3,3′-Difluoro-4,4′-(p-phenyl­enedi­oxy)dibenzonitrile

Zhang, J.; Wu, J.; Wang, J.; Li, Y.; Luo, S.

doi:10.1107/S1600536809035247

organic compounds

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Volume 65| Part 10| October 2009| Page o2340

doi:10.1107/S1600536809035247

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3,3′-Difluoro-4,4′-(p-phenylenedioxy)dibenzonitrile

Jixu Zhang,^a Jiayi Wu,^a Jianfeng Wang,^a Yiming Li ^a and Shuping Luo ^a ^*

^aState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zhangjixu123@163.com

(Received 18 August 2009; accepted 1 September 2009; online 5 September 2009)

The title compound, C₂₀H₁₀F₂N₂O₂, was synthesized from hydroquinone and 3,4-difluorobenzonitrile. The centroid of the central aromatic ring is on a crystallographic center of inversion. The dihedral angle between the central and terminal rings is 77.8 (3)°. In the crystal, chains linked by C—H⋯N bond occur.

Related literature

For the herbicidal actvity of hydroquinone derivatives, see: Bao et al. (2007 ). For related structures, see: Sørensen & Stuhr-Hansen (2009 ); Luo et al. (2009 ); Liu (2002 ).

Experimental

Crystal data

C₂₀H₁₀F₂N₂O₂
M_r = 348.30
Triclinic, $[P \overline 1]$
a = 6.980 (1) Å
b = 7.615 (1) Å
c = 8.294 (1) Å
α = 106.376 (3)°
β = 93.698 (3)°
γ = 109.085 (3)°
V = 393.7 (1) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.42 × 0.37 × 0.32 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.782, T_max = 1.000
2165 measured reflections
1529 independent reflections
1259 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.137
S = 1.07
1529 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯N1ⁱ	0.93	2.50	3.410 (2)	166
Symmetry code: (i) -x, -y, -z+2.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2000 ); data reduction: SHELXTL (Sheldrick, 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035247/im2138sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035247/im2138Isup2.hkl

checkCIF report

Comment top

There has been growing interest in the study of hydroquinone derivatives which are important intermediates in the synthesis of herbicides (Liu, 2002. Bao et al., 2007). Only a few compounds of this kind have been structurally characterized so far. As part of our studies, we have synthesized the title compound from hydroquinone and 3,4-difluorobenzonitrile and report it's crystal structure in this article.

The crystal structure of the title compound (Fig. 1) utilizes the symmetry of the crystallographic inversion center similarily to a related selenium compound (Sørensen et al., 2009). The two terminal (C1—C7) phenyl ring and the central ring together with the attached oxygen (C8—C10/O1) form three planes. Due to crystallograhic symmetry the two terminal phenyl rings are coplanar. The terminal (C1—C7) phenyl ring plane and the central ring plane enclose a dihedral angle of 77.8 (3)°. Otherwise, the molecule is bent with the C2—O1—C8 angle of 118.25°.

In the crystal structure, intermolecular C—H···N hydrogen bonds (Tab.1) connect neighboring molecules with each other to form a one-dimensional chain that stretches along the c axis (Fig.2).

Related literature top

For the herbicidal actvity of hydroquinone derivatives, see: Bao et al. (2007); For related structres, see: Sørensen & Stuhr-Hansen (2009); Luo et al. (2009); Liu (2002).

Experimental top

A DMF (10 ml) solution of hydroquinone (1 mmol) and 3,4-difluorobenzonitrile (2 mmol) was heated to 70°C in the presence of KOH and stirred for 37 h. Then the mixture was washed with water (30 ml) and extracted with ethyl acetate (three times). The organic solvent was removed under reduced pressure. Afterwards the product was purified by column chromatography on silica (pentane - ethyl acetate mixtures). Single crystals were obtained by slow evaporation of the solvent of an ethanolic solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Sheldrick, 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound with the atomic labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of title compound. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x, -y, -z + 2].

3,3'-Difluoro-4,4'-(p-phenylenedioxy)dibenzonitrile top

Crystal data top

C₂₀H₁₀F₂N₂O₂	Z = 1
M_r = 348.30	F(000) = 178
Triclinic, P1	D_x = 1.469 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.980 (1) Å	Cell parameters from 1140 reflections
b = 7.615 (1) Å	θ = 5.2–54.9°
c = 8.294 (1) Å	µ = 0.11 mm⁻¹
α = 106.376 (3)°	T = 293 K
β = 93.698 (3)°	Prismatic, colorless
γ = 109.085 (3)°	0.42 × 0.37 × 0.32 mm
V = 393.7 (1) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Radiation source: fine-focus sealed tube	1259 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
T_min = 0.782, T_max = 1.000	k = −9→8
2165 measured reflections	l = −10→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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.137	w = 1/[σ²(F_o²) + (0.0836P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1529 reflections	Δρ_max = 0.19 e Å⁻³
119 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (6)

Crystal data top

C₂₀H₁₀F₂N₂O₂	γ = 109.085 (3)°
M_r = 348.30	V = 393.7 (1) Å³
Triclinic, P1	Z = 1
a = 6.980 (1) Å	Mo Kα radiation
b = 7.615 (1) Å	µ = 0.11 mm⁻¹
c = 8.294 (1) Å	T = 293 K
α = 106.376 (3)°	0.42 × 0.37 × 0.32 mm
β = 93.698 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1259 reflections with I > 2σ(I)
T_min = 0.782, T_max = 1.000	R_int = 0.065
2165 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.07	Δρ_max = 0.19 e Å⁻³
1529 reflections	Δρ_min = −0.21 e Å⁻³
119 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

	x	y	z	U_iso*/U_eq
O1	0.31400 (15)	0.41880 (17)	0.64633 (14)	0.0546 (4)
N1	0.2645 (2)	0.0341 (2)	1.2835 (2)	0.0706 (5)
F1	0.21076 (16)	0.59370 (13)	0.94706 (13)	0.0663 (4)
C1	0.2380 (2)	0.4219 (2)	0.9251 (2)	0.0463 (4)
C2	0.2823 (2)	0.3307 (2)	0.77070 (18)	0.0443 (4)
C3	0.3137 (2)	0.1573 (2)	0.7484 (2)	0.0520 (4)
H3	0.3429	0.0941	0.6448	0.062*
C4	0.3023 (2)	0.0761 (2)	0.8780 (2)	0.0524 (4)
H4	0.3229	−0.0419	0.8619	0.063*
C5	0.2601 (2)	0.1714 (2)	1.03224 (18)	0.0460 (4)
C6	0.2256 (2)	0.3453 (2)	1.05636 (19)	0.0483 (4)
H6	0.1949	0.4084	1.1592	0.058*
C7	0.2590 (2)	0.0934 (2)	1.1718 (2)	0.0535 (4)
C8	0.1518 (2)	0.4580 (2)	0.57622 (16)	0.0424 (4)
C9	−0.0514 (2)	0.3477 (2)	0.56761 (18)	0.0478 (4)
H9	−0.0856	0.2450	0.6129	0.057*
C10	0.2042 (2)	0.6087 (2)	0.50919 (18)	0.0472 (4)
H10	0.3420	0.6816	0.5152	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0475 (6)	0.0766 (8)	0.0542 (7)	0.0254 (5)	0.0116 (5)	0.0384 (6)
N1	0.0775 (11)	0.0788 (11)	0.0601 (9)	0.0206 (8)	0.0085 (8)	0.0390 (8)
F1	0.0825 (8)	0.0573 (7)	0.0671 (7)	0.0349 (5)	0.0118 (5)	0.0209 (5)
C1	0.0428 (8)	0.0463 (8)	0.0503 (9)	0.0176 (6)	0.0023 (6)	0.0158 (7)
C2	0.0385 (7)	0.0561 (9)	0.0407 (8)	0.0150 (6)	0.0028 (6)	0.0222 (7)
C3	0.0585 (9)	0.0626 (10)	0.0412 (8)	0.0290 (8)	0.0095 (7)	0.0172 (7)
C4	0.0578 (9)	0.0548 (9)	0.0510 (9)	0.0258 (7)	0.0070 (7)	0.0206 (7)
C5	0.0397 (8)	0.0560 (9)	0.0429 (8)	0.0144 (6)	0.0018 (6)	0.0211 (7)
C6	0.0451 (8)	0.0586 (9)	0.0389 (8)	0.0177 (7)	0.0049 (6)	0.0141 (7)
C7	0.0481 (9)	0.0621 (10)	0.0496 (9)	0.0149 (7)	0.0036 (7)	0.0238 (8)
C8	0.0453 (8)	0.0489 (8)	0.0338 (7)	0.0167 (6)	0.0029 (6)	0.0160 (6)
C9	0.0496 (9)	0.0461 (8)	0.0472 (9)	0.0093 (6)	0.0032 (6)	0.0247 (7)
C10	0.0401 (8)	0.0512 (9)	0.0454 (8)	0.0058 (6)	0.0033 (6)	0.0217 (7)

