Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053688/is2225sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053688/is2225Isup2.hkl |
CCDC reference: 672835
The title compound was synthesized according to the method of Hatton et al. (1993) and single crystals were obtained by slow evaporation of an acetone solution.
Three F atoms were split into approximately equal components with occupancies of 0.443 (18) for F1', F2' and F3' atoms, and 0.557 (18) for F1, F2 and F3 atoms. All H atoms were placed in calculated positions (O—H = 0.82 and C—H = 0.93 - 0.96 Å), and allowed to ride on their parent atoms, with Uiso(H) = 1.2–1.5 Ueq(C,O). The distances of C1—F1' and C1—F1 are restrained to be equal within a standard uncertainty of 0.01 Å. The same restraints have been applied for C1—F2' and C1—F2, and for C1—F3' and C1—F3.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
C14H11Cl2F3N4O2 | F(000) = 1600 |
Mr = 395.17 | Dx = 1.542 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2395 reflections |
a = 16.4987 (15) Å | θ = 2.3–24.0° |
b = 17.5642 (16) Å | µ = 0.43 mm−1 |
c = 11.8035 (11) Å | T = 273 K |
β = 95.626 (2)° | Block, colorless |
V = 3404.0 (5) Å3 | 0.33 × 0.24 × 0.17 mm |
Z = 8 |
Bruker APEX area-detector diffractometer | 3000 independent reflections |
Radiation source: fine-focus sealed tube | 2507 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scan | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −18→19 |
Tmin = 0.872, Tmax = 0.931 | k = −20→17 |
8810 measured reflections | l = −14→13 |
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.192 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0731P)2 + 12.0677P] where P = (Fo2 + 2Fc2)/3 |
3000 reflections | (Δ/σ)max < 0.001 |
233 parameters | Δρmax = 0.67 e Å−3 |
3 restraints | Δρmin = −0.43 e Å−3 |
C14H11Cl2F3N4O2 | V = 3404.0 (5) Å3 |
Mr = 395.17 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.4987 (15) Å | µ = 0.43 mm−1 |
b = 17.5642 (16) Å | T = 273 K |
c = 11.8035 (11) Å | 0.33 × 0.24 × 0.17 mm |
β = 95.626 (2)° |
Bruker APEX area-detector diffractometer | 3000 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2507 reflections with I > 2σ(I) |
Tmin = 0.872, Tmax = 0.931 | Rint = 0.032 |
8810 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 3 restraints |
wR(F2) = 0.192 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0731P)2 + 12.0677P] where P = (Fo2 + 2Fc2)/3 |
3000 reflections | Δρmax = 0.67 e Å−3 |
233 parameters | Δρmin = −0.43 e Å−3 |
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 | Occ. (<1) | |
Cl1 | 0.14889 (7) | 0.32685 (8) | −0.03790 (10) | 0.0589 (4) | |
