organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Fluazinam

aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

(Received 27 July 2013; accepted 19 August 2013; online 23 August 2013)

In the asymmetric unit of the title compound {systematic name: 3-chloro-N-[3-chloro-5-(tri­fluoro­meth­yl)pyridin-2-yl]-2,6-di­nitro-4-(tri­fluoro­methyl)­aniline}, C13H4Cl2F6N4O4, which is the fungicide fluazinam, the dihedral angle between the pyridine and benzene ring planes is 42.20 (4)°. In the crystal, pairs of N—H⋯F hydrogen bonds link the mol­ecules into inversion dimers which are linked by C—Cl⋯π [Cl⋯ring centroid = 3.3618 (4) A °] and N—O⋯π [O⋯ring centroid = 3.1885 (16) Å] inter­actions into chains along [100]. In addition, short Cl⋯Cl, O⋯Cl, and F⋯F contacts [3.4676 (7), 3.2371 (13) and 2.7910 (15) Å] are present which connect the chains, yielding a three-dimensional network.

Related literature

For information on the toxicity and fungicidal properties of the title compound, see: Yoshida & Yukimoto (1993[Yoshida, M. & Yukimoto, M. (1993). Pestic. Biochem. Physiol. 47, 171-177.]); Draper et al. (2003[Draper, A., Cullinan, P., Campbell, C., Jones, M. & Taylor, A. N. (2003). Occup. Environ. Med. 60, 76-77.]). For a related structure, see: McCullough et al. (1972[McCullough, J. D., Paul, I. C. & Curtin, D. Y. (1972). J. Am. Chem. Soc. 94, 883-889.]).

[Scheme 1]

Experimental

Crystal data
  • C13H4Cl2F6N4O4

  • Mr = 465.10

  • Triclinic, [P \overline 1]

  • a = 8.9546 (1) Å

  • b = 9.0724 (1) Å

  • c = 10.6818 (2) Å

  • α = 79.556 (1)°

  • β = 75.420 (1)°

  • γ = 83.451 (1)°

  • V = 823.79 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.49 mm−1

  • T = 173 K

  • 0.30 × 0.18 × 0.15 mm

Data collection
  • Bruker APEXII CCD detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.867, Tmax = 0.930

  • 15193 measured reflections

  • 4096 independent reflections

  • 3662 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.085

  • S = 1.04

  • 4096 reflections

  • 262 parameters

  • H-atom parameters constrained

  • Δρmax = 0.47 e Å−3

  • Δρmin = −0.45 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯F3i 0.88 2.52 3.0690 (15) 121
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1998[Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound fluazinam, C13H4Cl2F6N4O4, is a broad spectrum contact fungicide that can be applied as a foliar spray or soil treatment (Yoshida et al., 1993; Draper et al., 2003) and its crystal structure is reported herein. In this compound (Fig. 1), the dihedral angle between the pyridyl ring and the phenyl ring is 42.20 (4)°. All bond lengths and bond angles are normal and comparable to those observed in the crystal structures of a similar compound (McCullough et al., 1972). In the crystal structure (Fig. 2), an intermolecular N—H···F hydrogen bond is observed (Table 1), giving a dimer structure. In this structure there are both a C3—Cl1···π interaction with the pyridyl ring [Cl1···Cg1ii = 3.3618 (4) Å] and a N1—O1···π interaction with the phenyl ring [O1···Cg2ii = 3.1885 (16) Å]. In addition, short Cl···Cl, O···Cl, and F···F contacts [Cl2···Cl2iii, 3.4676 (7) Å, O3···Cl1iv, 3.2371 (13) Å, and F3···F6v, 2.7910 (15) Å] are present [for symmetry codes: (ii), -x+1, -y+1, -z+1, (iii), -x+1, -y+1, -z+2, (iv), x, y - 1, z, and (v), x + 1, y + 1, z + 1]. A three-dimensional network is formed by the hydrogen bond and these interactions.

Related literature top

For information on the toxicity and fungicidal properties of the title compound, see: Yoshida & Yukimoto (1993); Draper et al. (2003). For a related structure, see: McCullough et al. (1972).

