0545 (17) | 0.0643 (18) | 0.0173 (14) | −0.0047 (14) | 0.0014 (14) |
N1 | 0.0515 (15) | 0.0472 (15) | 0.0485 (15) | 0.0085 (12) | 0.0000 (12) | 0.0053 (12) |
C1 | 0.0500 (18) | 0.0494 (19) | 0.0431 (18) | 0.0019 (15) | −0.0056 (14) | 0.0070 (14) |
C2 | 0.065 (2) | 0.054 (2) | 0.053 (2) | −0.0017 (17) | 0.0039 (17) | 0.0002 (16) |
C3 | 0.080 (3) | 0.085 (3) | 0.064 (2) | 0.011 (2) | 0.018 (2) | 0.002 (2) |
C4 | 0.076 (3) | 0.102 (4) | 0.079 (3) | −0.015 (3) | 0.013 (2) | 0.029 (3) |
C5 | 0.084 (3) | 0.067 (3) | 0.082 (3) | −0.023 (2) | −0.011 (2) | 0.022 (2) |
C6 | 0.073 (2) | 0.051 (2) | 0.058 (2) | 0.0012 (18) | −0.0109 (18) | 0.0091 (16) |
C7 | 0.064 (2) | 0.079 (3) | 0.112 (3) | 0.024 (2) | 0.008 (2) | −0.010 (3) |
C8 | 0.054 (2) | 0.062 (2) | 0.066 (2) | 0.0130 (17) | −0.0017 (18) | −0.0075 (18) |
C9 | 0.053 (2) | 0.061 (2) | 0.065 (2) | 0.0075 (17) | 0.0068 (17) | 0.0033 (17) |
C10 | 0.0494 (18) | 0.0469 (19) | 0.0505 (18) | 0.0063 (15) | −0.0021 (14) | 0.0010 (15) |
C11 | 0.058 (2) | 0.067 (2) | 0.057 (2) | 0.0100 (18) | 0.0079 (17) | 0.0176 (18) |
C12 | 0.0460 (17) | 0.0428 (18) | 0.059 (2) | −0.0013 (14) | −0.0071 (15) | 0.0020 (15) |
C13 | 0.0552 (19) | 0.053 (2) | 0.060 (2) | −0.0023 (16) | −0.0103 (16) | 0.0082 (16) |
C14 | 0.072 (2) | 0.060 (2) | 0.065 (2) | 0.0095 (19) | −0.0226 (19) | 0.0025 (18) |
C15 | 0.070 (2) | 0.055 (2) | 0.076 (3) | 0.0148 (18) | −0.027 (2) | −0.0166 (19) |
C16 | 0.070 (2) | 0.066 (2) | 0.064 (2) | 0.0132 (19) | −0.0097 (18) | −0.0158 (18) |
C17 | 0.058 (2) | 0.0495 (19) | 0.055 (2) | 0.0036 (15) | −0.0055 (16) | −0.0031 (15) |
Cl1—C13 | 1.729 (4) | C6—H6 | 0.9300 |
Cl2—C15 | 1.742 (4) | C7—C8 | 1.507 (5) |
O1—C11 | 1.352 (4) | C7—H7A | 0.9600 |
O1—C10 | 1.373 (4) | C7—H7B | 0.9600 |
O2—C11 | 1.184 (4) | C7—H7C | 0.9600 |
N2—C8 | 1.327 (4) | C8—C9 | 1.406 (5) |
N2—N1 | 1.374 (3) | C9—C10 | 1.353 (4) |
N1—C10 | 1.355 (4) | C9—H9 | 0.9300 |
N1—C1 | 1.411 (4) | C11—C12 | 1.469 (4) |
C1—C2 | 1.380 (4) | C12—C17 | 1.394 (4) |
C1—C6 | 1.385 (4) | C12—C13 | 1.399 (4) |
C2—C3 | 1.383 (5) | C13—C14 | 1.377 (5) |
C2—H2 | 0.9300 | C14—C15 | 1.365 (5) |
C3—C4 | 1.370 (6) | C14—H14 | 0.9300 |
C3—H3 | 0.9300 | C15—C16 | 1.386 (5) |
C4—C5 | 1.370 (6) | C16—C17 | 1.365 (5) |
C4—H4 | 0.9300 | C16—H16 | 0.9300 |
C5—C6 | 1.377 (5) | C17—H17 | 0.9300 |
C5—H5 | 0.9300 | ||
C11—O1—C10 | 120.7 (2) | N2—C8—C7 | 119.9 (3) |
C8—N2—N1 | 104.5 (3) | C9—C8—C7 | 128.0 (4) |
C10—N1—N2 | 110.3 (2) | C10—C9—C8 | 104.2 (3) |
C10—N1—C1 | 129.5 (3) | C10—C9—H9 | 127.9 |
N2—N1—C1 | 120.2 (3) | C8—C9—H9 | 127.9 |
C2—C1—C6 | 120.5 (3) | C9—C10—N1 | 108.8 (3) |
C2—C1—N1 | 120.4 (3) | C9—C10—O1 | 135.4 (3) |
C6—C1—N1 | 119.2 (3) | N1—C10—O1 | 115.8 (3) |
C1—C2—C3 | 119.3 (3) | O2—C11—O1 | 121.4 (3) |
C1—C2—H2 | 120.4 | O2—C11—C12 | 126.3 (3) |
C3—C2—H2 | 120.4 | O1—C11—C12 | 112.1 (3) |
C4—C3—C2 | 120.5 (4) | C17—C12—C13 | 118.0 (3) |
C4—C3—H3 | 119.8 | C17—C12—C11 | 120.3 (3) |
C2—C3—H3 | 119.8 | C13—C12—C11 | 121.7 (3) |