Cl2 | 0.36248 (9) | 0.41783 (9) | 0.30881 (12) | 0.0749 (5) | |
F1 | 0.5128 (6) | 0.3254 (7) | −0.0513 (10) | 0.095 (3) | 0.443 (18) |
F2 | 0.4306 (6) | 0.3471 (8) | −0.1977 (7) | 0.095 (3) | 0.443 (18) |
F3 | 0.4852 (7) | 0.4397 (5) | −0.0970 (11) | 0.095 (3) | 0.443 (18) |
F1' | 0.4841 (6) | 0.3031 (4) | −0.0965 (10) | 0.099 (3) | 0.557 (18) |
F2' | 0.4231 (4) | 0.3860 (7) | −0.2011 (6) | 0.099 (3) | 0.557 (18) |
F3' | 0.5109 (5) | 0.4214 (5) | −0.0690 (9) | 0.099 (3) | 0.557 (18) |
O1 | 0.0486 (2) | 0.51875 (17) | 0.3874 (3) | 0.0524 (8) | |
O2 | 0.0227 (2) | 0.40406 (17) | 0.4549 (3) | 0.0531 (8) | |
H2 | −0.0039 | 0.4292 | 0.4966 | 0.080* | |
N1 | 0.1993 (2) | 0.37409 (19) | 0.2005 (3) | 0.0414 (8) | |
N2 | 0.1734 (2) | 0.30728 (19) | 0.2448 (3) | 0.0479 (9) | |
N3 | 0.1879 (2) | 0.50406 (19) | 0.1939 (3) | 0.0413 (8) | |
N4 | 0.1740 (3) | 0.6305 (2) | 0.1563 (3) | 0.0559 (10) | |
C1 | 0.4523 (4) | 0.3719 (4) | −0.0896 (5) | 0.0700 (16) | |
C2 | 0.3847 (3) | 0.3741 (3) | −0.0164 (4) | 0.0533 (12) | |
C3 | 0.3074 (3) | 0.3531 (3) | −0.0585 (4) | 0.0514 (12) | |
H3 | 0.2963 | 0.3388 | −0.1343 | 0.062* | |
C4 | 0.2465 (3) | 0.3536 (2) | 0.0134 (4) | 0.0426 (10) | |
C5 | 0.2623 (3) | 0.3735 (2) | 0.1267 (4) | 0.0410 (10) | |
C6 | 0.3407 (3) | 0.3938 (3) | 0.1672 (4) | 0.0498 (11) | |
C7 | 0.4024 (3) | 0.3947 (3) | 0.0958 (5) | 0.0577 (13) | |
H7 | 0.4550 | 0.4090 | 0.1232 | 0.069* | |
C8 | 0.1186 (3) | 0.3302 (2) | 0.3104 (4) | 0.0449 (11) | |
H8 | 0.0893 | 0.2970 | 0.3523 | 0.054* | |
C9 | 0.1080 (2) | 0.4092 (2) | 0.3116 (3) | 0.0371 (9) | |
C10 | 0.1622 (2) | 0.4376 (2) | 0.2361 (3) | 0.0352 (9) | |
C11 | 0.0578 (2) | 0.4502 (2) | 0.3855 (3) | 0.0371 (9) | |
C12 | 0.1481 (3) | 0.5665 (2) | 0.1987 (3) | 0.0421 (10) | |
H12 | 0.0998 | 0.5666 | 0.2331 | 0.050* | |
C13 | 0.2477 (4) | 0.6321 (3) | 0.0987 (5) | 0.0806 (18) | |
H13A | 0.2814 | 0.5894 | 0.1230 | 0.121* | |
H13B | 0.2768 | 0.6785 | 0.1172 | 0.121* | |
H13C | 0.2337 | 0.6294 | 0.0180 | 0.121* | |
C14 | 0.1268 (4) | 0.7004 (3) | 0.1562 (5) | 0.0836 (19) | |
H14A | 0.1114 | 0.7159 | 0.0791 | 0.125* | |
H14B | 0.1592 | 0.7396 | 0.1951 | 0.125* | |
H14C | 0.0788 | 0.6919 | 0.1943 | 0.125* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0473 (7) | 0.0747 (9) | 0.0558 (7) | 0.0095 (6) | 0.0110 (5) | 0.0027 (6) |
Cl2 | 0.0635 (8) | 0.1047 (12) | 0.0589 (8) | −0.0124 (7) | 0.0179 (6) | −0.0245 (7) |
F1 | 0.080 (4) | 0.094 (5) | 0.123 (5) | 0.007 (3) | 0.069 (4) | −0.008 (3) |
F2 | 0.080 (4) | 0.094 (5) | 0.123 (5) | 0.007 (3) | 0.069 (4) | −0.008 (3) |
