supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2009). E65, o556    [ doi:10.1107/S1600536809005224 ]

Ethyl 4-fluoro-3-nitrobenzoate

S. N. Narendra Babu, A. S. Abdul Rahim, H. Osman, I. A. Razak and H.-K. Fun

Abstract top

In the title compound, C9H8FNO4, C-H...O intermolecular interactions form dimers with R22(10) motifs. These dimers are arranged into chains parallel to the b axis and the chains are stacked down the c axis.

Comment top

The nitro benzoic acid intermediates are convenient starting materials for the synthesis of various biologically active heterocycles e.g. benzimidazoles (Ishida et al., 2006) and benzoxazoles (Rida et al., 2005). As a part of our ongoing studies on new nitro benzoic acid derivatives (Mohd. Maidin, Abdul Rahim, Abdul Hamid et al., 2008), we have synthesized the title compound as an intermediate and report its structure here.

The bond lengths (Allen et al., 1987) and angles observed in (I) are within normal ranges and are consistent with other related structures (Mohd. Maidin, Abdul Rahim, Osman et al., 2008; Li et al., 2009; Li et al., 2008). The C1—H1A···O4i intermolecular interactions (Table 2) linked the molecules into dimers forming 10-membered rings with R22(10) motifs (Bernstein et al., 1995). In the crystal structure, these dimers are arranged into chains parallel to the b axis. The chains are stacked down the c axis (Fig. 2).

Related literature top

For general background, see: Ishida et al. (2006); Rida et al. (2005); Mohd. Maidin, Abdul Rahim, Abdul Hamid et al. (2008). For bond-length data, see: Allen et al. (1987). For related structures, see: Mohd. Maidin, Abdul Rahim, Osman et al. (2008); Li et al. (2008, 2009). For details of hydrogen-bond motifs, see: Bernstein et al. (1995). For details on the stability of the temperature controller, see: Cosier & Glazer (1986).

Experimental top

For the preparation of the title compound, 4-fluoro-3-nitro-benzoic acid (5.0 g, 0.027 mol) was refluxed in absolute ethanol (50 ml) and conc. H2SO4 (2.0 ml) for 8 h. Upon reaction completion, ethanol was evaporated and the reaction mixture was diluted with water. The aqueous layer was extracted with ethyl acetate (25 x 2 ml). The combined organic layer was collected and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to afford yellow oil as the crude product. Recrystallization with hot ethyl acetate and petroleum ether (60–80) yielded colourless crystals that were found suitable for X-ray analysis.

Refinement top

All the H atoms were positioned geometrically and refined using a riding model with C—H = 0.93Å for aromatic and 0.96Å for CH3. The Uiso values were constrained to be -1.5Ueq of the carrier atom for the methyl H atoms and -1.2Uequ for the remaining hydrogen atoms. The rotating model group was considered for the methyl group.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed down the c axis. Intermolecular hydrogen bondings are shown as dotted lines.
Ethyl 4-fluoro-3-nitrobenzoate top
Crystal data top
C9H8FNO4F(000) = 440
Mr = 213.16Dx = 1.554 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5027 reflections
a = 9.9246 (3) Åθ = 2.6–30.8°
b = 13.2883 (3) ŵ = 0.14 mm−1
c = 6.9310 (2) ÅT = 100 K
β = 94.410 (2)°Block, colourless
V = 911.36 (4) Å30.55 × 0.22 × 0.09 mm
Z = 4
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2913 independent reflections
Radiation source: sealed tube2411 reflections with I > 2σ(I)
graphiteRint = 0.028
φ and ω scansθmax = 31.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −14→14
Tmin = 0.929, Tmax = 0.988k = −18→19
12540 measured reflectionsl = −10→10
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)] = 0.045H-atom parameters constrained
wR(F2) = 0.139 w = 1/[σ2(Fo2) + (0.0772P)2 + 0.1955P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2913 reflectionsΔρmax = 0.55 e Å−3
138 parametersΔρmin = −0.36 e Å−3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.018 (4)
Crystal data top
C9H8FNO4V = 911.36 (4) Å3
Mr = 213.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.9246 (3) ŵ = 0.14 mm−1
b = 13.2883 (3) ÅT = 100 K
c = 6.9310 (2) Å0.55 × 0.22 × 0.09 mm
β = 94.410 (2)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		2913 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2411 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.988Rint = 0.028
12540 measured reflectionsθmax = 31.1°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.139Δρmax = 0.55 e Å−3
S = 1.11Δρmin = −0.36 e Å−3
2913 reflectionsAbsolute structure: ?
138 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
xyzUiso*/Ueq
F10.04351 (7)0.10679 (6)0.18019 (12)0.0241 (2)
O10.07165 (9)0.29746 (7)0.29028 (14)0.0240 (2)
O2−0.04092 (9)0.39394 (6)0.08249 (15)0.0247 (2)
O3−0.52330 (8)0.30897 (6)−0.00372 (14)0.0203 (2)
O4−0.58597 (9)0.14638 (7)−0.02358 (16)0.0276 (2)
N1−0.02296 (10)0.31401 (7)0.16902 (15)0.0172 (2)
C1−0.31523 (12)0.08546 (9)0.06256 (18)0.0197 (2)
H1A−0.38040.03560.04100.024*
C2−0.18146 (12)0.05833 (9)0.10726 (19)0.0211 (3)
H2A−0.1566−0.00910.11390.025*
C3−0.08581 (11)0.13301 (9)0.14173 (17)0.0181 (2)
C4−0.12280 (11)0.23409 (8)0.12960 (16)0.0154 (2)
C5−0.25648 (11)0.26145 (8)0.08154 (16)0.0154 (2)
H5A−0.28070.32900.07100.018*
C6−0.35338 (11)0.18648 (8)0.04945 (17)0.0161 (2)
C7−0.49936 (11)0.21032 (9)0.00323 (18)0.0179 (2)
C8−0.66549 (12)0.33789 (10)−0.0398 (2)0.0231 (3)
H8A−0.71700.31450.06480.028*
H8B−0.70350.3081−0.15970.028*
C9−0.67127 (13)0.45039 (10)−0.0529 (2)0.0280 (3)
H9A−0.76380.4716−0.07130.042*
H9B−0.62330.4725−0.16030.042*
H9C−0.63040.47910.06460.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0168 (3)0.0239 (4)0.0312 (4)0.0077 (3)0.0003 (3)0.0020 (3)
O10.0153 (4)0.0295 (5)0.0264 (5)0.0006 (3)−0.0037 (3)0.0008 (4)
O20.0228 (4)0.0174 (4)0.0333 (5)−0.0018 (3)−0.0025 (4)0.0042 (4)
O30.0123 (4)0.0155 (4)0.0324 (5)0.0009 (3)−0.0017 (3)0.0002 (3)
O40.0191 (4)0.0176 (4)0.0453 (6)−0.0038 (3)−0.0041 (4)0.0012 (4)
N10.0141 (4)0.0180 (5)0.0196 (5)0.0007 (3)0.0017 (3)−0.0015 (4)
C10.0201 (5)0.0148 (5)0.0242 (6)−0.0008 (4)0.0010 (4)−0.0002 (4)
C20.0229 (6)0.0140 (5)0.0263 (6)0.0037 (4)0.0015 (5)0.0004 (4)
C30.0166 (5)0.0185 (5)0.0192 (5)0.0049 (4)0.0015 (4)0.0006 (4)
C40.0144 (5)0.0158 (5)0.0159 (5)0.0007 (4)0.0010 (4)0.0001 (4)
C50.0144 (5)0.0149 (5)0.0169 (5)0.0018 (4)0.0014 (4)0.0005 (4)
C60.0148 (5)0.0152 (5)0.0181 (5)0.0005 (4)0.0004 (4)−0.0001 (4)
C70.0157 (5)0.0162 (5)0.0216 (5)−0.0003 (4)0.0005 (4)0.0003 (4)
C80.0119 (5)0.0218 (6)0.0350 (7)0.0007 (4)−0.0013 (4)0.0022 (5)
C90.0188 (6)0.0213 (6)0.0426 (8)0.0040 (4)−0.0050 (5)−0.0051 (5)
Geometric parameters (Å, °) top
F1—C31.3368 (13)C3—C41.3932 (16)
O1—N11.2308 (13)C4—C51.3912 (14)
O2—N11.2261 (13)C5—C61.3906 (15)
O3—C71.3326 (14)C5—H5A0.9300
O3—C81.4653 (13)C6—C71.4935 (15)
O4—C71.2127 (14)C8—C91.4984 (19)
N1—C41.4638 (15)C8—H8A0.9700
C1—C21.3876 (16)C8—H8B0.9700
C1—C61.3959 (16)C9—H9A0.9600
C1—H1A0.9300C9—H9B0.9600
C2—C31.3814 (17)C9—H9C0.9600
C2—H2A0.9300
C7—O3—C8115.52 (9)C5—C6—C1119.85 (10)
O2—N1—O1124.29 (10)C5—C6—C7122.00 (10)
O2—N1—C4117.80 (9)C1—C6—C7118.14 (10)
O1—N1—C4117.89 (10)O4—C7—O3124.15 (11)
C2—C1—C6120.96 (11)O4—C7—C6123.28 (11)
C2—C1—H1A119.5O3—C7—C6112.57 (9)
C6—C1—H1A119.5O3—C8—C9107.69 (9)
C3—C2—C1119.01 (11)O3—C8—H8A110.2
C3—C2—H2A120.5C9—C8—H8A110.2
C1—C2—H2A120.5O3—C8—H8B110.2
F1—C3—C2118.93 (10)C9—C8—H8B110.2
F1—C3—C4120.52 (10)H8A—C8—H8B108.5
C2—C3—C4120.51 (10)C8—C9—H9A109.5
C5—C4—C3120.56 (10)C8—C9—H9B109.5
C5—C4—N1118.32 (10)H9A—C9—H9B109.5
C3—C4—N1121.11 (10)C8—C9—H9C109.5
C6—C5—C4119.08 (10)H9A—C9—H9C109.5
C6—C5—H5A120.5H9B—C9—H9C109.5
C4—C5—H5A120.5
C6—C1—C2—C30.93 (19)N1—C4—C5—C6−178.04 (10)
C1—C2—C3—F1−178.41 (11)C4—C5—C6—C1−1.07 (18)
C1—C2—C3—C4−0.74 (19)C4—C5—C6—C7178.12 (10)
F1—C3—C4—C5177.27 (10)C2—C1—C6—C5−0.02 (19)
C2—C3—C4—C5−0.36 (18)C2—C1—C6—C7−179.25 (11)
F1—C3—C4—N1−3.44 (17)C8—O3—C7—O42.20 (18)
C2—C3—C4—N1178.93 (11)C8—O3—C7—C6−177.35 (10)
O2—N1—C4—C5−31.36 (16)C5—C6—C7—O4−179.29 (12)
O1—N1—C4—C5146.88 (11)C1—C6—C7—O4−0.09 (19)
O2—N1—C4—C3149.33 (12)C5—C6—C7—O30.26 (16)
O1—N1—C4—C3−32.42 (16)C1—C6—C7—O3179.47 (11)
C3—C4—C5—C61.27 (17)C7—O3—C8—C9−177.07 (11)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4i0.932.443.2380 (15)144
Symmetry codes: (i) −x−1, −y, −z.
Table 1
Selected geometric parameters (Å) top
F1—C31.3368 (13)O3—C81.4653 (13)
O1—N11.2308 (13)O4—C71.2127 (14)
O2—N11.2261 (13)N1—C41.4638 (15)
O3—C71.3326 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O4i0.932.443.2380 (15)144
Symmetry codes: (i) −x−1, −y, −z.
Acknowledgements top

HKF and IAR thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. Funding from the Malaysian Government and Universiti Sains Malaysia (USM) under USM Research University grant (1001/PFARMASI/815026) is gratefully acknowledged. SNNB thanks Universiti Sains Malaysia for a Postdoctoral Research Fellowship.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.

Ishida, T., Suzuki, T., Hirashima, S., Mizutani, K., Yoshida, A., Ando, I., Ikeda, S., Adachi, T. & Hashimoto, H. (2006). Bioorg. Med. Chem. Lett. 16, 1859–1863.

Li, H.-Y., Liu, B.-N., Tang, S.-G. & Guo, C. (2009). Acta Cryst. E65, o91.

Li, H.-Y., Liu, B.-N., Tang, S.-G., Xu, Y.-M. & Guo, C. (2008). Acta Cryst. E64, o523.

Mohd. Maidin, S. M., Abdul Rahim, A. S., Abdul Hamid, S., Kia, R. & Fun, H.-K. (2008). Acta Cryst. E64, o1501–o1502.

Mohd. Maidin, S. M., Abdul Rahim, A. S., Osman, H., Kia, R. & Fun, H.-K. (2008). Acta Cryst. E64, o1550–o1551.

Rida, S. M., Ashour, F. A., El-Hawash, S. A. M., ElSemary, M. M., Badr, M. H. & Shalaby, M. A. (2005). Eur. J. Med. Chem. 40, 949–959.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.