C5—C4—C3 | 119.8 (4) | C14—C13—C12 | 120.6 (3) |
C5—C4—H4 | 120.1 | C14—C13—Cl1 | 116.5 (3) |
C3—C4—H4 | 120.1 | C12—C13—Cl1 | 122.8 (3) |
C4—C5—C6 | 120.9 (4) | C15—C14—C13 | 119.4 (3) |
C4—C5—H5 | 119.6 | C15—C14—H14 | 120.3 |
C6—C5—H5 | 119.6 | C13—C14—H14 | 120.3 |
C5—C6—C1 | 119.0 (4) | C14—C15—C16 | 121.8 (3) |
C5—C6—H6 | 120.5 | C14—C15—Cl2 | 119.2 (3) |
C1—C6—H6 | 120.5 | C16—C15—Cl2 | 119.0 (3) |
C8—C7—H7A | 109.5 | C17—C16—C15 | 118.5 (4) |
C8—C7—H7B | 109.5 | C17—C16—H16 | 120.8 |
H7A—C7—H7B | 109.5 | C15—C16—H16 | 120.8 |
C8—C7—H7C | 109.5 | C16—C17—C12 | 121.8 (3) |
H7A—C7—H7C | 109.5 | C16—C17—H17 | 119.1 |
H7B—C7—H7C | 109.5 | C12—C17—H17 | 119.1 |
N2—C8—C9 | 112.1 (3) | ||
C8—N2—N1—C10 | 0.8 (3) | C1—N1—C10—O1 | −2.9 (5) |
C8—N2—N1—C1 | −177.8 (3) | C11—O1—C10—C9 | 20.3 (5) |
C10—N1—C1—C2 | −46.6 (5) | C11—O1—C10—N1 | −158.4 (3) |
N2—N1—C1—C2 | 131.8 (3) | C10—O1—C11—O2 | −7.1 (6) |
C10—N1—C1—C6 | 134.8 (3) | C10—O1—C11—C12 | 178.4 (3) |
N2—N1—C1—C6 | −46.8 (4) | O2—C11—C12—C17 | −155.6 (4) |
C6—C1—C2—C3 | 0.1 (5) | O1—C11—C12—C17 | 18.6 (4) |
N1—C1—C2—C3 | −178.5 (3) | O2—C11—C12—C13 | 22.2 (6) |
C1—C2—C3—C4 | 1.0 (5) | O1—C11—C12—C13 | −163.6 (3) |
C2—C3—C4—C5 | −0.9 (6) | C17—C12—C13—C14 | 0.8 (5) |
C3—C4—C5—C6 | −0.3 (6) | C11—C12—C13—C14 | −177.1 (3) |
C4—C5—C6—C1 | 1.4 (5) | C17—C12—C13—Cl1 | −176.2 (2) |
C2—C1—C6—C5 | −1.3 (5) | C11—C12—C13—Cl1 | 6.0 (4) |
N1—C1—C6—C5 | 177.3 (3) | C12—C13—C14—C15 | 0.0 (5) |
N1—N2—C8—C9 | −0.9 (4) | Cl1—C13—C14—C15 | 177.1 (3) |
N1—N2—C8—C7 | 179.9 (3) | C13—C14—C15—C16 | −0.7 (5) |
N2—C8—C9—C10 | 0.6 (4) | C13—C14—C15—Cl2 | −179.3 (3) |
C7—C8—C9—C10 | 179.8 (4) | C14—C15—C16—C17 | 0.6 (5) |
C8—C9—C10—N1 | −0.1 (4) | Cl2—C15—C16—C17 | 179.2 (3) |
C8—C9—C10—O1 | −178.9 (3) | C15—C16—C17—C12 | 0.2 (5) |
N2—N1—C10—C9 | −0.5 (4) | C13—C12—C17—C16 | −0.8 (5) |
C1—N1—C10—C9 | 178.1 (3) | C11—C12—C17—C16 | 177.1 (3) |
N2—N1—C10—O1 | 178.6 (2) |
Experimental details
Crystal data | |
Chemical formula | C17H12Cl2N2O2 |
Mr | 347.19 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 10.799 (3), 10.385 (3), 14.656 (4) |
β (°) | 91.292 (4) |
V (Å3) | 1643.3 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.24 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.892, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9043, 3354, 1837 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.178, 1.02 |
No. of reflections | 3354 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.48 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
The title compound, (I), and some of its previously reported analogs possess herbicidal and growth-regulating activities (Vasilev et al., 1981) and anti-inflammatory properties (Terebenina et al., 1980).
In the molecular structure of (I) (Fig. 1), the dihedral angle formed between the dichlorobenzene and pyrazolyl rings is 38.3 (3)°, that between the phenyl and pyrazolyl rings is 46.8 (3)°, and that between the two phenyl rings is 69.4 (3)°.