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

Sreenivasa, S.; Nanjundaswamy, M.S.; Manojkumar, K.E.; Madankumar, S.; Lokanath, N.K.; Suchetan, P.A.

doi:10.1107/S1600536814000348

organic compounds

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doi:10.1107/S1600536814000348

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

S. Sreenivasa,^a M. S. Nanjundaswamy,^b K. E. Manojkumar,^a S. Madankumar,^c N. K. Lokanath ^c and P. A. Suchetan ^d ^*

^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].

CCDC reference: 980205

Related literature

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

Experimental

Crystal data

C₈H₆FNO₂
M_r = 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 ) T_min = 0.761, T_max = 0.815
8417 measured reflections
1095 independent reflections
892 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; 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.

Supporting information

CCDC reference: 980205

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814000348/hb7182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000348/hb7182Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814000348/hb7182Isup3.cml

checkCIF report

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

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

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

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

	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.
	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

C₈H₆FNO₂	Prism
M_r = 167.14	D_x = 1.490 Mg m⁻³
Orthorhombic, Pna2₁	Melting point: 395 K
Hall symbol: P 2c -2n	Cu Kα radiation, λ = 1.54178 Å
a = 16.0965 (14) Å	Cell parameters from 1213 reflections
b = 4.8453 (4) Å	θ = 5.5–64.6°
c = 9.5538 (9) Å	µ = 1.08 mm⁻¹
V = 745.12 (11) Å³	T = 293 K
Z = 4	Prism, colourless
F(000) = 344	0.33 × 0.25 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	1095 independent reflections
Radiation source: fine-focus sealed tube	892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.100
φ and ω scans	θ_max = 64.1°, θ_min = 5.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
T_min = 0.761, T_max = 0.815	k = −5→5
8417 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)] = 0.078	H-atom parameters constrained
wR(F²) = 0.203	w = 1/[σ²(F_o²) + (0.1544P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.011
1095 reflections	Δρ_max = 0.34 e Å⁻³
129 parameters	Δρ_min = −0.27 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (4)

Crystal data top

C₈H₆FNO₂	V = 745.12 (11) Å³
M_r = 167.14	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 16.0965 (14) Å	µ = 1.08 mm⁻¹
b = 4.8453 (4) Å	T = 293 K
c = 9.5538 (9) Å	0.33 × 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)
T_min = 0.761, T_max = 0.815	R_int = 0.100
8417 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	1 restraint
wR(F²) = 0.203	H-atom parameters constrained
S = 1.07	Δρ_max = 0.34 e Å⁻³
1095 reflections	Δρ_min = −0.27 e Å⁻³
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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.22198 (14)	0.0813 (5)	0.4662 (8)	0.0574 (9)
C2	0.1931 (4)	0.1773 (11)	0.3445 (6)	0.0639 (15)
H2	0.2131	0.1031	0.2613	0.077*
C3	0.1370 (4)	0.3748 (12)	0.3401 (6)	0.0701 (15)
H3	0.1195	0.4429	0.2540	0.084*
C4	0.10325 (17)	0.4839 (6)	0.4642 (12)	0.0776 (13)
C5	0.1310 (3)	0.3844 (12)	0.5870 (7)	0.0758 (17)
H5	0.1087	0.4542	0.6696	0.091*
C6	0.1934 (3)	0.1761 (12)	0.5954 (7)	0.0671 (16)
H6	0.2134	0.1088	0.6802	0.080*
C7	0.0410 (7)	0.708 (2)	0.4198 (14)	0.036 (4)	0.44 (3)
H7	0.0324	0.7490	0.3259	0.043*	0.44 (3)
C8	0.0004 (8)	0.839 (2)	0.5188 (15)	0.045 (4)	0.44 (3)
H8	0.0090	0.8030	0.6134	0.053*	0.44 (3)
C7A	0.0409 (6)	0.687 (2)	0.5181 (13)	0.056 (4)	0.56 (3)
H7A	0.0311	0.7124	0.6132	0.067*	0.56 (3)
C8A	0.0010 (7)	0.828 (3)	0.4217 (14)	0.057 (4)	0.56 (3)
H8A	0.0100	0.7943	0.3270	0.068*	0.56 (3)
N1	−0.05955 (14)	1.0454 (5)	0.4692 (7)	0.0588 (8)
F1	0.27937 (11)	−0.1214 (4)	0.4674 (6)	0.0848 (9)
O1	−0.0826 (3)	1.1361 (12)	0.3561 (5)	0.0967 (15)
O2	−0.0840 (3)	1.1298 (12)	0.5777 (4)	0.0886 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0495 (14)	0.0531 (15)	0.070 (2)	0.0015 (10)	−0.001 (3)	−0.012 (3)
C2	0.081 (4)	0.061 (3)	0.050 (3)	−0.004 (3)	0.007 (3)	−0.005 (2)
C3	0.063 (3)	0.077 (4)	0.070 (4)	−0.004 (3)	−0.004 (3)	0.022 (3)
C4	0.0459 (15)	0.0480 (15)	0.139 (4)	−0.0036 (12)	0.012 (4)	0.006 (4)
C5	0.064 (3)	0.063 (3)	0.100 (4)	−0.011 (3)	0.030 (4)	−0.019 (3)
C6	0.060 (3)	0.082 (4)	0.059 (3)	−0.011 (3)	−0.004 (2)	−0.003 (3)
C7	0.039 (6)	0.044 (5)	0.025 (7)	0.011 (4)	0.012 (4)	0.001 (4)
C8	0.062 (8)	0.041 (6)	0.030 (9)	0.009 (5)	−0.013 (5)	0.008 (4)
C7A	0.066 (7)	0.067 (7)	0.035 (7)	−0.017 (5)	0.016 (4)	0.000 (4)
C8A	0.058 (6)	0.085 (8)	0.028 (7)	−0.003 (6)	−0.007 (4)	0.004 (4)
N1	0.0559 (13)	0.0616 (13)	0.0589 (18)	0.0046 (10)	−0.015 (2)	0.003 (3)
F1	0.0633 (11)	0.0673 (12)	0.124 (2)	0.0142 (7)	−0.004 (2)	0.018 (3)
O1	0.103 (4)	0.118 (3)	0.069 (3)	−0.007 (3)	−0.003 (3)	0.014 (3)
O2	0.104 (3)	0.129 (4)	0.033 (2)	−0.003 (3)	0.007 (3)	0.005 (2)

Geometric parameters (Å, º) top

C1—C2	1.335 (10)	C6—H6	0.9300
C1—F1	1.348 (3)	C7—C8	1.31 (2)
C1—C6	1.395 (9)	C7—H7	0.9300
C2—C3	1.317 (8)	C8—N1	1.470 (13)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.407 (12)	C7A—C8A	1.31 (2)
C3—H3	0.9300	C7A—H7A	0.9300
C4—C5	1.345 (12)	C8A—N1	1.506 (16)
C4—C7A	1.499 (13)	C8A—H8A	0.9300
C4—C7	1.536 (14)	N1—O2	1.182 (8)
C5—C6	1.426 (9)	N1—O1	1.224 (8)
C5—H5	0.9300

C2—C1—F1	119.9 (6)	C5—C6—H6	122.7
C2—C1—C6	122.8 (3)	C8—C7—C4	117.8 (14)
F1—C1—C6	117.3 (6)	C8—C7—H7	121.1
C3—C2—C1	121.3 (5)	C4—C7—H7	121.1
C3—C2—H2	119.4	C7—C8—N1	115.1 (13)
C1—C2—H2	119.4	C7—C8—H8	122.5
C2—C3—C4	120.7 (5)	N1—C8—H8	122.5
C2—C3—H3	119.6	C8A—C7A—C4	115.3 (13)
C4—C3—H3	119.6	C8A—C7A—H7A	122.3
C5—C4—C3	118.2 (3)	C4—C7A—H7A	122.3
C5—C4—C7A	99.1 (9)	C7A—C8A—N1	117.9 (13)
C3—C4—C7A	142.7 (10)	C7A—C8A—H8A	121.0
C5—C4—C7	135.3 (9)	N1—C8A—H8A	121.0
C3—C4—C7	106.5 (9)	O2—N1—O1	123.3 (3)
C4—C5—C6	122.5 (5)	O2—N1—C8	99.9 (8)
C4—C5—H5	118.8	O1—N1—C8	136.7 (8)
C6—C5—H5	118.8	O2—N1—C8A	136.2 (7)
C1—C6—C5	114.5 (5)	O1—N1—C8A	100.5 (7)
C1—C6—H6	122.7

F1—C1—C2—C3	179.9 (5)	C3—C4—C7—C8	179.3 (7)
C6—C1—C2—C3	2.0 (6)	C7A—C4—C7—C8	2.0 (7)
C1—C2—C3—C4	−2.5 (9)	C4—C7—C8—N1	−178.6 (6)
C2—C3—C4—C5	1.2 (6)	C5—C4—C7A—C8A	179.5 (7)
C2—C3—C4—C7A	−177.6 (6)	C3—C4—C7A—C8A	−1.5 (12)
C2—C3—C4—C7	179.8 (6)	C7—C4—C7A—C8A	2.8 (7)
C3—C4—C5—C6	0.5 (6)	C4—C7A—C8A—N1	−177.2 (5)
C7A—C4—C5—C6	179.8 (6)	C7—C8—N1—O2	−178.5 (8)
C7—C4—C5—C6	−177.5 (6)	C7—C8—N1—O1	−1.1 (13)
C2—C1—C6—C5	−0.2 (5)	C7—C8—N1—C8A	3.3 (7)
F1—C1—C6—C5	−178.2 (3)	C7A—C8A—N1—O2	−1.2 (12)
C4—C5—C6—C1	−1.0 (8)	C7A—C8A—N1—O1	178.4 (7)
C5—C4—C7—C8	−2.5 (11)	C7A—C8A—N1—C8	1.4 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7A—H7A···O1ⁱ	0.93	2.57	3.408 (13)	150

Symmetry code: (i) −x, −y+2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7A—H7A···O1ⁱ	0.93	2.57	3.408 (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

Belestskaya, I. P. & Cheprakov, A. V. (2000). Chem. Rev. 100, 3009–3066. PubMed Google Scholar
Bruker (2009). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Heck, R. F. (1968). J. Am. Chem. Soc. 90, 5518–5526. CrossRef CAS Web of Science Google Scholar
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. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Page o124

doi:10.1107/S1600536814000348

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