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CH2Cl2 gave single crystals suitable for X-ray analysis.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model with d(N—H) = 0.88 Å, Uiso = 1.2Ueq(C) for amine and d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for Csp2—H.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
[Figure 2] Fig. 2. Crystal packing of the title compound with N—H···F hydrogen bonds and weak intermolecular Cl···Cl and F···F interactions shown as dashed lines.
3-Chloro-N-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2,6-dinitro-4-(trifluoromethyl)aniline top
Crystal data top
C13H4Cl2F6N4O4Z = 2
Mr = 465.10F(000) = 460
Triclinic, P1Dx = 1.875 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9546 (1) ÅCell parameters from 8261 reflections
b = 9.0724 (1) Åθ = 2.4–28.3°
c = 10.6818 (2) ŵ = 0.49 mm1
α = 79.556 (1)°T = 173 K
β = 75.420 (1)°Block, yellow
γ = 83.451 (1)°0.30 × 0.18 × 0.15 mm
V = 823.79 (2) Å3
Data collection top
Bruker APEXII CCD detector
diffractometer
4096 independent reflections
Radiation source: fine-focus sealed tube3662 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2006)
h = 1111
Tmin = 0.867, Tmax = 0.930k = 1210
15193 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0402P)2 + 0.3959P]
where P = (Fo2 + 2Fc2)/3
4096 reflections(Δ/σ)max < 0.001
262 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
C13H4Cl2F6N4O4γ = 83.451 (1)°
Mr = 465.10V = 823.79 (2) Å3
Triclinic, P1Z = 2
a = 8.9546 (1) ÅMo Kα radiation
b = 9.0724 (1) ŵ = 0.49 mm1
c = 10.6818 (2) ÅT = 173 K
α = 79.556 (1)°0.30 × 0.18 × 0.15 mm
β = 75.420 (1)°
Data collection top
Bruker APEXII CCD detector
diffractometer
4096 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2006)
3662 reflections with I > 2σ(I)
Tmin = 0.867, Tmax = 0.930Rint = 0.022
15193 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.04Δρmax = 0.47 e Å3
4096 reflectionsΔρmin = 0.45 e Å3
262 parameters
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
xyzUiso*/Ueq
Cl10.83432 (5)0.72367 (4)0.34806 (4)0.03069 (10)
Cl20.43809 (5)0.32745 (5)0.99480 (4)0.03760 (11)
F11.06852 (11)0.34123 (11)0.15585 (9)0.0342 (2)
F20.90981 (11)0.53398 (12)0.12664 (9)0.0369 (2)
F31.11164 (11)0.55470 (11)0.19484 (10)0.0357 (2)
F40.25749 (13)0.25110 (12)0.84106 (12)0.0484 (3)
F50.07528 (12)0.07681 (13)0.86228 (14)0.0542 (3)
F60.17049 (16)0.17401 (14)1.02625 (11)0.0572 (3)
N10.63148 (15)0.61200 (13)0.60382 (12)0.0257 (3)
N20.82927 (13)0.07922 (13)0.58834 (12)0.0239 (2)
N30.62868 (14)0.31709 (14)0.72658 (11)0.0234 (2)
H30.63290.37640.78210.028*
N40.52522 (14)0.10739 (14)0.69279 (12)0.0240 (2)
O10.51649 (16)0.65800 (18)0.56501 (17)0.0595 (4)
O20.6693 (2)0.65407 (19)0.68990 (16)0.0653 (5)
O30.83309 (13)0.01445 (12)0.51781 (11)0.0321 (2)
O40.84483 (13)0.05111 (13)0.70083 (11)0.0321 (2)
C11.00024 (17)0.46373 (17)0.20469 (14)0.0257 (3)
C20.90782 (15)0.42479 (15)0.34387 (13)0.0210 (3)
