Ethyl 4-fluoro-3-nitro­benzoate

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

doi:10.1107/S1600536809005224

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o556

doi:10.1107/S1600536809005224

Open

access

Ethyl 4-fluoro-3-nitrobenzoate

Shivanagere Nagojappa Narendra Babu,^a Aisyah Saad Abdul Rahim,^a ‡ Hasnah Osman,^b Ibrahim Abdul Razak ^c and Hoong-Kun Fun ^c ^*

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 12 February 2009; accepted 13 February 2009; online 21 February 2009)

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.

Related literature

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

Crystal data

C₉H₈FNO₄
M_r = 213.16
Monoclinic, P 2₁ /c
a = 9.9246 (3) Å
b = 13.2883 (3) Å
c = 6.9310 (2) Å
β = 94.410 (2)°
V = 911.36 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 K
0.55 × 0.22 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.929, T_max = 0.988
12540 measured reflections
2913 independent reflections
2411 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.139
S = 1.11
2913 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.93	2.44	3.2380 (15)	144
Symmetry code: (i) -x-1, -y, -z.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005224/at2723sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005224/at2723Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme.
	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

C₉H₈FNO₄	F(000) = 440
M_r = 213.16	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5027 reflections
a = 9.9246 (3) Å	θ = 2.6–30.8°
b = 13.2883 (3) Å	µ = 0.14 mm⁻¹
c = 6.9310 (2) Å	T = 100 K
β = 94.410 (2)°	Block, colourless
V = 911.36 (4) Å³	0.55 × 0.22 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2913 independent reflections
Radiation source: sealed tube	2411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 31.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
T_min = 0.929, T_max = 0.988	k = −18→19
12540 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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.139	w = 1/[σ²(F_o²) + (0.0772P)² + 0.1955P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2913 reflections	Δρ_max = 0.55 e Å⁻³
138 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (4)

Crystal data top

C₉H₈FNO₄	V = 911.36 (4) Å³
M_r = 213.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9246 (3) Å	µ = 0.14 mm⁻¹
b = 13.2883 (3) Å	T = 100 K
c = 6.9310 (2) Å	0.55 × 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)
T_min = 0.929, T_max = 0.988	R_int = 0.028
12540 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.11	Δρ_max = 0.55 e Å⁻³
2913 reflections	Δρ_min = −0.36 e Å⁻³
138 parameters

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

	x	y	z	U_iso*/U_eq
F1	0.04351 (7)	0.10679 (6)	0.18019 (12)	0.0241 (2)
O1	0.07165 (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	−0.3804	0.0356	0.0410	0.024*
C2	−0.18146 (12)	0.05833 (9)	0.10726 (19)	0.0211 (3)
H2A	−0.1566	−0.0091	0.1139	0.025*
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	−0.2807	0.3290	0.0710	0.018*
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	−0.7170	0.3145	0.0648	0.028*
H8B	−0.7035	0.3081	−0.1597	0.028*
C9	−0.67127 (13)	0.45039 (10)	−0.0529 (2)	0.0280 (3)
H9A	−0.7638	0.4716	−0.0713	0.042*
H9B	−0.6233	0.4725	−0.1603	0.042*
H9C	−0.6304	0.4791	0.0646	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0168 (3)	0.0239 (4)	0.0312 (4)	0.0077 (3)	0.0003 (3)	0.0020 (3)
O1	0.0153 (4)	0.0295 (5)	0.0264 (5)	0.0006 (3)	−0.0037 (3)	0.0008 (4)
O2	0.0228 (4)	0.0174 (4)	0.0333 (5)	−0.0018 (3)	−0.0025 (4)	0.0042 (4)
O3	0.0123 (4)	0.0155 (4)	0.0324 (5)	0.0009 (3)	−0.0017 (3)	0.0002 (3)
O4	0.0191 (4)	0.0176 (4)	0.0453 (6)	−0.0038 (3)	−0.0041 (4)	0.0012 (4)
N1	0.0141 (4)	0.0180 (5)	0.0196 (5)	0.0007 (3)	0.0017 (3)	−0.0015 (4)
C1	0.0201 (5)	0.0148 (5)	0.0242 (6)	−0.0008 (4)	0.0010 (4)	−0.0002 (4)
C2	0.0229 (6)	0.0140 (5)	0.0263 (6)	0.0037 (4)	0.0015 (5)	0.0004 (4)
C3	0.0166 (5)	0.0185 (5)	0.0192 (5)	0.0049 (4)	0.0015 (4)	0.0006 (4)
C4	0.0144 (5)	0.0158 (5)	0.0159 (5)	0.0007 (4)	0.0010 (4)	0.0001 (4)
C5	0.0144 (5)	0.0149 (5)	0.0169 (5)	0.0018 (4)	0.0014 (4)	0.0005 (4)
C6	0.0148 (5)	0.0152 (5)	0.0181 (5)	0.0005 (4)	0.0004 (4)	−0.0001 (4)
C7	0.0157 (5)	0.0162 (5)	0.0216 (5)	−0.0003 (4)	0.0005 (4)	0.0003 (4)
C8	0.0119 (5)	0.0218 (6)	0.0350 (7)	0.0007 (4)	−0.0013 (4)	0.0022 (5)
C9	0.0188 (6)	0.0213 (6)	0.0426 (8)	0.0040 (4)	−0.0050 (5)	−0.0051 (5)

Geometric parameters (Å, º) top

F1—C3	1.3368 (13)	C3—C4	1.3932 (16)
O1—N1	1.2308 (13)	C4—C5	1.3912 (14)
O2—N1	1.2261 (13)	C5—C6	1.3906 (15)
O3—C7	1.3326 (14)	C5—H5A	0.9300
O3—C8	1.4653 (13)	C6—C7	1.4935 (15)
O4—C7	1.2127 (14)	C8—C9	1.4984 (19)
N1—C4	1.4638 (15)	C8—H8A	0.9700
C1—C2	1.3876 (16)	C8—H8B	0.9700
C1—C6	1.3959 (16)	C9—H9A	0.9600
C1—H1A	0.9300	C9—H9B	0.9600
C2—C3	1.3814 (17)	C9—H9C	0.9600
C2—H2A	0.9300

C7—O3—C8	115.52 (9)	C5—C6—C1	119.85 (10)
O2—N1—O1	124.29 (10)	C5—C6—C7	122.00 (10)
O2—N1—C4	117.80 (9)	C1—C6—C7	118.14 (10)
O1—N1—C4	117.89 (10)	O4—C7—O3	124.15 (11)
C2—C1—C6	120.96 (11)	O4—C7—C6	123.28 (11)
C2—C1—H1A	119.5	O3—C7—C6	112.57 (9)
C6—C1—H1A	119.5	O3—C8—C9	107.69 (9)
C3—C2—C1	119.01 (11)	O3—C8—H8A	110.2
C3—C2—H2A	120.5	C9—C8—H8A	110.2
C1—C2—H2A	120.5	O3—C8—H8B	110.2
F1—C3—C2	118.93 (10)	C9—C8—H8B	110.2
F1—C3—C4	120.52 (10)	H8A—C8—H8B	108.5
C2—C3—C4	120.51 (10)	C8—C9—H9A	109.5
C5—C4—C3	120.56 (10)	C8—C9—H9B	109.5
C5—C4—N1	118.32 (10)	H9A—C9—H9B	109.5
C3—C4—N1	121.11 (10)	C8—C9—H9C	109.5
C6—C5—C4	119.08 (10)	H9A—C9—H9C	109.5
C6—C5—H5A	120.5	H9B—C9—H9C	109.5
C4—C5—H5A	120.5

C6—C1—C2—C3	0.93 (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—C7	178.12 (10)
F1—C3—C4—C5	177.27 (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—O4	2.20 (18)
C2—C3—C4—N1	178.93 (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—C5	146.88 (11)	C1—C6—C7—O4	−0.09 (19)
O2—N1—C4—C3	149.33 (12)	C5—C6—C7—O3	0.26 (16)
O1—N1—C4—C3	−32.42 (16)	C1—C6—C7—O3	179.47 (11)
C3—C4—C5—C6	1.27 (17)	C7—O3—C8—C9	−177.07 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.93	2.44	3.2380 (15)	144

Symmetry code: (i) −x−1, −y, −z.

Experimental details

Crystal data
Chemical formula	C₉H₈FNO₄
M_r	213.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.9246 (3), 13.2883 (3), 6.9310 (2)
β (°)	94.410 (2)
V (Å³)	911.36 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.55 × 0.22 × 0.09

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.929, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	12540, 2913, 2411
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.727

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.139, 1.11
No. of reflections	2913
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

F1—C3	1.3368 (13)	O3—C8	1.4653 (13)
O1—N1	1.2308 (13)	O4—C7	1.2127 (14)
O2—N1	1.2261 (13)	N1—C4	1.4638 (15)
O3—C7	1.3326 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.93	2.44	3.2380 (15)	144

Symmetry code: (i) −x−1, −y, −z.

Footnotes

‡Additional correspondence author, e-mail: aisyah@usm.my.

Acknowledgements

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

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. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar
Li, H.-Y., Liu, B.-N., Tang, S.-G. & Guo, C. (2009). Acta Cryst. E65, o91. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, H.-Y., Liu, B.-N., Tang, S.-G., Xu, Y.-M. & Guo, C. (2008). Acta Cryst. E64, o523. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mohd. Maidin, S. M., Abdul Rahim, A. S., Abdul Hamid, S., Kia, R. & Fun, H.-K. (2008). Acta Cryst. E64, o1501–o1502. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mohd. Maidin, S. M., Abdul Rahim, A. S., Osman, H., Kia, R. & Fun, H.-K. (2008). Acta Cryst. E64, o1550–o1551. Web of Science CSD CrossRef IUCr Journals Google Scholar
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. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar