PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o430.
Published online 2008 January 11. doi:  10.1107/S1600536807060205
PMCID: PMC2960342

3-Chloro-5-(trifluoro­meth­yl)pyridin-2-amine

Abstract

In the title compound, C6H4ClF3N2, an inter­mediate in the synthesis of the fungicide fluazinam, the F atoms of the trifluoro­methyl group are disordered over two sites in a 0.683 (14):0.317 (14) ratio. In the crystal structure, centrosymmetric dimers arise from pairs of N—H(...)N hydrogen bonds.

Related literature

For related literature, see: Guo et al. (1991 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o430-scheme1.jpg

Experimental

Crystal data

  • C6H4ClF3N2
  • M r = 196.56
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o430-efi1.jpg
  • a = 5.801 (1) Å
  • b = 17.978 (5) Å
  • c = 7.578 (2) Å
  • β = 100.19 (4)°
  • V = 777.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.49 mm−1
  • T = 294 (2) K
  • 0.24 × 0.22 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.893, T max = 0.909
  • 3820 measured reflections
  • 1368 independent reflections
  • 904 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.137
  • S = 1.01
  • 1368 reflections
  • 145 parameters
  • 39 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807060205/hb2620sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807060205/hb2620Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the fund of the Ordnance Technology Institute for support.

supplementary crystallographic information

Comment

The title compound, (I), is an intermediate in the preparation of fluazinam or 3-chloro-N-[3-chloro-2,6-dinitro- 4-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-2-pyridinamine which is a kind of pyridine fungicide (Guo et al., 1991).

The F atoms of the trifluoromethyl group are disordered over two sites in a 0.683 (14):0.317 (14) ratio (Fig. 1). An acute intramolecular N—H···Cl interaction occurs and the packing is consolidated by an N—H···N hydrogen bond (Table 1) resulting in inversion dimers.

Experimental

A mixture of 2,3-dichloro-5-(trifluoromethyl)pyridine (216 g, 1 mol) and NH~3 (68 g, 4 mol) in ethanol was heated to 50 atm. After 10 h, the reaction was complete, the resulting solid was filtered off and washed with a little cool ethanol. 50 mg of (I) was dissolved in 20 ml e thanol and the solution was kept at room temperature for 10 d; natural evaporation gave colourless blocks of (I).

Refinement

The N-bound H atoms were located in a difference map and freely refined. The C-bound H atoms were positioned geometrically, with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability ellipsoids (arbitrary spheres for the H atoms). Only one orientation of the –CF3 group is shown. The N—H···Cl interaction is shown as a double-dashed line. ...
Fig. 2.
The formation of the title compound.

Crystal data

C6H4ClF3N2F000 = 392
Mr = 196.56Dx = 1.678 Mg m3
Monoclinic, P21/nMelting point = 145–146 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 5.801 (1) ÅCell parameters from 1210 reflections
b = 17.978 (5) Åθ = 2.9–25.9º
c = 7.578 (2) ŵ = 0.49 mm1
β = 100.19 (4)ºT = 294 (2) K
V = 777.8 (3) Å3Block, colourless
Z = 40.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer1368 independent reflections
Radiation source: fine-focus sealed tube904 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.054
T = 294(2) Kθmax = 25.0º
ω scansθmin = 2.3º
Absorption correction: multi-scan(SADABS; Bruker, 1997)h = −5→6
Tmin = 0.893, Tmax = 0.909k = −21→20
3820 measured reflectionsl = −9→5

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.137  w = 1/[σ2(Fo2) + (0.0614P)2 + 0.3792P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
1368 reflectionsΔρmax = 0.22 e Å3
145 parametersΔρmin = −0.18 e Å3
39 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/UeqOcc. (<1)
Cl10.19339 (18)0.59163 (5)0.35440 (14)0.0682 (4)
F10.075 (2)0.2514 (7)0.3252 (15)0.117 (4)0.683 (14)
F20.2861 (13)0.2807 (3)0.1285 (11)0.108 (2)0.683 (14)
F30.4036 (17)0.3071 (3)0.3974 (16)0.131 (4)0.683 (14)
F1'0.078 (4)0.2487 (13)0.256 (3)0.097 (6)0.317 (14)
F2'0.392 (4)0.2973 (9)0.246 (4)0.127 (6)0.317 (14)
F3'0.267 (3)0.3002 (6)0.4870 (18)0.107 (5)0.317 (14)
N1−0.2580 (5)0.44234 (16)0.1206 (4)0.0537 (8)
N2−0.2851 (6)0.56838 (18)0.1481 (5)0.0658 (9)
C1−0.1364 (6)0.3800 (2)0.1569 (5)0.0548 (9)
H1−0.20720.33550.11450.066*
C20.0859 (6)0.3770 (2)0.2526 (5)0.0540 (9)
C30.1917 (6)0.4434 (2)0.3143 (5)0.0540 (9)
H30.34410.44390.37810.065*
C40.0705 (6)0.50724 (19)0.2804 (4)0.0460 (8)
C5−0.1582 (6)0.50666 (18)0.1823 (4)0.0468 (9)
C60.2091 (10)0.3053 (3)0.2854 (8)0.0837 (15)
H2A−0.230 (5)0.6135 (10)0.181 (5)0.070 (13)*
H2B−0.426 (4)0.5678 (18)0.078 (4)0.076 (13)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0704 (7)0.0546 (6)0.0765 (7)−0.0139 (5)0.0049 (5)−0.0129 (5)
F10.143 (5)0.074 (5)0.141 (7)0.016 (4)0.037 (6)0.046 (5)
F20.132 (4)0.077 (3)0.116 (5)0.042 (3)0.027 (4)−0.011 (3)
F30.120 (5)0.092 (3)0.150 (6)0.039 (3)−0.065 (5)−0.017 (4)
F1'0.110 (9)0.053 (7)0.115 (10)0.006 (6)−0.014 (8)−0.012 (8)
F2'0.114 (9)0.123 (8)0.153 (11)0.054 (7)0.052 (9)0.024 (8)
F3'0.135 (9)0.077 (6)0.097 (7)0.039 (6)−0.009 (7)0.020 (5)
N10.0483 (17)0.0481 (17)0.0600 (19)−0.0008 (14)−0.0036 (14)−0.0038 (14)
N20.060 (2)0.0489 (19)0.082 (2)0.0067 (17)−0.0063 (18)−0.0031 (17)
C10.058 (2)0.046 (2)0.059 (2)−0.0055 (18)0.0029 (18)−0.0059 (16)
C20.055 (2)0.049 (2)0.055 (2)0.0041 (18)0.0020 (18)0.0006 (16)
C30.046 (2)0.059 (2)0.054 (2)0.0014 (18)−0.0015 (16)−0.0009 (17)
C40.048 (2)0.048 (2)0.0419 (19)−0.0069 (16)0.0080 (16)−0.0039 (15)
C50.052 (2)0.0460 (19)0.0430 (19)0.0037 (17)0.0091 (16)0.0007 (15)
C60.076 (4)0.060 (3)0.105 (4)0.000 (3)−0.012 (3)0.002 (3)

Geometric parameters (Å, °)

Cl1—C41.727 (5)N2—H2A0.891 (11)
F1—C61.311 (13)N2—H2B0.895 (11)
F2—C61.414 (9)C1—C21.364 (6)
F3—C61.287 (7)C1—H10.9300
F1'—C61.27 (2)C2—C31.385 (6)
F2'—C61.162 (14)C2—C61.474 (6)
F3'—C61.508 (15)C3—C41.347 (5)
N1—C11.327 (5)C3—H30.9300
N1—C51.340 (5)C4—C51.401 (6)
N2—C51.332 (5)
C1—N1—C5118.4 (3)F2'—C6—F355.6 (11)
C5—N2—H2A123 (2)F1'—C6—F3124.4 (11)
C5—N2—H2B121 (2)F2'—C6—F1125.0 (11)
H2A—N2—H2B115.1 (19)F1'—C6—F123.6 (11)
N1—C1—C2124.1 (3)F3—C6—F1110.7 (8)
N1—C1—H1117.9F2'—C6—F246.1 (14)
C2—C1—H1117.9F1'—C6—F282.5 (11)
C1—C2—C3117.8 (3)F3—C6—F2101.0 (7)
C1—C2—C6120.6 (4)F1—C6—F2104.5 (7)
C3—C2—C6121.6 (4)F2'—C6—C2120.2 (8)
C4—C3—C2119.0 (4)F1'—C6—C2114.6 (12)
C4—C3—H3120.5F3—C6—C2115.6 (5)
C2—C3—H3120.5F1—C6—C2113.4 (8)
C3—C4—C5120.5 (3)F2—C6—C2110.4 (5)
C3—C4—Cl1121.0 (3)F2'—C6—F3'101.6 (12)
C5—C4—Cl1118.4 (3)F1'—C6—F3'98.5 (10)
N2—C5—N1117.5 (3)F3—C6—F3'47.3 (6)
N2—C5—C4122.4 (3)F1—C6—F3'75.9 (8)
N1—C5—C4120.1 (3)F2—C6—F3'141.9 (7)
F2'—C6—F1'113.8 (16)C2—C6—F3'103.8 (6)
C5—N1—C1—C2−0.5 (5)C1—C2—C6—F2'125.8 (19)
N1—C1—C2—C3−0.6 (6)C3—C2—C6—F2'−53 (2)
N1—C1—C2—C6−179.5 (4)C1—C2—C6—F1'−15.4 (13)
C1—C2—C3—C41.2 (5)C3—C2—C6—F1'165.7 (12)
C6—C2—C3—C4−179.9 (4)C1—C2—C6—F3−170.6 (9)
C2—C3—C4—C5−0.8 (5)C3—C2—C6—F310.5 (11)
C2—C3—C4—Cl1179.9 (3)C1—C2—C6—F1−41.3 (9)
C1—N1—C5—N2−178.4 (3)C3—C2—C6—F1139.8 (7)
C1—N1—C5—C40.9 (5)C1—C2—C6—F275.5 (6)
C3—C4—C5—N2179.0 (3)C3—C2—C6—F2−103.3 (6)
Cl1—C4—C5—N2−1.6 (5)C1—C2—C6—F3'−121.6 (9)
C3—C4—C5—N1−0.3 (5)C3—C2—C6—F3'59.5 (10)
Cl1—C4—C5—N1179.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl10.89 (2)2.60 (3)2.965 (9)105.3 (19)
N2—H2B···N1i0.89 (3)2.16 (3)3.049 (9)171 (3)

Symmetry codes: (i) −x−1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2620).

References

  • Bruker (1997). SADABS (Version 2.0), SMART (Version 5.611), SAINT (Version 6.0) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Guo, Z.-J., Miyoshi, H., Komyoji, T., Haga, T. & Fujita, T. (1991). Biochim. Biophys. Acta, 1056, 89–92.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography