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1-Fluoro-4-[(E)-2-nitro­vin­yl]benzene

aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, bDepartment of Chemistry, AVK College for Women, Davangere-2, India, cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore, India, and dDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India
*Correspondence e-mail: pasuchetan@yahoo.co.in

(Received 5 January 2014; accepted 7 January 2014; online 11 January 2014)

The title compound, C8H6FNO2, is almost planar (r.m.s. deviation for the non-H atoms = 0.019 Å) and the conformation across the C=C bond is trans. The C and H atoms of the side chain are disordered over two sets of sites in a 0.56 (3):0.44 (3) ratio. In the crystal, mol­ecules are linked by C—H⋯O inter­actions, thus forming C(5) chains propagating in [001].

Related literature

For the biological activity of fluorinated aromatic compounds, see: Belestskaya & Cheprakov (2000[Belestskaya, I. P. & Cheprakov, A. V. (2000). Chem. Rev. 100, 3009-3066.]). For the preparation of the title compound, see: Heck (1968[Heck, R. F. (1968). J. Am. Chem. Soc. 90, 5518-5526.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6FNO2

  • Mr = 167.14

  • Orthorhombic, P n a 21

  • a = 16.0965 (14) Å

  • b = 4.8453 (4) Å

  • c = 9.5538 (9) Å

  • V = 745.12 (11) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 1.08 mm−1

  • T = 293 K

  • 0.33 × 0.25 × 0.19 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.761, Tmax = 0.815

  • 8417 measured reflections

  • 1095 independent reflections

  • 892 reflections with I > 2σ(I)

  • Rint = 0.100

Refinement
  • R[F2 > 2σ(F2)] = 0.078

  • wR(F2) = 0.203

  • S = 1.07

  • 1095 reflections

  • 129 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.34 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C7A—H7A⋯O1i 0.93 2.57 3.408 (13) 150
Symmetry code: (i) [-x, -y+2, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; 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: Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97.

Supporting information


Introduction top

Fluorinated aromatic compounds exhibit different biological activities such as anti­bacterial, analgesic, anti­cancer, diuretic, anti­convulsant, insecticidal, anti­fungal and anti­viral (Belestskaya et al., 2000). Further, halogenated aromatic derivatives act as a potent peptide de­formyl­ase inhibiter. As part of our studies in this area, the title compound was synthesized and its crystal structure determined.

Experimental top

The title compound was synthesized by using the method reported in literature (Heck et al., 1968).

Synthesis and crystallization top

1-Bromo-4-fluoro­benzene (5.7 mmol), tetra­butyl­ammonium­bromide (11.4 mmol), cesium carbonate (17.1 mmol) and palladium acetate (5.0 mmol) were taken in N,N-di­methyl­formamide (DMF) (20 mL) and stirred for 30 minutes. To this, nitro­ethene (8.5 mmol) was added and the reaction mixture was stirred at 353K for 14 h under nitro­gen atmosphere. The confirmation of the reaction was confirmed by TLC. The organic layer was filtered and DMF was removed under vacuum. The crude product obtained was purified by column chromatography using petroleum ether and ethyl acetate (7:3) as eluent.

Colourless prisms of the title compound was obtained from slow evaporation of the solvent system: petroleum ether : ethyl acetate (8:2).

Refinement top

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 Å. The isotropic displacement parameters for all H atoms were set to 1.2 times Ueq(C).

Results and discussion top

The title compound, C8H6FNO2, is almost planar (r.m.s. deviation for the non-H atoms = 0.019 Å) and the conformation across the C=C bond is trans. The two carbon atoms of the side chain are disordered over two sets of sites with occupancy factors 0.56 (3):0.44 (3). In the crystal structure, the molecules are linked into one another through C7A—H7A···O1 inter­actions thus forming C(5) chains.

Related literature top

For the biological activity of fluorinated aromatic compounds, see: Belestskaya & Cheprakov (2000). For the preparation of the title compound, see: Heck (1968).

Structure description top

Fluorinated aromatic compounds exhibit different biological activities such as anti­bacterial, analgesic, anti­cancer, diuretic, anti­convulsant, insecticidal, anti­fungal and anti­viral (Belestskaya et al., 2000). Further, halogenated aromatic derivatives act as a potent peptide de­formyl­ase inhibiter. As part of our studies in this area, the title compound was synthesized and its crystal structure determined.

The title compound was synthesized by using the method reported in literature (Heck et al., 1968).

The title compound, C8H6FNO2, is almost planar (r.m.s. deviation for the non-H atoms = 0.019 Å) and the conformation across the C=C bond is trans. The two carbon atoms of the side chain are disordered over two sets of sites with occupancy factors 0.56 (3):0.44 (3). In the crystal structure, the molecules are linked into one another through C7A—H7A···O1 inter­actions thus forming C(5) chains.

For the biological activity of fluorinated aromatic compounds, see: Belestskaya & Cheprakov (2000). For the preparation of the title compound, see: Heck (1968).

