Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808037604/hb2777sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536808037604/hb2777Isup2.hkl |
CCDC reference: 712479
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.034
- wR factor = 0.082
- Data-to-parameter ratio = 11.5
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT431_ALERT_2_A Short Inter HL..A Contact F2' .. F2' .. 2.30 Ang.
Author Response: A disorder artifact |
Alert level B PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O2 .. 2.83 Ang.
Alert level C PLAT083_ALERT_2_C SHELXL Second Parameter in WGHT unusually Large. 9.00 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7
Author Response: disorder of C7-F bonds |
PLAT301_ALERT_3_C Main Residue Disorder ......................... 9.00 Perc. PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT234_ALERT_4_C Large Hirshfeld Difference C3 -- C4 .. 0.11 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.03 From the CIF: _reflns_number_total 3565 Count of symmetry unique reflns 1944 Completeness (_total/calc) 183.38% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1621 Fraction of Friedel pairs measured 0.834 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 49 PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ...... 42.60 Deg. F2' -C7 -F3 1.555 1.555 1.555
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 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 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by the literature method (Lahm et al., 2003). The crude products were purified by silica-gel column chromatography and then grown from acetone to afford colourless blocks of (I).
Anal. Calcd for C12H14N4O3: C, 48.32; H, 2.99; N, 14.83. Found: C, 48.47; H, 3.04; N, 14.66. 1H NMR(CDCl3): 2.19 (s, 3H, CH3), 2.70 (d, J=4.5 Hz, 3H, CH3), 7.30–7.31 (m, 2H, Ph), 7.57 (dd, 1H), 8.05 (d, J=8.1 Hz, 1H), 8.22 (br s, J=4.5 Hz, 1H, NH), 8.46 (d, J=4.8 Hz, 1H), 7.64 (s, 1H), 10.43 (s, 1H, NH).
Although all H atoms were visible in difference maps, they were placed in geometrically calculated positions, with C—H distances in the range 0.93–0.96Å and N—H distances of 0.86 Å, andincluded in the final refinement in the riding model approximation,with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C). The F atoms of the -CF3 are disordered over two sets of sites in a 0.800 (8):0.200 (8) ratio.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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: SHELXTL (Sheldrick, 2008).
C19H14Cl2F3N5O2 | Dx = 1.524 Mg m−3 |
Mr = 472.25 | Melting point: 492(1) K |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
a = 26.4612 (16) Å | Cell parameters from 3952 reflections |
b = 32.8657 (19) Å | θ = 2.4–23.9° |
c = 9.4679 (6) Å | µ = 0.37 mm−1 |
V = 8233.9 (9) Å3 | T = 296 K |
Z = 16 | Block, colourless |
F(000) = 3840 | 0.24 × 0.20 × 0.18 mm |
Bruker SMART CCD diffractometer | 3565 independent reflections |
Radiation source: fine-focus sealed tube | 3284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −31→24 |
Tmin = 0.917, Tmax = 0.937 | k = −34→38 |
10439 measured reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0387P)2 + 8.8659P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3565 reflections | Δρmax = 0.18 e Å−3 |
310 parameters | Δρmin = −0.20 e Å−3 |
49 restraints | Absolute structure: Flack (1983), 1621 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (7) |
C19H14Cl2F3N5O2 | V = 8233.9 (9) Å3 |
Mr = 472.25 | Z = 16 |
Orthorhombic, Fdd2 | Mo Kα radiation |
a = 26.4612 (16) Å | µ = 0.37 mm−1 |
b = 32.8657 (19) Å | T = 296 K |
c = 9.4679 (6) Å | 0.24 × 0.20 × 0.18 mm |
Bruker SMART CCD diffractometer | 3565 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3284 reflections with I > 2σ(I) |
Tmin = 0.917, Tmax = 0.937 | Rint = 0.021 |
10439 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.082 | Δρmax = 0.18 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
3565 reflections | Absolute structure: Flack (1983), 1621 Friedel pairs |
310 parameters | Absolute structure parameter: −0.01 (7) |
49 restraints |
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 | 0.28309 (3) | 1.00598 (3) | 0.40561 (10) | 0.0647 (3) | |
Cl2 | 0.46782 (4) | 0.85540 (5) | −0.17854 (12) | 0.1075 (5) | |
F1 | 0.39895 (14) | 1.06805 (12) | 0.8595 (6) | 0.1059 (17) | 0.800 (8) |
F2 | 0.4312 (2) | 1.01859 (14) | 0.9614 (4) | 0.1148 (18) | 0.800 (8) |
F3 | 0.47071 (12) | 1.04708 (16) | 0.7981 (5) | 0.0958 (15) | 0.800 (8) |
F1' | 0.4028 (5) | 1.0381 (5) | 0.9535 (11) | 0.074 (4) | 0.200 (8) |
F2' | 0.4714 (4) | 1.0263 (5) | 0.8653 (18) | 0.087 (5) | 0.200 (8) |
F3' | 0.4283 (7) | 1.0724 (3) | 0.7878 (16) | 0.106 (6) | 0.200 (8) |
O1 | 0.36097 (7) | 0.91496 (6) | 0.4022 (2) | 0.0453 (5) | |
O2 | 0.52136 (8) | 0.96046 (6) | 0.3535 (3) | 0.0576 (6) | |
N1 | 0.35642 (9) | 0.99358 (8) | 0.7518 (3) | 0.0445 (6) | |
N2 | 0.34753 (8) | 0.97021 (6) | 0.6376 (2) | 0.0360 (5) | |
N3 | 0.28654 (9) | 0.92344 (8) | 0.7109 (3) | 0.0479 (6) | |
N4 | 0.42127 (8) | 0.95772 (6) | 0.3170 (2) | 0.0342 (5) | |
H4 | 0.4359 | 0.9808 | 0.3291 | 0.041* | |
N5 | 0.56488 (8) | 0.90701 (7) | 0.2779 (3) | 0.0419 (6) | |
H5 | 0.5672 | 0.8873 | 0.2186 | 0.050* | |
C1 | 0.26575 (11) | 0.96695 (9) | 0.5174 (3) | 0.0448 (7) | |
C2 | 0.21856 (11) | 0.94974 (11) | 0.5056 (4) | 0.0566 (9) | |
H2 | 0.1958 | 0.9587 | 0.4375 | 0.068* | |
C3 | 0.20605 (12) | 0.91908 (11) | 0.5966 (4) | 0.0602 (10) | |
H3 | 0.1747 | 0.9064 | 0.5899 | 0.072* | |
C4 | 0.23980 (14) | 0.90720 (10) | 0.6975 (4) | 0.0592 (9) | |
H4A | 0.2302 | 0.8869 | 0.7604 | 0.071* | |
C5 | 0.29811 (10) | 0.95245 (8) | 0.6209 (3) | 0.0379 (6) | |
C6 | 0.40279 (10) | 1.00776 (9) | 0.7321 (3) | 0.0434 (7) | |
C7 | 0.42585 (12) | 1.03518 (11) | 0.8368 (4) | 0.0596 (9) | |
C8 | 0.42392 (10) | 0.99401 (9) | 0.6056 (3) | 0.0429 (7) | |
H8 | 0.4558 | 1.0000 | 0.5695 | 0.052* | |
C9 | 0.38752 (10) | 0.96987 (8) | 0.5464 (3) | 0.0346 (6) | |
C10 | 0.38824 (9) | 0.94496 (7) | 0.4152 (3) | 0.0329 (6) | |
C11 | 0.43316 (10) | 0.93476 (7) | 0.1941 (3) | 0.0323 (6) | |
C12 | 0.48281 (9) | 0.92011 (7) | 0.1738 (3) | 0.0319 (6) | |
C13 | 0.49293 (10) | 0.89622 (9) | 0.0565 (3) | 0.0415 (6) | |
H13 | 0.5254 | 0.8864 | 0.0410 | 0.050* | |
C14 | 0.45484 (12) | 0.88718 (10) | −0.0367 (3) | 0.0534 (8) | |
C15 | 0.40693 (11) | 0.90324 (10) | −0.0207 (3) | 0.0507 (8) | |
H15 | 0.3822 | 0.8976 | −0.0875 | 0.061* | |
C16 | 0.39557 (10) | 0.92751 (9) | 0.0935 (3) | 0.0401 (6) | |
C17 | 0.34412 (11) | 0.94686 (11) | 0.1030 (4) | 0.0565 (8) | |
H17A | 0.3290 | 0.9476 | 0.0108 | 0.085* | |
H17B | 0.3474 | 0.9741 | 0.1385 | 0.085* | |
H17C | 0.3232 | 0.9313 | 0.1656 | 0.085* | |
C18 | 0.52432 (10) | 0.93058 (8) | 0.2762 (3) | 0.0334 (6) | |
C19 | 0.60538 (12) | 0.91391 (11) | 0.3778 (4) | 0.0597 (9) | |
H19A | 0.6216 | 0.9394 | 0.3571 | 0.090* | |
H19B | 0.6296 | 0.8923 | 0.3708 | 0.090* | |
H19C | 0.5918 | 0.9147 | 0.4718 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0572 (5) | 0.0631 (5) | 0.0737 (6) | 0.0044 (4) | −0.0053 (4) | 0.0203 (5) |
Cl2 | 0.0781 (7) | 0.1621 (12) | 0.0821 (8) | 0.0360 (7) | −0.0273 (6) | −0.0839 (8) |
F1 | 0.090 (2) | 0.090 (2) | 0.137 (3) | 0.0050 (19) | −0.020 (2) | −0.063 (2) |
F2 | 0.168 (4) | 0.117 (3) | 0.059 (2) | −0.042 (3) | −0.040 (2) | −0.0052 (18) |
F3 | 0.067 (2) | 0.132 (3) | 0.088 (3) | −0.0499 (19) | 0.0139 (17) | −0.043 (2) |
F1' | 0.067 (6) | 0.095 (6) | 0.060 (6) | −0.014 (5) | 0.009 (4) | −0.021 (5) |
F2' | 0.072 (6) | 0.094 (6) | 0.094 (7) | 0.004 (5) | −0.017 (5) | −0.018 (5) |
F3' | 0.121 (8) | 0.094 (7) | 0.103 (7) | −0.008 (5) | −0.014 (5) | −0.004 (5) |
O1 | 0.0485 (11) | 0.0440 (11) | 0.0433 (11) | −0.0146 (9) | 0.0108 (10) | −0.0005 (9) |
O2 | 0.0434 (12) | 0.0537 (12) | 0.0757 (17) | 0.0105 (10) | −0.0185 (11) | −0.0324 (12) |
N1 | 0.0407 (13) | 0.0564 (15) | 0.0365 (13) | −0.0054 (11) | 0.0038 (10) | −0.0095 (11) |
N2 | 0.0312 (11) | 0.0441 (12) | 0.0326 (12) | −0.0019 (9) | 0.0043 (9) | −0.0051 (10) |
N3 | 0.0511 (15) | 0.0500 (14) | 0.0426 (14) | −0.0052 (12) | 0.0153 (11) | −0.0014 (12) |
N4 | 0.0332 (11) | 0.0331 (11) | 0.0364 (13) | −0.0044 (9) | 0.0052 (10) | −0.0030 (10) |
N5 | 0.0347 (12) | 0.0433 (13) | 0.0478 (14) | 0.0065 (10) | −0.0059 (10) | −0.0128 (11) |
C1 | 0.0378 (16) | 0.0472 (16) | 0.0492 (18) | 0.0027 (13) | 0.0053 (13) | −0.0069 (14) |
C2 | 0.0356 (17) | 0.067 (2) | 0.067 (2) | −0.0003 (15) | −0.0020 (16) | −0.0149 (18) |
C3 | 0.0381 (17) | 0.068 (2) | 0.075 (2) | −0.0137 (16) | 0.0124 (17) | −0.022 (2) |
C4 | 0.065 (2) | 0.0553 (19) | 0.058 (2) | −0.0176 (17) | 0.0271 (17) | −0.0078 (16) |
C5 | 0.0335 (14) | 0.0422 (15) | 0.0380 (16) | −0.0023 (11) | 0.0100 (12) | −0.0074 (12) |
C6 | 0.0380 (16) | 0.0545 (17) | 0.0376 (16) | −0.0054 (13) | −0.0001 (12) | −0.0042 (13) |
C7 | 0.0503 (19) | 0.077 (2) | 0.052 (2) | −0.0108 (18) | 0.0062 (16) | −0.0155 (18) |
C8 | 0.0326 (14) | 0.0557 (17) | 0.0405 (16) | −0.0058 (13) | 0.0051 (12) | −0.0010 (13) |
C9 | 0.0337 (14) | 0.0392 (14) | 0.0307 (13) | 0.0022 (11) | 0.0021 (11) | 0.0020 (11) |
C10 | 0.0288 (13) | 0.0351 (13) | 0.0347 (14) | 0.0006 (11) | 0.0028 (11) | 0.0050 (11) |
C11 | 0.0330 (13) | 0.0329 (13) | 0.0310 (14) | −0.0043 (11) | 0.0016 (11) | 0.0042 (10) |
C12 | 0.0314 (13) | 0.0310 (12) | 0.0333 (14) | −0.0044 (10) | 0.0008 (11) | 0.0008 (11) |
C13 | 0.0357 (14) | 0.0499 (16) | 0.0391 (15) | 0.0027 (12) | 0.0002 (12) | −0.0068 (13) |
C14 | 0.0502 (18) | 0.069 (2) | 0.0405 (17) | 0.0035 (16) | −0.0066 (13) | −0.0218 (16) |
C15 | 0.0422 (17) | 0.071 (2) | 0.0392 (17) | −0.0054 (15) | −0.0108 (13) | −0.0092 (16) |
C16 | 0.0319 (14) | 0.0501 (16) | 0.0383 (16) | −0.0040 (12) | 0.0012 (11) | 0.0034 (13) |
C17 | 0.0365 (15) | 0.085 (2) | 0.0481 (19) | 0.0068 (16) | −0.0051 (14) | 0.0040 (16) |
C18 | 0.0335 (14) | 0.0308 (13) | 0.0359 (15) | −0.0015 (11) | −0.0003 (11) | −0.0020 (11) |
C19 | 0.0393 (17) | 0.073 (2) | 0.067 (2) | 0.0107 (15) | −0.0141 (15) | −0.0186 (19) |
Cl1—C1 | 1.725 (3) | C2—H2 | 0.9300 |
Cl2—C14 | 1.736 (3) | C3—C4 | 1.365 (5) |
F1—C7 | 1.311 (4) | C3—H3 | 0.9300 |
F2—C7 | 1.307 (4) | C4—H4A | 0.9300 |
F3—C7 | 1.303 (4) | C6—C8 | 1.397 (4) |
F1'—C7 | 1.266 (8) | C6—C7 | 1.472 (4) |
F2'—C7 | 1.269 (8) | C8—C9 | 1.368 (4) |
F3'—C7 | 1.310 (8) | C8—H8 | 0.9300 |
O1—C10 | 1.228 (3) | C9—C10 | 1.488 (4) |
O2—C18 | 1.227 (3) | C11—C16 | 1.397 (4) |
N1—C6 | 1.326 (4) | C11—C12 | 1.412 (4) |
N1—N2 | 1.347 (3) | C12—C13 | 1.387 (4) |
N2—C9 | 1.366 (3) | C12—C18 | 1.505 (3) |
N2—C5 | 1.441 (3) | C13—C14 | 1.372 (4) |
N3—C5 | 1.315 (4) | C13—H13 | 0.9300 |
N3—C4 | 1.353 (4) | C14—C15 | 1.382 (4) |
N4—C10 | 1.343 (3) | C15—C16 | 1.377 (4) |
N4—C11 | 1.423 (3) | C15—H15 | 0.9300 |
N4—H4 | 0.8600 | C16—C17 | 1.505 (4) |
N5—C18 | 1.324 (3) | C17—H17A | 0.9600 |
N5—C19 | 1.447 (4) | C17—H17B | 0.9600 |
N5—H5 | 0.8600 | C17—H17C | 0.9600 |
C1—C2 | 1.375 (4) | C19—H19A | 0.9600 |
C1—C5 | 1.386 (4) | C19—H19B | 0.9600 |
C2—C3 | 1.367 (5) | C19—H19C | 0.9600 |
C6—N1—N2 | 104.4 (2) | F3—C7—C6 | 111.8 (3) |
N1—N2—C9 | 112.1 (2) | F2—C7—C6 | 113.4 (3) |
N1—N2—C5 | 118.5 (2) | F3'—C7—C6 | 110.7 (7) |
C9—N2—C5 | 129.1 (2) | F1—C7—C6 | 112.9 (3) |
C5—N3—C4 | 116.0 (3) | C9—C8—C6 | 104.9 (2) |
C10—N4—C11 | 123.0 (2) | C9—C8—H8 | 127.5 |
C10—N4—H4 | 118.5 | C6—C8—H8 | 127.5 |
C11—N4—H4 | 118.5 | N2—C9—C8 | 106.3 (2) |
C18—N5—C19 | 121.1 (2) | N2—C9—C10 | 122.9 (2) |
C18—N5—H5 | 119.5 | C8—C9—C10 | 130.7 (2) |
C19—N5—H5 | 119.5 | O1—C10—N4 | 124.3 (2) |
C2—C1—C5 | 118.5 (3) | O1—C10—C9 | 121.2 (2) |
C2—C1—Cl1 | 119.8 (3) | N4—C10—C9 | 114.5 (2) |
C5—C1—Cl1 | 121.7 (2) | C16—C11—C12 | 120.8 (2) |
C3—C2—C1 | 118.1 (3) | C16—C11—N4 | 119.4 (2) |
C3—C2—H2 | 120.9 | C12—C11—N4 | 119.8 (2) |
C1—C2—H2 | 120.9 | C13—C12—C11 | 118.8 (2) |
C4—C3—C2 | 119.6 (3) | C13—C12—C18 | 120.3 (2) |
C4—C3—H3 | 120.2 | C11—C12—C18 | 120.9 (2) |
C2—C3—H3 | 120.2 | C14—C13—C12 | 119.7 (3) |
N3—C4—C3 | 123.4 (3) | C14—C13—H13 | 120.1 |
N3—C4—H4A | 118.3 | C12—C13—H13 | 120.1 |
C3—C4—H4A | 118.3 | C13—C14—C15 | 121.4 (3) |
N3—C5—C1 | 124.3 (3) | C13—C14—Cl2 | 118.8 (2) |
N3—C5—N2 | 115.7 (3) | C15—C14—Cl2 | 119.8 (2) |
C1—C5—N2 | 119.9 (2) | C16—C15—C14 | 120.5 (3) |
N1—C6—C8 | 112.2 (3) | C16—C15—H15 | 119.7 |
N1—C6—C7 | 120.2 (3) | C14—C15—H15 | 119.7 |
C8—C6—C7 | 127.6 (3) | C15—C16—C11 | 118.6 (3) |
F1'—C7—F2' | 106.9 (8) | C15—C16—C17 | 119.3 (3) |
F1'—C7—F3 | 131.5 (6) | C11—C16—C17 | 122.1 (3) |
F2'—C7—F3 | 42.6 (7) | C16—C17—H17A | 109.5 |
F1'—C7—F2 | 45.3 (7) | C16—C17—H17B | 109.5 |
F2'—C7—F2 | 67.0 (8) | H17A—C17—H17B | 109.5 |
F3—C7—F2 | 106.3 (4) | C16—C17—H17C | 109.5 |
F1'—C7—F3' | 105.2 (8) | H17A—C17—H17C | 109.5 |
F2'—C7—F3' | 104.1 (8) | H17B—C17—H17C | 109.5 |
F3—C7—F3' | 64.8 (8) | O2—C18—N5 | 120.9 (2) |
F2—C7—F3' | 134.7 (7) | O2—C18—C12 | 121.4 (2) |
F1'—C7—F1 | 62.1 (7) | N5—C18—C12 | 117.7 (2) |
F2'—C7—F1 | 132.1 (7) | N5—C19—H19A | 109.5 |
F3—C7—F1 | 107.1 (4) | N5—C19—H19B | 109.5 |
F2—C7—F1 | 104.8 (4) | H19A—C19—H19B | 109.5 |
F3'—C7—F1 | 46.8 (8) | N5—C19—H19C | 109.5 |
F1'—C7—C6 | 115.8 (6) | H19A—C19—H19C | 109.5 |
F2'—C7—C6 | 113.3 (7) | H19B—C19—H19C | 109.5 |
C6—N1—N2—C9 | −0.5 (3) | N1—N2—C9—C10 | 177.2 (2) |
C6—N1—N2—C5 | −175.3 (2) | C5—N2—C9—C10 | −8.7 (4) |
C5—C1—C2—C3 | −0.1 (4) | C6—C8—C9—N2 | −0.2 (3) |
Cl1—C1—C2—C3 | −179.5 (3) | C6—C8—C9—C10 | −176.6 (3) |
C1—C2—C3—C4 | 1.5 (5) | C11—N4—C10—O1 | −8.6 (4) |
C5—N3—C4—C3 | 1.0 (4) | C11—N4—C10—C9 | 170.3 (2) |
C2—C3—C4—N3 | −2.0 (5) | N2—C9—C10—O1 | −22.0 (4) |
C4—N3—C5—C1 | 0.5 (4) | C8—C9—C10—O1 | 154.0 (3) |
C4—N3—C5—N2 | 178.7 (2) | N2—C9—C10—N4 | 159.1 (2) |
C2—C1—C5—N3 | −1.0 (4) | C8—C9—C10—N4 | −24.9 (4) |
Cl1—C1—C5—N3 | 178.5 (2) | C10—N4—C11—C16 | 64.7 (3) |
C2—C1—C5—N2 | −179.1 (3) | C10—N4—C11—C12 | −116.2 (3) |
Cl1—C1—C5—N2 | 0.4 (4) | C16—C11—C12—C13 | −3.9 (4) |
N1—N2—C5—N3 | −69.8 (3) | N4—C11—C12—C13 | 177.1 (2) |
C9—N2—C5—N3 | 116.4 (3) | C16—C11—C12—C18 | 175.2 (2) |
N1—N2—C5—C1 | 108.4 (3) | N4—C11—C12—C18 | −3.8 (3) |
C9—N2—C5—C1 | −65.4 (4) | C11—C12—C13—C14 | −0.3 (4) |
N2—N1—C6—C8 | 0.4 (3) | C18—C12—C13—C14 | −179.4 (3) |
N2—N1—C6—C7 | 179.6 (3) | C12—C13—C14—C15 | 3.7 (5) |
N1—C6—C7—F1' | 11.8 (10) | C12—C13—C14—Cl2 | −177.2 (2) |
C8—C6—C7—F1' | −169.1 (10) | C13—C14—C15—C16 | −2.8 (5) |
N1—C6—C7—F2' | 135.8 (10) | Cl2—C14—C15—C16 | 178.0 (3) |
C8—C6—C7—F2' | −45.1 (11) | C14—C15—C16—C11 | −1.4 (4) |
N1—C6—C7—F3 | −177.9 (4) | C14—C15—C16—C17 | 175.9 (3) |
C8—C6—C7—F3 | 1.1 (6) | C12—C11—C16—C15 | 4.7 (4) |
N1—C6—C7—F2 | 61.9 (5) | N4—C11—C16—C15 | −176.2 (2) |
C8—C6—C7—F2 | −119.0 (5) | C12—C11—C16—C17 | −172.5 (3) |
N1—C6—C7—F3' | −107.7 (10) | N4—C11—C16—C17 | 6.6 (4) |
C8—C6—C7—F3' | 71.4 (11) | C19—N5—C18—O2 | 4.6 (4) |
N1—C6—C7—F1 | −57.1 (5) | C19—N5—C18—C12 | −177.1 (3) |
C8—C6—C7—F1 | 122.0 (4) | C13—C12—C18—O2 | 157.4 (3) |
N1—C6—C8—C9 | −0.2 (3) | C11—C12—C18—O2 | −21.8 (4) |
C7—C6—C8—C9 | −179.3 (3) | C13—C12—C18—N5 | −21.0 (4) |
N1—N2—C9—C8 | 0.4 (3) | C11—C12—C18—N5 | 159.9 (2) |
C5—N2—C9—C8 | 174.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O2 | 0.86 | 2.37 | 2.673 (3) | 101 |
N4—H4···O2i | 0.86 | 2.25 | 3.107 (3) | 176 |
N5—H5···O1ii | 0.86 | 2.16 | 2.915 (3) | 146 |
C8—H8···O2i | 0.93 | 2.50 | 3.168 (4) | 129 |
Symmetry codes: (i) −x+1, −y+2, z; (ii) x+1/4, −y+7/4, z−1/4. |
Experimental details
Crystal data | |
Chemical formula | C19H14Cl2F3N5O2 |
Mr | 472.25 |
Crystal system, space group | Orthorhombic, Fdd2 |
Temperature (K) | 296 |
a, b, c (Å) | 26.4612 (16), 32.8657 (19), 9.4679 (6) |
V (Å3) | 8233.9 (9) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.24 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.917, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10439, 3565, 3284 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.082, 1.04 |
No. of reflections | 3565 |
No. of parameters | 310 |
No. of restraints | 49 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 |
Absolute structure | Flack (1983), 1621 Friedel pairs |
Absolute structure parameter | −0.01 (7) |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O2 | 0.86 | 2.37 | 2.673 (3) | 101 |
N4—H4···O2i | 0.86 | 2.25 | 3.107 (3) | 176 |
N5—H5···O1ii | 0.86 | 2.16 | 2.915 (3) | 146 |
C8—H8···O2i | 0.93 | 2.50 | 3.168 (4) | 129 |
Symmetry codes: (i) −x+1, −y+2, z; (ii) x+1/4, −y+7/4, z−1/4. |
Anthranilamide compounds containing an N-pyridyl pyrazole grouping are a new class of inseticides showing potent activity against a broad spectrum of Lepidoptera and no-cross resistance to existing insecticides (Lahm et al., 2003) and their mode of action has been been established (Lahm et al., 2005). Anthranilamides show little effect on mammalian ryanodine receptors and as a result they show excellent insect versus mammalian selectivity. As part of our studies in this area, we now report the crystal structures of the title compound, (I), (Fig. 1) which possesses high insecticidal activity.
The pyrazole ring and pyridine rings are not coplanar, the dihedral angle formed by the least-squares planes of the rings being equal to 68.15 (16)°. The dihedral angle between the mean plane of the pyrazole ring and the plane of the C10/O1/N4 group is 23.4 (2)° and the dihedral angle between the mean plane of the phenyl ring and the plane of the C10/O1/N4 group is 59.9 (2)°.
An intramolecular N—H···O hydrogen bond (Table 1) is observed, which helps to establish the molecular conformation. Intermolecular N—H···O and C—H···O bonds result in a three-dimensional network.