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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811054523/xu5407Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

N-bound H atom was located in a differece Fourier map and positional parameters were refined, U_iso(H) = 1.5U_eq(N). Other H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Figures

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].

Crystal data

C12H6F2N2O2	Z = 2
Mr = 248.19	F(000) = 252
Triclinic, P1	Dx = 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

Rigaku R-AXIS RAPID diffractometer	2359 independent reflections
Radiation source: fine-focus sealed tube	1485 reflections with I > 2σ(I)
graphite	Rint = 0.026
ω scan	θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
Tmin = 0.950, Tmax = 0.980	k = −10→10
5120 measured reflections	l = −11→10

Refinement

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(Fo2) + (0.0612P)2 + 0.0143P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2359 reflections	Δρmax = 0.19 e Å−3
167 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x+1, y, z.