PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2340.
Published online 2009 September 5. doi:  10.1107/S1600536809035247
PMCID: PMC2970212

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

Abstract

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 [triangle]). For related structures, see: Sørensen & Stuhr-Hansen (2009 [triangle]); Luo et al. (2009 [triangle]); Liu (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2340-scheme1.jpg

Experimental

Crystal data

  • C20H10F2N2O2
  • M r = 348.30
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2340-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.137
  • S = 1.07
  • 1529 reflections
  • 119 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were placed in calculated positions with C—H=0.93 Å. All H atoms were included in the final cycles of refinement using a riding model, with Uiso(H)=1.2Ueq of the carrier atoms.

Figures

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].

Crystal data

C20H10F2N2O2Z = 1
Mr = 348.30F(000) = 178
Triclinic, P1Dx = 1.469 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.980 (1) ÅCell parameters from 1140 reflections
b = 7.615 (1) Åθ = 5.2–54.9°
c = 8.294 (1) ŵ = 0.11 mm1
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

Bruker SMART CCD area-detector diffractometer1529 independent reflections
Radiation source: fine-focus sealed tube1259 reflections with I > 2σ(I)
graphiteRint = 0.065
[var phi] and ω scansθmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→7
Tmin = 0.782, Tmax = 1.000k = −9→8
2165 measured reflectionsl = −10→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.137w = 1/[σ2(Fo2) + (0.0836P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1529 reflectionsΔρmax = 0.19 e Å3
119 parametersΔρmin = −0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.027 (6)

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*/Ueq
O10.31400 (15)0.41880 (17)0.64633 (14)0.0546 (4)
N10.2645 (2)0.0341 (2)1.2835 (2)0.0706 (5)
F10.21076 (16)0.59370 (13)0.94706 (13)0.0663 (4)
C10.2380 (2)0.4219 (2)0.9251 (2)0.0463 (4)
C20.2823 (2)0.3307 (2)0.77070 (18)0.0443 (4)
C30.3137 (2)0.1573 (2)0.7484 (2)0.0520 (4)
H30.34290.09410.64480.062*
C40.3023 (2)0.0761 (2)0.8780 (2)0.0524 (4)
H40.3229−0.04190.86190.063*
C50.2601 (2)0.1714 (2)1.03224 (18)0.0460 (4)
C60.2256 (2)0.3453 (2)1.05636 (19)0.0483 (4)
H60.19490.40841.15920.058*
C70.2590 (2)0.0934 (2)1.1718 (2)0.0535 (4)
C80.1518 (2)0.4580 (2)0.57622 (16)0.0424 (4)
C9−0.0514 (2)0.3477 (2)0.56761 (18)0.0478 (4)
H9−0.08560.24500.61290.057*
C100.2042 (2)0.6087 (2)0.50919 (18)0.0472 (4)
H100.34200.68160.51520.057*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0475 (6)0.0766 (8)0.0542 (7)0.0254 (5)0.0116 (5)0.0384 (6)
N10.0775 (11)0.0788 (11)0.0601 (9)0.0206 (8)0.0085 (8)0.0390 (8)
F10.0825 (8)0.0573 (7)0.0671 (7)0.0349 (5)0.0118 (5)0.0209 (5)
C10.0428 (8)0.0463 (8)0.0503 (9)0.0176 (6)0.0023 (6)0.0158 (7)
C20.0385 (7)0.0561 (9)0.0407 (8)0.0150 (6)0.0028 (6)0.0222 (7)
C30.0585 (9)0.0626 (10)0.0412 (8)0.0290 (8)0.0095 (7)0.0172 (7)
C40.0578 (9)0.0548 (9)0.0510 (9)0.0258 (7)0.0070 (7)0.0206 (7)
C50.0397 (8)0.0560 (9)0.0429 (8)0.0144 (6)0.0018 (6)0.0211 (7)
C60.0451 (8)0.0586 (9)0.0389 (8)0.0177 (7)0.0049 (6)0.0141 (7)
C70.0481 (9)0.0621 (10)0.0496 (9)0.0149 (7)0.0036 (7)0.0238 (8)
C80.0453 (8)0.0489 (8)0.0338 (7)0.0167 (6)0.0029 (6)0.0160 (6)
C90.0496 (9)0.0461 (8)0.0472 (9)0.0093 (6)0.0032 (6)0.0247 (7)
C100.0401 (8)0.0512 (9)0.0454 (8)0.0058 (6)0.0033 (6)0.0217 (7)

Geometric parameters (Å, °)

O1—C21.3731 (16)C4—H40.9300
O1—C81.3943 (16)C5—C61.385 (2)
N1—C71.143 (2)C5—C71.442 (2)
F1—C11.3469 (17)C6—H60.9300
C1—C61.368 (2)C8—C101.3678 (19)
C1—C21.381 (2)C8—C91.377 (2)
C2—C31.372 (2)C9—C10i1.385 (2)
C3—C41.378 (2)C9—H90.9300
C3—H30.9300C10—C9i1.385 (2)
C4—C51.384 (2)C10—H100.9300
C2—O1—C8118.23 (11)C6—C5—C7119.29 (14)
F1—C1—C6119.41 (14)C1—C6—C5118.30 (14)
F1—C1—C2118.49 (13)C1—C6—H6120.8
C6—C1—C2122.08 (14)C5—C6—H6120.8
C3—C2—O1119.59 (13)N1—C7—C5177.94 (17)
C3—C2—C1118.81 (13)C10—C8—C9120.96 (13)
O1—C2—C1121.32 (13)C10—C8—O1116.41 (12)
C2—C3—C4120.60 (14)C9—C8—O1122.58 (12)
C2—C3—H3119.7C8—C9—C10i119.29 (13)
C4—C3—H3119.7C8—C9—H9120.4
C3—C4—C5119.53 (15)C10i—C9—H9120.4
C3—C4—H4120.2C8—C10—C9i119.75 (13)
C5—C4—H4120.2C8—C10—H10120.1
C4—C5—C6120.67 (13)C9i—C10—H10120.1
C4—C5—C7120.00 (15)
C8—O1—C2—C3123.31 (15)C2—C1—C6—C50.4 (2)
C8—O1—C2—C1−62.84 (18)C4—C5—C6—C1−1.1 (2)
F1—C1—C2—C3178.88 (13)C7—C5—C6—C1176.65 (13)
C6—C1—C2—C30.4 (2)C4—C5—C7—N180 (5)
F1—C1—C2—O15.0 (2)C6—C5—C7—N1−98 (5)
C6—C1—C2—O1−173.52 (13)C2—O1—C8—C10154.42 (13)
O1—C2—C3—C4173.66 (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—C61.2 (2)C9—C8—C10—C9i0.4 (2)
C3—C4—C5—C7−176.60 (14)O1—C8—C10—C9i177.93 (12)
F1—C1—C6—C5−178.13 (13)

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9···N1ii0.932.503.410 (2)166

Symmetry codes: (ii) −x, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2138).

References

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

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