C30.82543 (16)0.53636 (15)0.41309 (13)0.0210 (3)
C40.73336 (15)0.49449 (15)0.53729 (13)0.0209 (3)
C50.72421 (15)0.34551 (15)0.60148 (13)0.0197 (3)
C60.81363 (15)0.23826 (15)0.53006 (13)0.0204 (3)
C70.90021 (16)0.27574 (15)0.40317 (13)0.0215 (3)
H70.95480.19870.35640.026*
C80.52749 (15)0.20410 (15)0.77180 (13)0.0208 (3)
C90.42873 (16)0.19730 (16)0.89770 (14)0.0238 (3)
C100.32506 (17)0.08814 (17)0.94103 (14)0.0267 (3)
H100.25640.08181.02530.032*
C110.32343 (17)0.01298 (16)0.85797 (15)0.0257 (3)
C120.42492 (17)0.00019 (16)0.73578 (15)0.0261 (3)
H120.42340.06980.68000.031*
C130.20746 (19)0.12907 (18)0.89734 (17)0.0332 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0402 (2)0.01712 (16)0.03235 (19)0.00298 (13)0.00704 (15)0.00063 (13)
Cl20.0392 (2)0.0455 (2)0.02904 (19)0.01359 (17)0.00518 (15)0.02051 (17)
F10.0373 (5)0.0320 (5)0.0270 (4)0.0033 (4)0.0067 (4)0.0076 (4)
F20.0418 (5)0.0452 (6)0.0211 (4)0.0003 (4)0.0090 (4)0.0013 (4)
F30.0328 (5)0.0331 (5)0.0372 (5)0.0146 (4)0.0007 (4)0.0018 (4)
F40.0441 (6)0.0303 (5)0.0704 (8)0.0134 (4)0.0029 (5)0.0154 (5)
F50.0303 (5)0.0468 (7)0.0869 (9)0.0104 (5)0.0176 (6)0.0038 (6)
F60.0738 (8)0.0510 (7)0.0409 (6)0.0357 (6)0.0012 (6)0.0069 (5)
N10.0302 (6)0.0191 (6)0.0264 (6)0.0011 (5)0.0048 (5)0.0047 (5)
N20.0218 (6)0.0194 (6)0.0264 (6)0.0010 (4)0.0003 (4)0.0018 (5)
N30.0264 (6)0.0231 (6)0.0203 (5)0.0068 (4)0.0004 (4)0.0074 (5)
N40.0246 (6)0.0230 (6)0.0237 (6)0.0033 (4)0.0018 (4)0.0067 (5)
O10.0400 (7)0.0658 (10)0.0874 (11)0.0247 (7)0.0296 (8)0.0471 (9)
O20.0887 (12)0.0629 (10)0.0628 (10)0.0380 (9)0.0454 (9)0.0464 (8)
O30.0366 (6)0.0195 (5)0.0370 (6)0.0018 (4)0.0002 (5)0.0092 (4)
O40.0354 (6)0.0287 (6)0.0283 (6)0.0002 (4)0.0075 (4)0.0039 (4)
C10.0263 (7)0.0261 (7)0.0224 (7)0.0049 (5)0.0024 (5)0.0013 (5)
C20.0211 (6)0.0221 (6)0.0195 (6)0.0036 (5)0.0044 (5)0.0021 (5)
C30.0245 (6)0.0168 (6)0.0227 (6)0.0032 (5)0.0081 (5)0.0009 (5)
C40.0232 (6)0.0184 (6)0.0223 (6)0.0007 (5)0.0057 (5)0.0064 (5)
C50.0199 (6)0.0205 (6)0.0191 (6)0.0034 (5)0.0040 (5)0.0044 (5)
C60.0213 (6)0.0175 (6)0.0218 (6)0.0019 (5)0.0042 (5)0.0025 (5)
C70.0225 (6)0.0199 (6)0.0218 (6)0.0011 (5)0.0032 (5)0.0052 (5)
C80.0205 (6)0.0200 (6)0.0209 (6)0.0011 (5)0.0033 (5)0.0031 (5)
C90.0254 (7)0.0250 (7)0.0209 (6)0.0016 (5)0.0027 (5)0.0072 (5)
C100.0248 (7)0.0299 (8)0.0220 (7)0.0044 (6)0.0000 (5)0.0020 (6)
C110.0246 (7)0.0215 (7)0.0296 (7)0.0035 (5)0.0054 (5)0.0005 (6)
C120.0268 (7)0.0219 (7)0.0298 (7)0.0030 (5)0.0046 (6)0.0070 (6)
C130.0321 (8)0.0272 (8)0.0377 (8)0.0090 (6)0.0032 (6)0.0014 (6)
Geometric parameters (Å, º) top
Cl1—C31.7180 (13)N4—C81.3280 (18)
Cl2—C91.7283 (14)N4—C121.3391 (18)
F1—C11.3326 (17)C1—C21.5090 (19)
F2—C11.3366 (17)C2—C71.3868 (19)
F3—C11.3382 (17)C2—C31.3936 (19)
F4—C131.334 (2)C3—C41.3864 (19)
F5—C131.340 (2)C4—C51.4017 (19)
F6—C131.330 (2)C5—C61.3978 (18)
N1—O21.1911 (18)C6—C71.3849 (18)