Geometric parameters (Å, º) top

O1—C2	1.3731 (16)	C4—H4	0.9300
O1—C8	1.3943 (16)	C5—C6	1.385 (2)
N1—C7	1.143 (2)	C5—C7	1.442 (2)
F1—C1	1.3469 (17)	C6—H6	0.9300
C1—C6	1.368 (2)	C8—C10	1.3678 (19)
C1—C2	1.381 (2)	C8—C9	1.377 (2)
C2—C3	1.372 (2)	C9—C10ⁱ	1.385 (2)
C3—C4	1.378 (2)	C9—H9	0.9300
C3—H3	0.9300	C10—C9ⁱ	1.385 (2)
C4—C5	1.384 (2)	C10—H10	0.9300

C2—O1—C8	118.23 (11)	C6—C5—C7	119.29 (14)
F1—C1—C6	119.41 (14)	C1—C6—C5	118.30 (14)
F1—C1—C2	118.49 (13)	C1—C6—H6	120.8
C6—C1—C2	122.08 (14)	C5—C6—H6	120.8
C3—C2—O1	119.59 (13)	N1—C7—C5	177.94 (17)
C3—C2—C1	118.81 (13)	C10—C8—C9	120.96 (13)
O1—C2—C1	121.32 (13)	C10—C8—O1	116.41 (12)
C2—C3—C4	120.60 (14)	C9—C8—O1	122.58 (12)
C2—C3—H3	119.7	C8—C9—C10ⁱ	119.29 (13)
C4—C3—H3	119.7	C8—C9—H9	120.4
C3—C4—C5	119.53 (15)	C10ⁱ—C9—H9	120.4
C3—C4—H4	120.2	C8—C10—C9ⁱ	119.75 (13)
C5—C4—H4	120.2	C8—C10—H10	120.1
C4—C5—C6	120.67 (13)	C9ⁱ—C10—H10	120.1
C4—C5—C7	120.00 (15)

C8—O1—C2—C3	123.31 (15)	C2—C1—C6—C5	0.4 (2)
C8—O1—C2—C1	−62.84 (18)	C4—C5—C6—C1	−1.1 (2)
F1—C1—C2—C3	178.88 (13)	C7—C5—C6—C1	176.65 (13)
C6—C1—C2—C3	0.4 (2)	C4—C5—C7—N1	80 (5)
F1—C1—C2—O1	5.0 (2)	C6—C5—C7—N1	−98 (5)
C6—C1—C2—O1	−173.52 (13)	C2—O1—C8—C10	154.42 (13)
O1—C2—C3—C4	173.66 (13)	C2—O1—C8—C9	−28.1 (2)
C1—C2—C3—C4	−0.3 (2)	C10—C8—C9—C10ⁱ	−0.4 (2)
C2—C3—C4—C5	−0.4 (2)	O1—C8—C9—C10ⁱ	−177.78 (13)
C3—C4—C5—C6	1.2 (2)	C9—C8—C10—C9ⁱ	0.4 (2)
C3—C4—C5—C7	−176.60 (14)	O1—C8—C10—C9ⁱ	177.93 (12)
F1—C1—C6—C5	−178.13 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N1ⁱⁱ	0.93	2.50	3.410 (2)	166

Symmetry code: (ii) −x, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₀F₂N₂O₂
M_r	348.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.980 (1), 7.615 (1), 8.294 (1)
α, β, γ (°)	106.376 (3), 93.698 (3), 109.085 (3)
V (Å³)	393.7 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.42 × 0.37 × 0.32

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.782, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2165, 1529, 1259
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.137, 1.07
No. of reflections	1529
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N1ⁱ	0.93	2.50	3.410 (2)	166.0

Symmetry code: (i) −x, −y, −z+2.

References

Bao, W. J., Wu, Y. G., Mao, C. H., Chen, M. & Huang, M. Z. (2007). Fine Chem. Intermed. 37, 9–13. CAS Google Scholar
Bruker (2000). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, C. L. (2002). Pesticides, 41, 38. Final page number?. Google Scholar
Luo, S., Zhang, J., Wang, J. & Li, B. (2009). Acta Cryst. E65, o2011. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sørensen, H. O. & Stuhr-Hansen, N. (2009). Acta Cryst. E65, o13. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2340

doi:10.1107/S1600536809035247

Open

access