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access4,6-Bis[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]pyrimidine
aKey Laboratory of Pesticide Chemistry and Applications, Ministry of Agriculture, Institute of Plant Protection Academy of Agricultural Sciences, Beijing 100193, People's Republic of China
*Correspondence e-mail: jning502@yahoo.com.cn
The complete molecule of the the title compound, C14H10F6N6, is generated by crystallographic twofold symmetry, with two C atoms lying on the roatation axis. The dihedral angle between the central and peripheral rings is 25.97 (8)°.
Related literature
For background to fluorine-containing heterocycles and their properties, see: Krishnaiah & Narsaiah (2002![[Krishnaiah, A. & Narsaiah, B. (2002). J. Fluorine Chem. 115, 9-11.]](../../../../../../logos/arrows/e_arr.gif "Krishnaiah, A. & Narsaiah, B. (2002). J. Fluorine Chem. 115, 9-11.")
); Ohno et al. (2004).
![[Scheme 1]](hb5156scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear; data reduction: CrystalClear; 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: SHELXL97.
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809043657/hb5156sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043657/hb5156Isup2.hkl
The title compound (0.1 g) was dissolved in anhydrous methanol (20 ml) at room temperature. Colourless blocks of (I) were obtained through slow evaporation after two weeks.
All the hydrogen atoms were placed in idealised positions with C—H = 0.93–0.98Å and Uiso (H) = 1.2–1.5Uep (C).
Strategically positioned fluorine in especially those containing trifluromethyl groups plays an important role in medicines and agrochemicals (e.g. Krishnaiah & Narsaiah, 2002). Specifically, the fluorinated pyrazoles have been shown to possess high biological activities (e.g. Ohno et al. 2004) as herbicides, fungicides, insecticides, analgesics, antipyretics and antiinflammatories. Pyrazolopyrimidine and related fuesd heterocycles are of interest as potential bioactive molecules. Recently, the new title compound (I) was synthesized in our group with high herbicidal activity. The of the compound (I) is shown in Fig. 1.
For background to fluorine-containing heterocycles and their properties, see: Krishnaiah & Narsaiah (2002); Ohno et al. (2004). Please provide caption for Fig. 1 (including probability level)
Data collection: CrystalClear (Rigaku, 2008); cell CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hb5156fig1thm.gif) | Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids and atom-numbering scheme. |
| C14H10F6N6 | F(000) = 760 |
| Mr = 376.28 | Dx = 1.670 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 648 reflections |
| a = 8.5387 (14) Å | θ = 2.2–27.5° |
| b = 16.110 (6) Å | µ = 0.16 mm−1 |
| c = 11.022 (5) Å | T = 173 K |
| β = 99.295 (5)° | Block, colorless |
| V = 1496.2 (9) Å3 | 0.41 × 0.36 × 0.26 mm |
| Z = 4 |
| Rigaku Saturn724+ CCD diffractometer | 1706 independent reflections |
| Radiation source: sealed tube | 1678 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.033 |
| ω scans at fixed χ = 45° | θmax = 27.5°, θmin = 2.7° |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2008) | h = −11→11 |
| Tmin = 0.938, Tmax = 0.960 | k = −20→20 |
| 8915 measured reflections | l = −14→14 |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.100 | H-atom parameters constrained |
| S = 1.19 | w = 1/[σ2(Fo2) + (0.0291P)2 + 1.4916P] where P = (Fo2 + 2Fc2)/3 |
| 1706 reflections | (Δ/σ)max < 0.001 |
| 120 parameters | Δρmax = 0.23 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
| C14H10F6N6 | V = 1496.2 (9) Å3 |
| Mr = 376.28 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 8.5387 (14) Å | µ = 0.16 mm−1 |
| b = 16.110 (6) Å | T = 173 K |
| c = 11.022 (5) Å | 0.41 × 0.36 × 0.26 mm |
| β = 99.295 (5)° |
| Rigaku Saturn724+ CCD diffractometer | 1706 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2008) | 1678 reflections with I > 2σ(I) |
| Tmin = 0.938, Tmax = 0.960 | Rint = 0.033 |
| 8915 measured reflections |
| R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
| wR(F2) = 0.100 | H-atom parameters constrained |
| S = 1.19 | Δρmax = 0.23 e Å−3 |
| 1706 reflections | Δρmin = −0.22 e Å−3 |
| 120 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 | ||
| F1 | 0.53252 (12) | 0.61885 (7) | 0.61601 (11) | 0.0484 (3) | |
| F2 | 0.39212 (17) | 0.66320 (8) | 0.45033 (11) | 0.0610 (4) | |
| F3 | 0.31154 (14) | 0.67824 (7) | 0.62363 (12) | 0.0544 (3) | |
| N1 | 0.22004 (15) | 0.52452 (8) | 0.43231 (12) | 0.0284 (3) | |
| N2 | 0.16127 (15) | 0.44751 (8) | 0.45125 (11) | 0.0269 (3) | |
| N3 | 0.07685 (16) | 0.32384 (8) | 0.35077 (13) | 0.0311 (3) | |
| C1 | 0.30268 (18) | 0.54413 (10) | 0.54059 (14) | 0.0288 (3) | |
| C2 | 0.29725 (19) | 0.48203 (10) | 0.62924 (14) | 0.0310 (4) | |
| H2A | 0.3470 | 0.4829 | 0.7128 | 0.037* | |
| C3 | 0.20539 (18) | 0.42006 (10) | 0.57018 (14) | 0.0289 (3) | |
| C4 | 0.1508 (2) | 0.34123 (11) | 0.62036 (16) | 0.0369 (4) | |
| H4A | 0.1750 | 0.3423 | 0.7103 | 0.055* | |
| H4B | 0.2054 | 0.2942 | 0.5892 | 0.055* | |
| H4C | 0.0360 | 0.3353 | 0.5945 | 0.055* | |
| C5 | 0.07580 (17) | 0.40647 (10) | 0.34787 (13) | 0.0266 (3) | |
| C6 | 0.0000 | 0.45258 (14) | 0.2500 | 0.0265 (4) | |
| H6A | 0.0000 | 0.5115 | 0.2500 | 0.032* | |
| C7 | 0.0000 | 0.28736 (15) | 0.2500 | 0.0331 (5) | |
| H7A | 0.0000 | 0.2284 | 0.2500 | 0.040* | |
| C8 | 0.3840 (2) | 0.62608 (11) | 0.55639 (15) | 0.0342 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0298 (5) | 0.0524 (7) | 0.0594 (7) | −0.0036 (5) | −0.0038 (5) | −0.0096 (5) |
| F2 | 0.0863 (10) | 0.0544 (7) | 0.0384 (6) | −0.0291 (7) | −0.0011 (6) | 0.0066 (5) |
| F3 | 0.0461 (7) | 0.0431 (6) | 0.0754 (9) | 0.0017 (5) | 0.0146 (6) | −0.0206 (6) |
| N1 | 0.0275 (6) | 0.0310 (7) | 0.0259 (6) | −0.0002 (5) | 0.0011 (5) | −0.0002 (5) |
| N2 | 0.0254 (6) | 0.0302 (7) | 0.0242 (6) | 0.0013 (5) | 0.0014 (5) | 0.0006 (5) |
| N3 | 0.0300 (7) | 0.0313 (7) | 0.0311 (7) | 0.0019 (5) | 0.0023 (5) | 0.0010 (6) |
| C1 | 0.0251 (7) | 0.0353 (8) | 0.0256 (7) | 0.0034 (6) | 0.0027 (6) | −0.0028 (6) |
| C2 | 0.0288 (8) | 0.0393 (9) | 0.0239 (7) | 0.0063 (6) | 0.0013 (6) | −0.0011 (6) |
| C3 | 0.0270 (7) | 0.0350 (8) | 0.0244 (7) | 0.0070 (6) | 0.0038 (6) | 0.0024 (6) |
| C4 | 0.0432 (10) | 0.0373 (9) | 0.0296 (8) | 0.0035 (7) | 0.0044 (7) | 0.0062 (7) |
| C5 | 0.0223 (7) | 0.0324 (8) | 0.0252 (7) | 0.0012 (6) | 0.0043 (6) | −0.0016 (6) |
| C6 | 0.0236 (10) | 0.0292 (11) | 0.0262 (10) | 0.000 | 0.0028 (8) | 0.000 |
| C7 | 0.0341 (12) | 0.0291 (11) | 0.0352 (12) | 0.000 | 0.0032 (9) | 0.000 |
| C8 | 0.0318 (8) | 0.0394 (9) | 0.0304 (8) | 0.0008 (7) | 0.0014 (6) | −0.0031 (7) |
| F1—C8 | 1.3359 (19) | C2—C3 | 1.368 (2) |
| F2—C8 | 1.325 (2) | C2—H2A | 0.9500 |
| F3—C8 | 1.336 (2) | C3—C4 | 1.490 (2) |
| N1—C1 | 1.323 (2) | C4—H4A | 0.9800 |
| N1—N2 | 1.3668 (19) | C4—H4B | 0.9800 |
| N2—C3 | 1.377 (2) | C4—H4C | 0.9800 |
| N2—C5 | 1.414 (2) | C5—C6 | 1.3815 (19) |
| N3—C5 | 1.331 (2) | C6—C5i | 1.3815 (19) |
| N3—C7 | 1.3319 (17) | C6—H6A | 0.9500 |
| C1—C2 | 1.404 (2) | C7—N3i | 1.3319 (17) |
| C1—C8 | 1.489 (2) | C7—H7A | 0.9500 |
| C1—N1—N2 | 103.56 (13) | H4A—C4—H4C | 109.5 |
| N1—N2—C3 | 112.71 (12) | H4B—C4—H4C | 109.5 |
| N1—N2—C5 | 117.12 (12) | N3—C5—C6 | 123.83 (15) |
| C3—N2—C5 | 130.02 (14) | N3—C5—N2 | 116.59 (13) |
| C5—N3—C7 | 114.87 (15) | C6—C5—N2 | 119.57 (15) |
| N1—C1—C2 | 112.63 (15) | C5i—C6—C5 | 114.9 (2) |
| N1—C1—C8 | 119.21 (14) | C5i—C6—H6A | 122.5 |
| C2—C1—C8 | 128.13 (15) | C5—C6—H6A | 122.5 |
| C3—C2—C1 | 105.64 (14) | N3—C7—N3i | 127.6 (2) |
| C3—C2—H2A | 127.2 | N3—C7—H7A | 116.2 |
| C1—C2—H2A | 127.2 | N3i—C7—H7A | 116.2 |
| C2—C3—N2 | 105.44 (14) | F2—C8—F1 | 107.01 (15) |
| C2—C3—C4 | 129.45 (15) | F2—C8—F3 | 107.49 (16) |
| N2—C3—C4 | 124.98 (15) | F1—C8—F3 | 105.65 (14) |
| C3—C4—H4A | 109.5 | F2—C8—C1 | 112.77 (14) |
| C3—C4—H4B | 109.5 | F1—C8—C1 | 111.59 (14) |
| H4A—C4—H4B | 109.5 | F3—C8—C1 | 111.93 (14) |
| C3—C4—H4C | 109.5 | ||
| C1—N1—N2—C3 | 0.68 (16) | N1—N2—C5—N3 | 152.46 (14) |
| C1—N1—N2—C5 | −175.36 (13) | C3—N2—C5—N3 | −22.8 (2) |
| N2—N1—C1—C2 | −0.63 (17) | N1—N2—C5—C6 | −26.16 (18) |
| N2—N1—C1—C8 | −179.10 (13) | C3—N2—C5—C6 | 158.62 (13) |
| N1—C1—C2—C3 | 0.37 (18) | N3—C5—C6—C5i | −0.48 (11) |
| C8—C1—C2—C3 | 178.67 (15) | N2—C5—C6—C5i | 178.03 (15) |
| C1—C2—C3—N2 | 0.07 (17) | C5—N3—C7—N3i | −0.43 (10) |
| C1—C2—C3—C4 | −175.86 (16) | N1—C1—C8—F2 | −14.0 (2) |
| N1—N2—C3—C2 | −0.47 (17) | C2—C1—C8—F2 | 167.76 (16) |
| C5—N2—C3—C2 | 174.92 (14) | N1—C1—C8—F1 | −134.52 (15) |
| N1—N2—C3—C4 | 175.69 (14) | C2—C1—C8—F1 | 47.3 (2) |
| C5—N2—C3—C4 | −8.9 (3) | N1—C1—C8—F3 | 107.31 (17) |
| C7—N3—C5—C6 | 0.9 (2) | C2—C1—C8—F3 | −70.9 (2) |
| C7—N3—C5—N2 | −177.66 (11) |
| Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C14H10F6N6 |
| Mr | 376.28 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 173 |
| a, b, c (Å) | 8.5387 (14), 16.110 (6), 11.022 (5) |
| β (°) | 99.295 (5) |
| V (Å3) | 1496.2 (9) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.16 |
| Crystal size (mm) | 0.41 × 0.36 × 0.26 |
| Data collection | |
| Diffractometer | Rigaku Saturn724+ CCD |
| Absorption correction | Multi-scan (CrystalClear; Rigaku, 2008) |
| Tmin, Tmax | 0.938, 0.960 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 8915, 1706, 1678 |
| Rint | 0.033 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.100, 1.19 |
| No. of reflections | 1706 |
| No. of parameters | 120 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.23, −0.22 |
Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the China Postdoctoral Science Foundation (No. 20070420444), the Major State Basic Research Development program of China (No. 2010CB126106 and No. 2006CB101907), and the 863 high-tech key project of China (2006AA10A203).
References
Krishnaiah, A. & Narsaiah, B. (2002). J. Fluorine Chem. 115, 9–11. Web of Science CrossRef CAS Google Scholar
Ohno, R., Watanabe, A., Nagaoka, M., Ueda, T., Sakurai, H., Hori, M. & Hirai, K. (2004). J. Pestic. Sci. 29, 15–26. Web of Science CrossRef CAS Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Toyko, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Strategically positioned fluorine in heterocyclic compounds, especially those containing trifluromethyl groups plays an important role in medicines and agrochemicals (e.g. Krishnaiah & Narsaiah, 2002). Specifically, the fluorinated pyrazoles have been shown to possess high biological activities (e.g. Ohno et al. 2004) as herbicides, fungicides, insecticides, analgesics, antipyretics and antiinflammatories. Pyrazolopyrimidine and related fuesd heterocycles are of interest as potential bioactive molecules. Recently, the new title compound (I) was synthesized in our group with high herbicidal activity. The crystal structure of the compound (I) is shown in Fig. 1.