N1—O11.2084 (18)C7—H70.9500
N1—C41.4834 (17)C8—C91.4065 (19)
N2—O41.2220 (16)C9—C101.373 (2)
N2—O31.2263 (16)C10—C111.391 (2)
N2—C61.4701 (17)C10—H100.9500
N3—C81.3846 (17)C11—C121.384 (2)
N3—C51.3906 (17)C11—C131.495 (2)
N3—H30.8800C12—H120.9500
O2—N1—O1125.30 (14)C7—C6—C5122.46 (12)
O2—N1—C4117.99 (13)C7—C6—N2115.65 (12)
O1—N1—C4116.71 (12)C5—C6—N2121.78 (12)
O4—N2—O3125.24 (12)C6—C7—C2120.52 (13)
O4—N2—C6117.51 (12)C6—C7—H7119.7
O3—N2—C6117.15 (12)C2—C7—H7119.7
C8—N3—C5126.00 (12)N4—C8—N3118.35 (12)
C8—N3—H3117.0N4—C8—C9122.28 (13)
C5—N3—H3117.0N3—C8—C9119.35 (12)
C8—N4—C12118.20 (12)C10—C9—C8119.38 (13)
F1—C1—F2107.50 (12)C10—C9—Cl2120.99 (11)
F1—C1—F3107.14 (12)C8—C9—Cl2119.63 (11)
F2—C1—F3106.99 (12)C9—C10—C11118.07 (13)
F1—C1—C2111.51 (12)C9—C10—H10121.0
F2—C1—C2111.11 (12)C11—C10—H10121.0
F3—C1—C2112.33 (12)C12—C11—C10119.23 (13)
C7—C2—C3119.09 (12)C12—C11—C13120.38 (14)
C7—C2—C1119.92 (12)C10—C11—C13120.30 (14)
C3—C2—C1120.96 (12)N4—C12—C11122.83 (14)
C4—C3—C2118.91 (12)N4—C12—H12118.6
C4—C3—Cl1119.39 (11)C11—C12—H12118.6
C2—C3—Cl1121.70 (10)F6—C13—F4107.38 (14)
C3—C4—C5123.74 (12)F6—C13—F5106.72 (14)
C3—C4—N1118.60 (12)F4—C13—F5106.11 (14)
C5—C4—N1117.56 (12)F6—C13—C11112.20 (14)
N3—C5—C6126.22 (12)F4—C13—C11112.41 (13)
N3—C5—C4118.65 (12)F5—C13—C11111.63 (13)
C6—C5—C4115.13 (12)
F1—C1—C2—C71.24 (18)O3—N2—C6—C741.24 (17)
F2—C1—C2—C7118.67 (14)O4—N2—C6—C540.98 (18)
F3—C1—C2—C7121.52 (14)O3—N2—C6—C5142.43 (13)
F1—C1—C2—C3179.22 (12)C5—C6—C7—C23.5 (2)
F2—C1—C2—C359.31 (17)N2—C6—C7—C2172.80 (12)
F3—C1—C2—C360.50 (17)C3—C2—C7—C60.9 (2)
C7—C2—C3—C42.56 (19)C1—C2—C7—C6178.88 (12)
C1—C2—C3—C4175.44 (12)C12—N4—C8—N3178.61 (13)
C7—C2—C3—Cl1177.84 (10)C12—N4—C8—C90.1 (2)
C1—C2—C3—Cl14.16 (18)C5—N3—C8—N43.9 (2)
C2—C3—C4—C53.7 (2)C5—N3—C8—C9174.67 (13)
Cl1—C3—C4—C5176.73 (10)N4—C8—C9—C100.5 (2)
C2—C3—C4—N1172.68 (12)N3—C8—C9—C10178.00 (13)
Cl1—C3—C4—N16.93 (17)N4—C8—C9—Cl2179.84 (11)
O2—N1—C4—C3104.70 (18)N3—C8—C9—Cl21.30 (19)
O1—N1—C4—C374.84 (19)C8—C9—C10—C110.6 (2)
O2—N1—C4—C578.73 (19)Cl2—C9—C10—C11179.93 (11)
O1—N1—C4—C5101.72 (17)C9—C10—C11—C120.2 (2)
C8—N3—C5—C643.9 (2)C9—C10—C11—C13176.82 (14)
C8—N3—C5—C4135.41 (14)C8—N4—C12—C110.5 (2)
C3—C4—C5—N3179.48 (12)C10—C11—C12—N40.4 (2)
N1—C4—C5—N34.14 (18)C13—C11—C12—N4176.21 (14)
C3—C4—C5—C61.2 (2)C12—C11—C13—F6151.47 (15)
N1—C4—C5—C6175.22 (12)C10—C11—C13—F631.9 (2)
N3—C5—C6—C7176.86 (13)C12—C11—C13—F430.3 (2)
C4—C5—C6—C72.45 (19)C10—C11—C13—F4153.10 (14)
N3—C5—C6—N27.1 (2)C12—C11—C13—F588.78 (18)
C4—C5—C6—N2173.63 (12)C10—C11—C13—F587.80 (19)
O4—N2—C6—C7135.34 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···F3i0.882.523.0690 (15)121
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···F3i0.882.523.0690 (15)121.2
Symmetry code: (i) x+2, y+1, z+1.
 

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2012R1A1B3003337).

References

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