Synthesis and crystallization top

1-Bromo-4-fluoro­benzene (5.7 mmol), tetra­butyl­ammonium­bromide (11.4 mmol), cesium carbonate (17.1 mmol) and palladium acetate (5.0 mmol) were taken in N,N-di­methyl­formamide (DMF) (20 mL) and stirred for 30 minutes. To this, nitro­ethene (8.5 mmol) was added and the reaction mixture was stirred at 353K for 14 h under nitro­gen atmosphere. The confirmation of the reaction was confirmed by TLC. The organic layer was filtered and DMF was removed under vacuum. The crude product obtained was purified by column chromatography using petroleum ether and ethyl acetate (7:3) as eluent.

Colourless prisms of the title compound was obtained from slow evaporation of the solvent system: petroleum ether : ethyl acetate (8:2).

Refinement details top

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 Å. The isotropic displacement parameters for all H atoms were set to 1.2 times Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level. Only major components of the disordered atoms are shown.
[Figure 2] Fig. 2. Linking of molecules into C(5) chains through C—H···O interactions.
1-Fluoro-4-[(E)-2-nitrovinyl]benzene top
Crystal data top
C8H6FNO2Prism
Mr = 167.14Dx = 1.490 Mg m3
Orthorhombic, Pna21Melting point: 395 K
Hall symbol: P 2c -2nCu Kα radiation, λ = 1.54178 Å
a = 16.0965 (14) ÅCell parameters from 1213 reflections
b = 4.8453 (4) Åθ = 5.5–64.6°
c = 9.5538 (9) ŵ = 1.08 mm1
V = 745.12 (11) Å3T = 293 K
Z = 4Prism, colourless
F(000) = 3440.33 × 0.25 × 0.19 mm
Data collection top
Bruker APEXII CCD
diffractometer
1095 independent reflections
Radiation source: fine-focus sealed tube892 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.100
φ and ω scansθmax = 64.1°, θmin = 5.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1818
Tmin = 0.761, Tmax = 0.815k = 55
8417 measured reflectionsl = 1110
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.078H-atom parameters constrained
wR(F2) = 0.203 w = 1/[σ2(Fo2) + (0.1544P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.011
1095 reflectionsΔρmax = 0.34 e Å3
129 parametersΔρmin = 0.27 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.013 (4)
Crystal data top
C8H6FNO2V = 745.12 (11) Å3
Mr = 167.14Z = 4
Orthorhombic, Pna21Cu Kα radiation
a = 16.0965 (14) ŵ = 1.08 mm1
b = 4.8453 (4) ÅT = 293 K
c = 9.5538 (9) Å0.33 × 0.25 × 0.19 mm
Data collection top
Bruker APEXII CCD
diffractometer
1095 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
892 reflections with I > 2σ(I)
Tmin = 0.761, Tmax = 0.815Rint = 0.100
8417 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0781 restraint
wR(F2) = 0.203H-atom parameters constrained
S = 1.07Δρmax = 0.34 e Å3
1095 reflectionsΔρmin = 0.27 e Å3
129 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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*/UeqOcc. (<1)
C10.22198 (14)0.0813 (5)0.4662 (8)0.0574 (9)
C20.1931 (4)0.1773 (11)0.3445 (6)0.0639 (15)
H20.21310.10310.26130.077*
C30.1370 (4)0.3748 (12)0.3401 (6)0.0701 (15)
H30.11950.44290.25400.084*
C40.10325 (17)0.4839 (6)0.4642 (12)0.0776 (13)
C50.1310 (3)0.3844 (12)0.5870 (7)0.0758 (17)
H50.10870.45420.66960.091*
C60.1934 (3)0.1761 (12)0.5954 (7)0.0671 (16)
H60.21340.10880.68020.080*
C70.0410 (7)0.708 (2)0.4198 (14)0.036 (4)0.44 (3)
H70.03240.74900.32590.043*0.44 (3)
C80.0004 (8)0.839 (2)0.5188 (15)0.045 (4)0.44 (3)
H80.00900.80300.61340.053*0.44 (3)
C7A0.0409 (6)0.687 (2)0.5181 (13)0.056 (4)0.56 (3)
H7A0.03110.71240.61320.067*0.56 (3)
C8A0.0010 (7)0.828 (3)0.4217 (14)0.057 (4)0.56 (3)
H8A0.01000.79430.32700.068*0.56 (3)
N10.05955 (14)1.0454 (5)0.4692 (7)0.0588 (8)
F10.27937 (11)0.1214 (4)0.4674 (6)0.0848 (9)
O10.0826 (3)1.1361 (12)0.3561 (5)0.0967 (15)
O20.0840 (3)1.1298 (12)0.5777 (4)0.0886 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0495 (14)0.0531 (15)0.070 (2)0.0015 (10)0.001 (3)0.012 (3)
C20.081 (4)0.061 (3)0.050 (3)0.004 (3)0.007 (3)0.005 (2)
C30.063 (3)0.077 (4)0.070 (4)0.004 (3)0.004 (3)0.022 (3)
C40.0459 (15)0.0480 (15)0.139 (4)0.0036 (12)0.012 (4)0.006 (4)
C50.064 (3)0.063 (3)0.100 (4)0.011 (3)0.030 (4)0.019 (3)
C60.060 (3)0.082 (4)0.059 (3)0.011 (3)0.004 (2)0.003 (3)
C70.039 (6)0.044 (5)0.025 (7)0.011 (4)0.012 (4)0.001 (4)
C80.062 (8)0.041 (6)0.030 (9)0.009 (5)0.013 (5)0.008 (4)
C7A0.066 (7)0.067 (7)0.035 (7)0.017 (5)0.016 (4)0.000 (4)
C8A0.058 (6)0.085 (8)0.028 (7)0.003 (6)0.007 (4)0.004 (4)
N10.0559 (13)0.0616 (13)0.0589 (18)0.0046 (10)0.015 (2)0.003 (3)
F10.0633 (11)0.0673 (12)0.124 (2)0.0142 (7)0.004 (2)0.018 (3)
O10.103 (4)0.118 (3)0.069 (3)0.007 (3)0.003 (3)0.014 (3)
O20.104 (3)0.129 (4)0.033 (2)0.003 (3)0.007 (3)0.005 (2)
Geometric parameters (Å, º) top
C1—C21.335 (10)C6—H60.9300
C1—F11.348 (3)C7—C81.31 (2)
C1—C61.395 (9)C7—H70.9300
C2—C31.317 (8)C8—N11.470 (13)
C2—H20.9300C8—H80.9300
C3—C41.407 (12)C7A—C8A1.31 (2)
C3—H30.9300C7A—H7A0.9300
C4—C51.345 (12)C8A—N11.506 (16)
C4—C7A1.499 (13)C8A—H8A0.9300
C4—C71.536 (14)N1—O21.182 (8)
C5—C61.426 (9)N1—O11.224 (8)
C5—H50.9300
C2—C1—F1119.9 (6)C5—C6—H6122.7
C2—C1—C6122.8 (3)C8—C7—C4117.8 (14)
F1—C1—C6117.3 (6)C8—C7—H7121.1
C3—C2—C1121.3 (5)C4—C7—H7121.1
C3—C2—H2119.4C7—C8—N1115.1 (13)
C1—C2—H2119.4C7—C8—H8122.5
C2—C3—C4120.7 (5)N1—C8—H8122.5
C2—C3—H3119.6C8A—C7A—C4115.3 (13)
C4—C3—H3119.6C8A—C7A—H7A122.3
C5—C4—C3118.2 (3)C4—C7A—H7A122.3
C5—C4—C7A99.1 (9)C7A—C8A—N1117.9 (13)
C3—C4—C7A142.7 (10)C7A—C8A—H8A121.0
C5—C4—C7135.3 (9)N1—C8A—H8A121.0
C3—C4—C7106.5 (9)O2—N1—O1123.3 (3)
C4—C5—C6122.5 (5)O2—N1—C899.9 (8)
C4—C5—H5118.8O1—N1—C8136.7 (8)
C6—C5—H5118.8O2—N1—C8A136.2 (7)
C1—C6—C5114.5 (5)O1—N1—C8A100.5 (7)
C1—C6—H6122.7
F1—C1—C2—C3179.9 (5)C3—C4—C7—C8179.3 (7)
C6—C1—C2—C32.0 (6)C7A—C4—C7—C82.0 (7)
C1—C2—C3—C42.5 (9)C4—C7—C8—N1178.6 (6)
C2—C3—C4—C51.2 (6)C5—C4—C7A—C8A179.5 (7)
C2—C3—C4—C7A177.6 (6)C3—C4—C7A—C8A1.5 (12)
C2—C3—C4—C7179.8 (6)C7—C4—C7A—C8A2.8 (7)
C3—C4—C5—C60.5 (6)C4—C7A—C8A—N1177.2 (5)
C7A—C4—C5—C6179.8 (6)C7—C8—N1—O2178.5 (8)
C7—C4—C5—C6177.5 (6)C7—C8—N1—O11.1 (13)
C2—C1—C6—C50.2 (5)C7—C8—N1—C8A3.3 (7)
F1—C1—C6—C5178.2 (3)C7A—C8A—N1—O21.2 (12)
C4—C5—C6—C11.0 (8)C7A—C8A—N1—O1178.4 (7)
C5—C4—C7—C82.5 (11)C7A—C8A—N1—C81.4 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7A—H7A···O1i0.932.573.408 (13)150
Symmetry code: (i) x, y+2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7A—H7A···O1i0.932.573.408 (13)150
Symmetry code: (i) x, y+2, z+1/2.
 

Acknowledgements

The authors acknowledge the IOE X-ray diffractometer facility, University of Mysore, Mysore, for the data collection.

References

First citationBelestskaya, I. P. & Cheprakov, A. V. (2000). Chem. Rev. 100, 3009–3066.  PubMed Google Scholar
First citationBruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHeck, R. F. (1968). J. Am. Chem. Soc. 90, 5518–5526.  CrossRef CAS Web of Science Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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