F3 | 0.080 (4) | 0.094 (5) | 0.123 (5) | 0.007 (3) | 0.069 (4) | −0.008 (3) |
F1' | 0.079 (3) | 0.101 (4) | 0.128 (5) | 0.004 (2) | 0.072 (3) | −0.013 (3) |
F2' | 0.079 (3) | 0.101 (4) | 0.128 (5) | 0.004 (2) | 0.072 (3) | −0.013 (3) |
F3' | 0.079 (3) | 0.101 (4) | 0.128 (5) | 0.004 (2) | 0.072 (3) | −0.013 (3) |
O1 | 0.068 (2) | 0.0393 (18) | 0.0565 (19) | 0.0054 (15) | 0.0407 (16) | −0.0021 (14) |
O2 | 0.066 (2) | 0.0448 (17) | 0.055 (2) | 0.0022 (15) | 0.0413 (16) | −0.0003 (15) |
N1 | 0.047 (2) | 0.0362 (19) | 0.045 (2) | 0.0019 (15) | 0.0259 (16) | −0.0005 (15) |
N2 | 0.057 (2) | 0.036 (2) | 0.056 (2) | 0.0019 (17) | 0.0310 (19) | 0.0012 (16) |
N3 | 0.046 (2) | 0.038 (2) | 0.043 (2) | −0.0018 (16) | 0.0222 (16) | 0.0004 (15) |
N4 | 0.079 (3) | 0.040 (2) | 0.051 (2) | −0.0044 (19) | 0.014 (2) | 0.0047 (17) |
C1 | 0.075 (4) | 0.070 (4) | 0.072 (4) | 0.001 (3) | 0.046 (3) | −0.006 (3) |
C2 | 0.053 (3) | 0.049 (3) | 0.064 (3) | 0.004 (2) | 0.032 (2) | 0.000 (2) |
C3 | 0.062 (3) | 0.053 (3) | 0.044 (3) | 0.012 (2) | 0.027 (2) | 0.002 (2) |
C4 | 0.044 (2) | 0.038 (2) | 0.049 (3) | 0.0120 (18) | 0.0189 (19) | 0.0025 (19) |
C5 | 0.043 (2) | 0.035 (2) | 0.049 (3) | 0.0066 (18) | 0.0245 (19) | −0.0009 (19) |
C6 | 0.049 (3) | 0.051 (3) | 0.053 (3) | 0.000 (2) | 0.020 (2) | −0.009 (2) |
C7 | 0.044 (3) | 0.060 (3) | 0.073 (4) | −0.004 (2) | 0.027 (2) | −0.007 (3) |
C8 | 0.053 (3) | 0.042 (2) | 0.045 (2) | −0.0051 (19) | 0.026 (2) | 0.0027 (19) |
C9 | 0.038 (2) | 0.041 (2) | 0.035 (2) | −0.0017 (17) | 0.0148 (17) | −0.0039 (17) |
C10 | 0.034 (2) | 0.037 (2) | 0.036 (2) | −0.0002 (17) | 0.0120 (16) | −0.0047 (17) |
C11 | 0.031 (2) | 0.046 (3) | 0.036 (2) | −0.0026 (17) | 0.0137 (16) | −0.0016 (18) |
C12 | 0.055 (3) | 0.037 (2) | 0.036 (2) | 0.000 (2) | 0.0121 (19) | −0.0035 (18) |
C13 | 0.091 (4) | 0.073 (4) | 0.082 (4) | −0.026 (3) | 0.030 (3) | 0.017 (3) |
C14 | 0.138 (6) | 0.040 (3) | 0.073 (4) | 0.013 (3) | 0.013 (4) | 0.005 (3) |
Cl1—C4 | 1.729 (5) | C1—C2 | 1.477 (7) |
Cl2—C6 | 1.728 (5) | C2—C3 | 1.374 (7) |
F1—C1 | 1.333 (9) | C2—C7 | 1.377 (7) |
F2—C1 | 1.362 (9) | C3—C4 | 1.377 (6) |
F3—C1 | 1.315 (9) | C3—H3 | 0.9300 |
F1'—C1 | 1.322 (8) | C4—C5 | 1.382 (6) |
F2'—C1 | 1.379 (9) | C5—C6 | 1.380 (6) |
F3'—C1 | 1.306 (8) | C6—C7 | 1.384 (6) |
O1—C11 | 1.214 (5) | C7—H7 | 0.9300 |
O2—C11 | 1.325 (5) | C8—C9 | 1.399 (6) |
O2—H2 | 0.8200 | C8—H8 | 0.9300 |
N1—C10 | 1.359 (5) | C9—C10 | 1.413 (5) |
N1—N2 | 1.370 (5) | C9—C11 | 1.452 (5) |
N1—C5 | 1.421 (5) | C12—H12 | 0.9300 |
N2—C8 | 1.310 (5) | C13—H13A | 0.9600 |
N3—C12 | 1.282 (5) | C13—H13B | 0.9600 |
N3—C10 | 1.353 (5) | C13—H13C | 0.9600 |
N4—C12 | 1.318 (5) | C14—H14A | 0.9600 |
N4—C13 | 1.451 (7) | C14—H14B | 0.9600 |
N4—C14 | 1.453 (7) | C14—H14C | 0.9600 |
C11—O2—H2 | 109.5 | C5—C6—C7 | 120.8 (4) |
C10—N1—N2 | 114.7 (3) | C5—C6—Cl2 | 119.8 (3) |
C10—N1—C5 | 125.0 (3) | C7—C6—Cl2 | 119.4 (4) |
N2—N1—C5 | 120.2 (3) | C2—C7—C6 | 118.9 (5) |
C8—N2—N1 | 102.8 (3) | C2—C7—H7 | 120.6 |
C12—N3—C10 | 122.8 (3) | C6—C7—H7 | 120.6 |
C12—N4—C13 | 120.7 (4) | N2—C8—C9 | 113.8 (4) |
C12—N4—C14 | 121.9 (5) | N2—C8—H8 | 123.1 |
C13—N4—C14 | 117.2 (4) | C9—C8—H8 | 123.1 |
F3'—C1—F1' | 109.2 (6) | C8—C9—C10 | 104.9 (3) |
F3—C1—F1 | 106.1 (7) | C8—C9—C11 | 125.2 (4) |
F3—C1—F2 | 107.4 (8) | C10—C9—C11 | 129.6 (4) |
F1—C1—F2 | 104.0 (7) | N3—C10—N1 | 115.3 (3) |
F3'—C1—F2' | 103.9 (7) | N3—C10—C9 | 141.0 (4) |
F1'—C1—F2' | 102.1 (6) | N1—C10—C9 | 103.7 (3) |
F3'—C1—C2 | 117.4 (6) | O1—C11—O2 | 122.2 (3) |
F3—C1—C2 | 110.7 (6) | O1—C11—C9 | 125.6 (4) |
F1'—C1—C2 | 112.8 (5) | O2—C11—C9 | 112.2 (4) |
F1—C1—C2 | 113.7 (6) | N3—C12—N4 | 121.8 (4) |
F2—C1—C2 | 114.3 (6) | N3—C12—H12 | 119.1 |
F2'—C1—C2 | 109.9 (6) | N4—C12—H12 | 119.1 |
C3—C2—C7 | 121.4 (4) | N4—C13—H13A | 109.5 |
C3—C2—C1 | 120.6 (5) | N4—C13—H13B | 109.5 |
C7—C2—C1 | 118.0 (5) | H13A—C13—H13B | 109.5 |
C2—C3—C4 | 118.9 (4) | N4—C13—H13C | 109.5 |
C2—C3—H3 | 120.6 | H13A—C13—H13C | 109.5 |
C4—C3—H3 | 120.6 | H13B—C13—H13C | 109.5 |
C3—C4—C5 | 121.2 (4) | N4—C14—H14A | 109.5 |
C3—C4—Cl1 | 119.5 (4) | N4—C14—H14B | 109.5 |
C5—C4—Cl1 | 119.3 (3) | H14A—C14—H14B | 109.5 |
C6—C5—C4 | 118.8 (4) | N4—C14—H14C | 109.5 |
C6—C5—N1 | 120.2 (4) | H14A—C14—H14C | 109.5 |
C4—C5—N1 | 121.0 (4) | H14B—C14—H14C | 109.5 |
C10—N1—N2—C8 | −0.3 (5) | N1—C5—C6—C7 | −178.9 (4) |
C5—N1—N2—C8 | 177.7 (4) | C4—C5—C6—Cl2 | −179.2 (3) |
F3'—C1—C2—C3 | 149.3 (8) | N1—C5—C6—Cl2 | 1.5 (6) |
F3—C1—C2—C3 | 120.9 (9) | C3—C2—C7—C6 | 0.2 (7) |
F1'—C1—C2—C3 | −82.4 (9) | C1—C2—C7—C6 | −177.0 (5) |
F1—C1—C2—C3 | −119.8 (9) | C5—C6—C7—C2 | −0.8 (7) |
F2—C1—C2—C3 | −0.6 (11) | Cl2—C6—C7—C2 | 178.8 (4) |
F2'—C1—C2—C3 | 30.8 (9) | N1—N2—C8—C9 | −0.5 (5) |
F3'—C1—C2—C7 | −33.5 (10) | N2—C8—C9—C10 | 1.0 (5) |
F3—C1—C2—C7 | −61.8 (10) | N2—C8—C9—C11 | −173.2 (4) |
F1'—C1—C2—C7 | 94.9 (9) | C12—N3—C10—N1 | 164.6 (4) |
F1—C1—C2—C7 | 57.5 (10) | C12—N3—C10—C9 | −17.8 (8) |
F2—C1—C2—C7 | 176.7 (9) | N2—N1—C10—N3 | 179.3 (4) |
F2'—C1—C2—C7 | −151.9 (7) | C5—N1—C10—N3 | 1.5 (6) |
C7—C2—C3—C4 | 0.7 (7) | N2—N1—C10—C9 | 0.9 (5) |
C1—C2—C3—C4 | 177.9 (5) | C5—N1—C10—C9 | −177.0 (4) |
C2—C3—C4—C5 | −1.1 (7) | C8—C9—C10—N3 | −178.8 (5) |
C2—C3—C4—Cl1 | −179.6 (4) | C11—C9—C10—N3 | −5.0 (9) |
C3—C4—C5—C6 | 0.6 (6) | C8—C9—C10—N1 | −1.1 (4) |
Cl1—C4—C5—C6 | 179.1 (3) | C11—C9—C10—N1 | 172.8 (4) |
C3—C4—C5—N1 | 179.9 (4) | C8—C9—C11—O1 | 179.7 (4) |
Cl1—C4—C5—N1 | −1.6 (5) | C10—C9—C11—O1 | 7.0 (7) |
C10—N1—C5—C6 | 75.9 (6) | C8—C9—C11—O2 | 0.8 (6) |
N2—N1—C5—C6 | −101.8 (5) | C10—C9—C11—O2 | −171.9 (4) |
C10—N1—C5—C4 | −103.4 (5) | C10—N3—C12—N4 | −179.5 (4) |
N2—N1—C5—C4 | 78.9 (5) | C13—N4—C12—N3 | 2.0 (7) |
C4—C5—C6—C7 | 0.4 (7) | C14—N4—C12—N3 | 176.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.86 | 2.668 (4) | 169 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H11Cl2F3N4O2 |
Mr | 395.17 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 16.4987 (15), 17.5642 (16), 11.8035 (11) |
β (°) | 95.626 (2) |
V (Å3) | 3404.0 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.43 |
Crystal size (mm) | 0.33 × 0.24 × 0.17 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.872, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8810, 3000, 2507 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.192, 1.13 |
No. of reflections | 3000 |
No. of parameters | 233 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0731P)2 + 12.0677P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.67, −0.43 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.86 | 2.668 (4) | 169 |
Symmetry code: (i) −x, −y+1, −z+1. |
Various biological activities of pyrazole derivatives, such as antitumor (Baraldi et al., 2001), anti-inflammatory (Smith et al., 2001) and antimicrobial activities (Hatton et al., 1993), have been indicated by a large number of reports. In addition, they have been used as ligands to investigate the relationship between the structure and the activity of the active site of metalloproteins (Dardari et al., 2006). For possible biological activity, the title compound was synthesized in our laboratory.
As shown in Fig. 1, the molecule has an overall L shape. The dihedral angel between the pyrazole ring and the benzene ring is 77.1 (3)°. The C—N bond lengths in the pyrazole ring range from 1.310 (5) to 1.361 (5) Å, which are shorter than a C—N single bond length of 1.443 Å, but longer than a typical C═N bond length of 1.269 Å (Jin et al., 2004), indicating the electron delocalization. Most bond lengths and angles in N-phenylpyrazole group are similar with the analogous molecules (Li et al., 2006; Zhong et al., 2006). Three disordered F atoms are observed in the trifluoromethyl group.
An O—H···O intermolecular interaction, which forms a dimeric motif typical for carboxylic acid, is an essential force in the crystal form (Fig. 2).