4-(2,2-Difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile

Meng, F.-W.; Hou, G.-F.; Yu, Y.-H.; Gao, J.-S.

doi:10.1107/S1600536811054523

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o222

doi:10.1107/S1600536811054523

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4-(2,2-Difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile

Fan-Wei Meng,^a Guang-Feng Hou,^a Ying-Hui Yu ^a and Jin-Sheng Gao ^a ^*

^aEngineering Research Center of Pesticides of Heilongjiang University, Heilongjiang University, Harbin 150050, People's Republic of China, and College of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 12 December 2011; accepted 19 December 2011; online 23 December 2011)

In the title compound, C₁₂H₆F₂N₂O₂, the 2,2-difluoro-1,3-benzodioxole ring system is approximately planar [maximum deviation = 0.012 (2) Å] and its mean plane is twisted with respect to the pyrrole ring, making a dihedral angle of 2.51 (9)°. In the crystal, N—H⋯N hydrogen bonds link the molecules into chains running along the a axis. π–π stacking is also observed between parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.7527 (13) Å.

Related literature

For background to the title compound, see: Li et al. (2009 ); Pfluger et al. (1990 ). For the synthesis, see: Nyfeler & Ehrenfreund (1986 ).

Experimental

Crystal data

C₁₂H₆F₂N₂O₂
M_r = 248.19
Triclinic, $[P \overline 1]$
a = 7.5726 (15) Å
b = 7.8114 (16) Å
c = 8.9785 (18) Å
α = 93.58 (3)°
β = 94.65 (3)°
γ = 97.47 (3)°
V = 523.42 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.39 × 0.32 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.950, T_max = 0.980
5120 measured reflections
2359 independent reflections
1485 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.118
S = 1.04
2359 reflections
167 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H101⋯N2ⁱ	0.89 (1)	2.15 (1)	3.034 (2)	169 (2)
Symmetry code: (i) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054523/xu5407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054523/xu5407Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054523/xu5407Isup3.cml

checkCIF report

Comment top

Fludioxonil also know as Maxim, which is kind of fungicide developed and produced by Novartis (Li et al., 2009; Pfluger et al., 1990). Herein we report its structure.

In the title compound, phenyl and pyrrole ring are almost coplanar with a small dihedral angle of 2.51 (9)° (Figure 1). Intermolecular N—H···N hydrogen bonds link molecules into chains along [100] (Figure 2, Table 1).

Related literature top

For background to the title compound, see: Li et al. (2009); Pfluger et al. (1990). For the synthesis, see: Nyfeler, R. & Ehrenfreund (1986);

Experimental top

The title compound was prepared by the reaction of 2-cyano-3-(2,2-difluoro-1,3-benzodioxol-4-yl)-2-propenamide and tosylmethyl isocyanide under alkaline condition (Robert & Josef, 1986). Colorless block crystals suitable for singl crystal X-ray diffraction were obtained by the recrystallization of title compound from a dichloromethane solution.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing the hydrogen-bonding chain structure along [100].

4-(2,2-Difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile top

Crystal data top

C₁₂H₆F₂N₂O₂	Z = 2
M_r = 248.19	F(000) = 252
Triclinic, P1	D_x = 1.575 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5726 (15) Å	Cell parameters from 3390 reflections
b = 7.8114 (16) Å	θ = 3.4–27.5°
c = 8.9785 (18) Å	µ = 0.13 mm⁻¹
α = 93.58 (3)°	T = 293 K
β = 94.65 (3)°	Block, colorless
γ = 97.47 (3)°	0.39 × 0.32 × 0.15 mm
V = 523.42 (18) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2359 independent reflections
Radiation source: fine-focus sealed tube	1485 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scan	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.950, T_max = 0.980	k = −10→10
5120 measured reflections	l = −11→10

Refinement top

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0612P)² + 0.0143P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2359 reflections	Δρ_max = 0.19 e Å⁻³
167 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (6)

