The molecular structure of the title compound, C
16H
9BrF
4N
2O
3S, is stabilized by an intramolecular C—H
O hydrogen bond. In the crystal structure, supramolecular layers are formed parallel to the
bc plane by an intermolecular C—H
F hydrogen bond. The CF
3 group was found to be disordered.
Supporting information
CCDC reference: 294133
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- Disorder in main residue
- R factor = 0.053
- wR factor = 0.152
- Data-to-parameter ratio = 11.6
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.96
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7
PLAT301_ALERT_3_C Main Residue Disorder ......................... 10.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 10
PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O3 .. 3.14 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 40.40 Deg.
F3 -C7 -F2' 1.555 1.555 1.555
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
8 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.
1-(4-Bromo-2-fluorophenyl)-3-trifluoromethyl-1
H-pyrazol-5-yl
benzenesulfonate
top
Crystal data top
C16H9BrF4N2O3S | F(000) = 920 |
Mr = 465.22 | Dx = 1.724 Mg m−3 |
Monoclinic, P21/c | Melting point = 342–343 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 19.740 (4) Å | Cell parameters from 1907 reflections |
b = 9.5361 (18) Å | θ = 2.4–22.6° |
c = 9.7230 (18) Å | µ = 2.47 mm−1 |
β = 101.699 (3)° | T = 293 K |
V = 1792.3 (6) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.24 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3161 independent reflections |
Radiation source: fine-focus sealed tube | 1656 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→23 |
Tmin = 0.525, Tmax = 0.638 | k = −11→11 |
8850 measured reflections | l = −11→8 |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0602P)2 + 2.3366P] where P = (Fo2 + 2Fc2)/3 |
3161 reflections | (Δ/σ)max = 0.001 |
272 parameters | Δρmax = 0.84 e Å−3 |
57 restraints | Δρmin = −0.71 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 1.01839 (4) | 0.57024 (10) | −0.23507 (9) | 0.0911 (4) | |
S1 | 0.79733 (9) | 0.42363 (19) | 0.28910 (17) | 0.0568 (5) | |
F1 | 0.8562 (2) | 0.7839 (4) | 0.0661 (4) | 0.0829 (12) | |
F2 | 0.5584 (4) | 0.7784 (9) | −0.1790 (13) | 0.093 (4) | 0.623 (15) |
F3 | 0.5256 (4) | 0.6402 (15) | −0.0387 (8) | 0.094 (3) | 0.623 (15) |
F4 | 0.5506 (5) | 0.5605 (13) | −0.2259 (13) | 0.115 (4) | 0.623 (15) |
F2' | 0.5351 (8) | 0.733 (2) | −0.0511 (17) | 0.106 (6) | 0.377 (15) |
F3' | 0.5350 (7) | 0.5281 (11) | −0.135 (2) | 0.095 (6) | 0.377 (15) |
F4' | 0.5619 (6) | 0.699 (2) | −0.2510 (12) | 0.085 (5) | 0.377 (15) |
O1 | 0.7885 (2) | 0.5816 (4) | 0.2221 (4) | 0.0516 (11) | |
O2 | 0.7924 (3) | 0.3284 (5) | 0.1752 (5) | 0.0784 (14) | |
O3 | 0.8579 (2) | 0.4355 (5) | 0.3932 (5) | 0.0773 (14) | |
N1 | 0.7505 (2) | 0.6024 (5) | −0.0239 (5) | 0.0448 (12) | |
N2 | 0.6913 (2) | 0.6210 (5) | −0.1215 (5) | 0.0508 (13) | |
C1 | 0.8155 (3) | 0.5891 (6) | −0.0660 (6) | 0.0424 (14) | |
C2 | 0.8669 (3) | 0.6833 (6) | −0.0243 (6) | 0.0466 (15) | |
C3 | 0.9285 (3) | 0.6799 (7) | −0.0700 (7) | 0.0592 (18) | |
H3 | 0.9632 | 0.7453 | −0.0392 | 0.071* | |
C4 | 0.9364 (3) | 0.5751 (8) | −0.1635 (7) | 0.0562 (17) | |
C5 | 0.8864 (4) | 0.4770 (7) | −0.2047 (7) | 0.0641 (19) | |
H5 | 0.8934 | 0.4053 | −0.2651 | 0.077* | |
C6 | 0.8257 (3) | 0.4837 (7) | −0.1573 (7) | 0.0565 (17) | |
H6 | 0.7913 | 0.4173 | −0.1866 | 0.068* | |
C7 | 0.5709 (3) | 0.6496 (7) | −0.1207 (7) | 0.0654 (19) | |
C8 | 0.6420 (3) | 0.6300 (6) | −0.0473 (6) | 0.0470 (15) | |
C9 | 0.6672 (3) | 0.6175 (6) | 0.0970 (6) | 0.0526 (16) | |
H9 | 0.6426 | 0.6204 | 0.1690 | 0.063* | |
C10 | 0.7363 (3) | 0.6001 (6) | 0.1068 (6) | 0.0467 (15) | |
C11 | 0.7245 (3) | 0.4085 (6) | 0.3642 (6) | 0.0454 (15) | |
C12 | 0.6722 (4) | 0.3153 (7) | 0.3083 (8) | 0.070 (2) | |
H12 | 0.6762 | 0.2586 | 0.2325 | 0.084* | |
C13 | 0.6149 (4) | 0.3079 (8) | 0.3657 (9) | 0.079 (2) | |
H13 | 0.5796 | 0.2457 | 0.3287 | 0.094* | |
C14 | 0.6087 (4) | 0.3909 (9) | 0.4773 (9) | 0.078 (2) | |
H14 | 0.5691 | 0.3859 | 0.5150 | 0.093* | |
C15 | 0.6610 (4) | 0.4815 (8) | 0.5332 (7) | 0.0663 (19) | |
H15 | 0.6566 | 0.5377 | 0.6090 | 0.080* | |
C16 | 0.7193 (3) | 0.4900 (7) | 0.4790 (6) | 0.0546 (17) | |
H16 | 0.7551 | 0.5499 | 0.5187 | 0.065* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0481 (5) | 0.1365 (8) | 0.0958 (7) | 0.0274 (5) | 0.0314 (4) | 0.0420 (6) |
S1 | 0.0523 (10) | 0.0693 (12) | 0.0477 (10) | 0.0145 (8) | 0.0074 (8) | 0.0059 (9) |
F1 | 0.077 (3) | 0.075 (3) | 0.094 (3) | −0.008 (2) | 0.013 (2) | −0.027 (2) |
F2 | 0.063 (4) | 0.085 (5) | 0.118 (7) | 0.011 (4) | −0.009 (5) | 0.034 (5) |
F3 | 0.051 (4) | 0.137 (8) | 0.097 (5) | 0.007 (5) | 0.022 (4) | 0.033 (6) |
F4 | 0.071 (5) | 0.140 (8) | 0.116 (7) | 0.028 (5) | −0.022 (5) | −0.041 (6) |
F2' | 0.072 (8) | 0.120 (10) | 0.125 (10) | 0.035 (7) | 0.021 (7) | −0.017 (8) |
F3' | 0.071 (7) | 0.085 (8) | 0.120 (10) | −0.022 (6) | −0.002 (7) | 0.020 (7) |
F4' | 0.057 (6) | 0.118 (10) | 0.073 (7) | −0.007 (7) | −0.002 (6) | 0.037 (7) |
O1 | 0.048 (2) | 0.066 (3) | 0.038 (2) | 0.001 (2) | 0.003 (2) | 0.000 (2) |
O2 | 0.105 (4) | 0.068 (3) | 0.067 (3) | 0.025 (3) | 0.029 (3) | −0.003 (3) |
O3 | 0.041 (3) | 0.121 (4) | 0.067 (3) | 0.017 (3) | 0.004 (2) | 0.028 (3) |
N1 | 0.039 (3) | 0.057 (3) | 0.038 (3) | 0.007 (2) | 0.005 (2) | 0.000 (2) |
N2 | 0.039 (3) | 0.068 (3) | 0.044 (3) | 0.007 (2) | 0.003 (3) | 0.002 (3) |
C1 | 0.035 (3) | 0.051 (4) | 0.040 (3) | 0.004 (3) | 0.004 (3) | 0.012 (3) |
C2 | 0.046 (4) | 0.044 (4) | 0.047 (4) | 0.005 (3) | 0.002 (3) | −0.003 (3) |
C3 | 0.031 (3) | 0.071 (5) | 0.070 (5) | −0.002 (3) | −0.003 (3) | 0.019 (4) |
C4 | 0.041 (4) | 0.072 (5) | 0.055 (4) | 0.015 (4) | 0.006 (3) | 0.021 (4) |
C5 | 0.069 (5) | 0.065 (5) | 0.061 (5) | 0.012 (4) | 0.020 (4) | −0.004 (4) |
C6 | 0.058 (4) | 0.055 (4) | 0.059 (4) | 0.005 (3) | 0.018 (3) | −0.004 (3) |
C7 | 0.048 (4) | 0.084 (6) | 0.069 (5) | 0.010 (4) | 0.021 (4) | 0.015 (5) |
C8 | 0.038 (3) | 0.054 (4) | 0.048 (4) | 0.005 (3) | 0.007 (3) | 0.005 (3) |
C9 | 0.051 (4) | 0.064 (4) | 0.045 (4) | 0.010 (3) | 0.016 (3) | 0.006 (3) |
C10 | 0.050 (4) | 0.051 (4) | 0.038 (3) | 0.002 (3) | 0.005 (3) | 0.001 (3) |
C11 | 0.047 (4) | 0.046 (4) | 0.040 (3) | 0.004 (3) | 0.000 (3) | 0.005 (3) |
C12 | 0.064 (5) | 0.069 (5) | 0.070 (5) | 0.001 (4) | −0.002 (4) | −0.010 (4) |
C13 | 0.054 (5) | 0.080 (6) | 0.094 (6) | −0.012 (4) | −0.003 (5) | −0.001 (5) |
C14 | 0.048 (4) | 0.096 (6) | 0.090 (6) | 0.008 (4) | 0.017 (4) | 0.033 (5) |
C15 | 0.075 (5) | 0.081 (5) | 0.046 (4) | −0.002 (4) | 0.019 (4) | 0.001 (4) |
C16 | 0.054 (4) | 0.064 (4) | 0.044 (4) | −0.012 (3) | 0.007 (3) | −0.002 (3) |
Geometric parameters (Å, º) top
Br1—C4 | 1.887 (6) | C4—C5 | 1.360 (9) |
S1—O3 | 1.406 (5) | C5—C6 | 1.370 (9) |
S1—O2 | 1.420 (5) | C5—H5 | 0.9300 |
S1—O1 | 1.637 (4) | C6—C1 | 1.382 (8) |
S1—C11 | 1.746 (6) | C6—H6 | 0.9300 |
F1—C2 | 1.346 (7) | C7—C8 | 1.452 (8) |
F2—C7 | 1.354 (7) | C8—C9 | 1.396 (8) |
F3—C7 | 1.316 (7) | C9—C10 | 1.358 (8) |
F4—C7 | 1.328 (7) | C9—H9 | 0.9300 |
F2'—C7 | 1.334 (9) | C11—C16 | 1.381 (8) |
F3'—C7 | 1.351 (8) | C11—C12 | 1.386 (8) |
F4'—C7 | 1.330 (8) | C12—C13 | 1.360 (10) |
O1—C10 | 1.371 (7) | C12—H12 | 0.9300 |
N1—C10 | 1.356 (7) | C13—C14 | 1.368 (10) |
N1—N2 | 1.358 (6) | C13—H13 | 0.9300 |
N1—C1 | 1.430 (7) | C14—C15 | 1.371 (10) |
N2—C8 | 1.327 (7) | C14—H14 | 0.9300 |
C2—C1 | 1.354 (8) | C15—C16 | 1.361 (9) |
C2—C3 | 1.378 (8) | C15—H15 | 0.9300 |
C3—C4 | 1.381 (9) | C16—H16 | 0.9300 |
C3—H3 | 0.9300 | | |
| | | |
O3—S1—O2 | 121.8 (3) | F3—C7—F2 | 103.1 (7) |
O3—S1—O1 | 102.7 (3) | F4—C7—F2 | 104.9 (7) |
O2—S1—O1 | 107.0 (2) | F4'—C7—F2 | 45.7 (7) |
O3—S1—C11 | 111.0 (3) | F2'—C7—F2 | 66.6 (8) |
O2—S1—C11 | 109.9 (3) | F3'—C7—F2 | 133.4 (8) |
O1—S1—C11 | 102.2 (2) | F3—C7—C8 | 113.7 (6) |
C10—O1—S1 | 116.5 (3) | F4—C7—C8 | 114.0 (6) |
C10—N1—N2 | 110.2 (5) | F4'—C7—C8 | 116.3 (7) |
C10—N1—C1 | 129.5 (5) | F2'—C7—C8 | 112.7 (8) |
N2—N1—C1 | 120.3 (4) | F3'—C7—C8 | 112.0 (8) |
C8—N2—N1 | 104.5 (4) | F2—C7—C8 | 113.5 (6) |
F1—C2—C1 | 117.5 (5) | N2—C8—C9 | 113.0 (5) |
F1—C2—C3 | 119.5 (6) | N2—C8—C7 | 119.0 (5) |
C1—C2—C3 | 123.0 (6) | C9—C8—C7 | 128.0 (6) |
C2—C3—C4 | 117.0 (6) | C10—C9—C8 | 103.2 (5) |
C2—C3—H3 | 121.5 | C10—C9—H9 | 128.4 |
C4—C3—H3 | 121.5 | C8—C9—H9 | 128.4 |
C5—C4—C3 | 121.3 (6) | N1—C10—C9 | 109.1 (5) |
C5—C4—Br1 | 120.0 (6) | N1—C10—O1 | 120.3 (5) |
C3—C4—Br1 | 118.7 (5) | C9—C10—O1 | 130.6 (5) |
C4—C5—C6 | 120.0 (6) | C16—C11—C12 | 120.4 (6) |
C4—C5—H5 | 120.0 | C16—C11—S1 | 119.6 (5) |
C6—C5—H5 | 120.0 | C12—C11—S1 | 120.0 (5) |
C5—C6—C1 | 120.2 (6) | C13—C12—C11 | 119.1 (7) |
C5—C6—H6 | 119.9 | C13—C12—H12 | 120.4 |
C1—C6—H6 | 119.9 | C11—C12—H12 | 120.4 |
C2—C1—C6 | 118.4 (6) | C12—C13—C14 | 120.7 (7) |
C2—C1—N1 | 121.1 (5) | C12—C13—H13 | 119.6 |
C6—C1—N1 | 120.3 (5) | C14—C13—H13 | 119.6 |
F3—C7—F4 | 106.7 (7) | C13—C14—C15 | 119.8 (7) |
F3—C7—F4' | 128.7 (8) | C13—C14—H14 | 120.1 |
F4—C7—F4' | 62.1 (7) | C15—C14—H14 | 120.1 |
F3—C7—F2' | 40.4 (7) | C16—C15—C14 | 120.8 (7) |
F4—C7—F2' | 131.5 (9) | C16—C15—H15 | 119.6 |
F4'—C7—F2' | 106.9 (9) | C14—C15—H15 | 119.6 |
F3—C7—F3' | 66.2 (7) | C15—C16—C11 | 119.1 (6) |
F4—C7—F3' | 45.7 (7) | C15—C16—H16 | 120.4 |
F4'—C7—F3' | 104.0 (8) | C11—C16—H16 | 120.4 |
F2'—C7—F3' | 103.9 (9) | | |
| | | |
O3—S1—O1—C10 | 174.1 (4) | F3—C7—C8—C9 | −7.2 (12) |
O2—S1—O1—C10 | 44.8 (5) | F4—C7—C8—C9 | −129.7 (10) |
C11—S1—O1—C10 | −70.8 (4) | F4'—C7—C8—C9 | 160.8 (12) |
C10—N1—N2—C8 | 0.1 (6) | F2'—C7—C8—C9 | 37.0 (14) |
C1—N1—N2—C8 | −179.6 (5) | F3'—C7—C8—C9 | −79.8 (13) |
F1—C1—C2—C3 | −179.5 (5) | F2—C7—C8—C9 | 110.3 (9) |
C1—C2—C3—C4 | 0.6 (9) | N2—C8—C9—C10 | 0.1 (7) |
C2—C3—C4—C5 | −2.2 (9) | C7—C8—C9—C10 | 179.5 (6) |
C2—C3—C4—Br1 | 177.5 (4) | N2—N1—C10—C9 | −0.1 (6) |
C3—C4—C5—C6 | 2.4 (10) | C1—N1—C10—C9 | 179.6 (5) |
Br1—C4—C5—C6 | −177.4 (5) | N2—N1—C10—O1 | 179.6 (5) |
C4—C5—C6—C1 | −0.9 (9) | C1—N1—C10—O1 | −0.7 (9) |
F1—C2—C1—C6 | −179.1 (5) | C8—C9—C10—N1 | 0.0 (7) |
C3—C2—C1—C6 | 0.8 (9) | C8—C9—C10—O1 | −179.7 (6) |
F1—C2—C1—N1 | 4.5 (8) | S1—O1—C10—N1 | −100.2 (5) |
C3—C2—C1—N1 | −175.5 (5) | S1—O1—C10—C9 | 79.4 (7) |
C5—C6—C1—C2 | −0.7 (9) | O3—S1—C11—C16 | 41.0 (6) |
C5—C6—C1—N1 | 175.7 (5) | O2—S1—C11—C16 | 178.7 (4) |
C10—N1—C1—C2 | −61.6 (8) | O1—S1—C11—C16 | −67.8 (5) |
N2—N1—C1—C2 | 118.0 (6) | O3—S1—C11—C12 | −139.1 (5) |
C10—N1—C1—C6 | 122.1 (7) | O2—S1—C11—C12 | −1.4 (6) |
N2—N1—C1—C6 | −58.2 (7) | O1—S1—C11—C12 | 112.0 (5) |
N1—N2—C8—C9 | −0.1 (7) | C16—C11—C12—C13 | 1.7 (9) |
N1—N2—C8—C7 | −179.6 (5) | S1—C11—C12—C13 | −178.1 (5) |
F3—C7—C8—N2 | 172.2 (9) | C11—C12—C13—C14 | −0.1 (11) |
F4—C7—C8—N2 | 49.7 (11) | C12—C13—C14—C15 | −0.8 (11) |
F4'—C7—C8—N2 | −19.8 (13) | C13—C14—C15—C16 | 0.0 (11) |
F2'—C7—C8—N2 | −143.6 (12) | C14—C15—C16—C11 | 1.6 (10) |
F3'—C7—C8—N2 | 99.6 (12) | C12—C11—C16—C15 | −2.5 (9) |
F2—C7—C8—N2 | −70.3 (9) | S1—C11—C16—C15 | 177.4 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O2 | 0.93 | 2.56 | 2.927 (10) | 104 |
C16—H16···F1i | 0.93 | 2.52 | 3.428 (7) | 166 |
Symmetry code: (i) x, −y+3/2, z+1/2. |