Crystal data top

C₁₂H₆F₂N₂O₂	γ = 97.47 (3)°
M_r = 248.19	V = 523.42 (18) Å³
Triclinic, P1	Z = 2
a = 7.5726 (15) Å	Mo Kα radiation
b = 7.8114 (16) Å	µ = 0.13 mm⁻¹
c = 8.9785 (18) Å	T = 293 K
α = 93.58 (3)°	0.39 × 0.32 × 0.15 mm
β = 94.65 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2359 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1485 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.980	R_int = 0.026
5120 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.19 e Å⁻³
2359 reflections	Δρ_min = −0.15 e Å⁻³
167 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	U_iso*/U_eq
C1	0.0680 (2)	0.6305 (2)	0.7663 (2)	0.0492 (4)
C2	−0.1137 (2)	0.6131 (3)	0.7677 (2)	0.0580 (5)
H2	−0.1723	0.5712	0.8478	0.070*
C3	−0.2036 (2)	0.6626 (3)	0.6407 (2)	0.0604 (5)
H3	−0.3277	0.6534	0.6348	0.072*
C4	−0.1158 (2)	0.7254 (2)	0.5222 (2)	0.0533 (5)
H4	−0.1833	0.7566	0.4395	0.064*
C5	0.0715 (2)	0.7442 (2)	0.52139 (18)	0.0412 (4)
C6	0.1551 (2)	0.6918 (2)	0.64884 (19)	0.0425 (4)
C7	0.3564 (2)	0.6277 (3)	0.8215 (2)	0.0580 (5)
C8	0.1679 (2)	0.8093 (2)	0.39662 (18)	0.0406 (4)
C9	0.0963 (2)	0.8705 (2)	0.25982 (19)	0.0424 (4)
C10	0.2365 (2)	0.9151 (2)	0.1754 (2)	0.0515 (5)
H10	0.2281	0.9581	0.0812	0.062*
C11	0.3488 (2)	0.8223 (3)	0.3852 (2)	0.0523 (5)
H11	0.4323	0.7921	0.4572	0.063*
C12	−0.0831 (2)	0.8924 (2)	0.2144 (2)	0.0474 (4)
F1	0.46357 (16)	0.74161 (18)	0.91577 (13)	0.0804 (4)
F2	0.43750 (16)	0.48669 (18)	0.81288 (16)	0.0803 (4)
N1	0.38690 (19)	0.8860 (2)	0.25235 (18)	0.0575 (5)
H101	0.4958 (17)	0.901 (3)	0.220 (3)	0.086*
N2	−0.2273 (2)	0.9115 (2)	0.17807 (19)	0.0631 (5)
O1	0.19296 (17)	0.5902 (2)	0.87638 (15)	0.0650 (4)
O2	0.33825 (15)	0.69183 (17)	0.68299 (13)	0.0540 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0499 (10)	0.0565 (11)	0.0440 (10)	0.0091 (8)	0.0105 (8)	0.0133 (8)
C2	0.0507 (10)	0.0722 (13)	0.0562 (12)	0.0089 (9)	0.0222 (9)	0.0210 (10)
C3	0.0379 (9)	0.0835 (14)	0.0652 (13)	0.0130 (9)	0.0160 (8)	0.0240 (11)
C4	0.0403 (9)	0.0718 (12)	0.0515 (11)	0.0115 (8)	0.0092 (8)	0.0185 (10)
C5	0.0381 (8)	0.0465 (9)	0.0405 (9)	0.0070 (7)	0.0077 (7)	0.0078 (7)
C6	0.0354 (8)	0.0514 (9)	0.0422 (9)	0.0057 (7)	0.0092 (7)	0.0078 (8)
C7	0.0467 (10)	0.0838 (14)	0.0474 (11)	0.0123 (10)	0.0066 (8)	0.0252 (10)
C8	0.0374 (8)	0.0470 (9)	0.0386 (9)	0.0068 (7)	0.0065 (7)	0.0072 (7)
C9	0.0382 (8)	0.0512 (10)	0.0396 (9)	0.0084 (7)	0.0061 (7)	0.0081 (7)
C10	0.0451 (9)	0.0727 (12)	0.0402 (10)	0.0117 (8)	0.0082 (7)	0.0193 (9)
C11	0.0388 (9)	0.0759 (12)	0.0461 (11)	0.0121 (8)	0.0066 (7)	0.0224 (9)
C12	0.0442 (10)	0.0602 (11)	0.0398 (10)	0.0085 (8)	0.0064 (7)	0.0134 (8)
F1	0.0666 (8)	0.1180 (11)	0.0512 (7)	−0.0057 (7)	−0.0045 (6)	0.0148 (7)
F2	0.0734 (8)	0.0941 (9)	0.0855 (10)	0.0318 (7)	0.0215 (6)	0.0415 (8)
N1	0.0377 (8)	0.0870 (12)	0.0525 (10)	0.0100 (8)	0.0134 (7)	0.0254 (8)
N2	0.0437 (9)	0.0914 (13)	0.0580 (11)	0.0144 (8)	0.0042 (7)	0.0246 (9)
O1	0.0525 (8)	0.1003 (11)	0.0473 (8)	0.0114 (7)	0.0113 (6)	0.0335 (7)
O2	0.0382 (6)	0.0824 (9)	0.0444 (7)	0.0082 (6)	0.0065 (5)	0.0242 (6)

Geometric parameters (Å, º) top

C1—C2	1.366 (3)	C7—F1	1.331 (2)
C1—C6	1.368 (2)	C7—O1	1.372 (2)
C1—O1	1.391 (2)	C7—O2	1.373 (2)
C2—C3	1.383 (3)	C8—C11	1.373 (2)
C2—H2	0.9300	C8—C9	1.437 (2)
C3—C4	1.382 (2)	C9—C10	1.375 (2)
C3—H3	0.9300	C9—C12	1.421 (2)
C4—C5	1.407 (2)	C10—N1	1.336 (2)
C4—H4	0.9300	C10—H10	0.9300
C5—C6	1.373 (2)	C11—N1	1.358 (2)
C5—C8	1.468 (2)	C11—H11	0.9300
C6—O2	1.3960 (19)	C12—N2	1.145 (2)
C7—F2	1.330 (2)	N1—H101	0.891 (10)

C2—C1—C6	122.93 (17)	F2—C7—O2	109.90 (18)
C2—C1—O1	127.94 (16)	F1—C7—O2	109.89 (16)
C6—C1—O1	109.12 (15)	O1—C7—O2	110.86 (15)
C1—C2—C3	114.73 (17)	C11—C8—C9	104.79 (14)
C1—C2—H2	122.6	C11—C8—C5	126.80 (15)
C3—C2—H2	122.6	C9—C8—C5	128.40 (14)
C4—C3—C2	122.42 (16)	C10—C9—C12	123.08 (16)
C4—C3—H3	118.8	C10—C9—C8	107.74 (15)
C2—C3—H3	118.8	C12—C9—C8	129.12 (15)
C3—C4—C5	122.74 (17)	N1—C10—C9	108.11 (15)
C3—C4—H4	118.6	N1—C10—H10	125.9
C5—C4—H4	118.6	C9—C10—H10	125.9
C6—C5—C4	112.87 (15)	N1—C11—C8	109.45 (15)
C6—C5—C8	123.29 (14)	N1—C11—H11	125.3
C4—C5—C8	123.83 (15)	C8—C11—H11	125.3
C1—C6—C5	124.29 (15)	N2—C12—C9	179.4 (2)
C1—C6—O2	108.24 (15)	C10—N1—C11	109.90 (14)
C5—C6—O2	127.46 (14)	C10—N1—H101	125.5 (15)
F2—C7—F1	105.63 (16)	C11—N1—H101	124.5 (15)
F2—C7—O1	110.18 (16)	C7—O1—C1	105.74 (14)
F1—C7—O1	110.26 (18)	C7—O2—C6	106.02 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H101···N2ⁱ	0.89 (1)	2.15 (1)	3.034 (2)	169 (2)

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₆F₂N₂O₂
M_r	248.19
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5726 (15), 7.8114 (16), 8.9785 (18)
α, β, γ (°)	93.58 (3), 94.65 (3), 97.47 (3)
V (Å³)	523.42 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.39 × 0.32 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.950, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	5120, 2359, 1485
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.118, 1.04
No. of reflections	2359
No. of parameters	167
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H101···N2ⁱ	0.891 (10)	2.154 (11)	3.034 (2)	169 (2)

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank the Project of Innovation Service Platform of Heilongjiang Province (PG09J001) and Heilongjiang University, China, for supporting the work.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, C., Miu, H.-D., Zeng, Z.-W., Wang, M.-J., Wu, Z.-X., Yang, F. & Shi, W.-J. (2009). Modern Agrochem. 8, 19–24. CAS Google Scholar
Nyfeler, R. & Ehrenfreund, J. (1986). Switzerland Patent No. EP0206999. Google Scholar
Pfluger, R. W., Indermühle, J. & Felix, F. (1990). Switzerland Patent No. EP0378046. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar