2-Fluoro-5-nitro­aniline

Moorthy, K.; NizamMohideen, M.; Vetrivel, S.; Vinoth, E.; Arun, A.

doi:10.1107/S241431461800425X

organic compounds

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ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180425

https://doi.org/10.1107/S241431461800425X

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2-Fluoro-5-nitroaniline

K. Moorthy,^a,^b M. NizamMohideen,^c ^* S. Vetrivel,^d E. Vinoth ^d and A. Arun ^b ^*

^aR&D centre, Bharathiyar University, Coimbatore 641 046, Tamil Nadu, India, ^bDepartment of Chemistry, Government Arts College, Tiruvannamalai 606 603, Tamil Nadu, India, ^cDepartment of Physics, The New College (Autonomous), Chennai 600 014, Tamil Nadu, India, and ^dDepartment of Physics, Government Arts College, Tiruvannamalai 606 603, Tamil Nadu, India
^*Correspondence e-mail: mnizam.new@gmail.com, aruna2075@yahoo.co.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 February 2018; accepted 13 March 2018; online 23 March 2018)

In the title compound, C₆H₅FN₂O₂, the dihedral angle between the nitro group and the benzene ring is 3.68 (2)°, and an intramolecular N—H⋯F hydrogen bond is observed. The crystal packing is consolidated by C—H⋯O and N—H⋯O hydrogen bonds; together, these generate [110] double chains.

Keywords: crystal structure; aniline; 5-nitroaniline; 2-fluoro-5-nitroaniline; hydrogen bonding.

CCDC reference: 1829279

Structure description

The title compound can be utilized to synthesize dyes and pigments (Qi et al., 2009 ; Hu et al., 2010 ) but its crystal structure has not yet been determined and is reported here.

The molecular conformation is essentially planar (Fig. 1), with a maximum deviation of 0.062 (2) Å for O2. The dihedral angle between the nitro group and the benzene ring is 3.68 (2)°. The C—N bond distance [1.379 (3) Å] of the NH₂ group is short for a C—N single bond, which may indicate a significant contribution from the imino resonance form to the structure. A weak intramolecular N—H⋯F hydrogen bond is observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯F1	0.85 (3)	2.37 (3)	2.718 (3)	105 (2)
N2—H2B⋯O1ⁱ	0.85 (3)	2.45 (3)	3.270 (3)	162 (2)
C6—H6⋯O2ⁱⁱ	0.93	2.51	3.348 (3)	150
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+3, -z+2.

Figure 1
The molecular structure with displacement ellipsoids drawn at the 50% probability level.

The crystal packing is consolidated by C—H⋯O and N—H⋯O hydrogen bonds (Fig. 2). The aromatic carbon (C6) atom interacts with the nitro group O atom to generate an R₂²(10) loop. The resulting dimeric units are connected via N—H⋯O hydrogen bonds, forming an R₄⁴(16) ring motif. Taken together, [110] double chains arise.

Figure 2
The crystal packing of the title compound, viewed down [010]. The hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

2-Fluoro-5-nitroaniline (4 g) was dissolved in the minimum quantity of ethanol and sonicated for 1 h and then placed in an microwave oven for about ten minutes. The resulting paste-like material was dissolved in 10 ml of ethanol and brown blocks were recovered after 48 h as the solvent evaporated.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₅FN₂O₂
M_r	156.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.1967 (9), 3.7559 (2), 14.4539 (10)
β (°)	102.143 (3)
V (Å³)	647.31 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.14
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.666, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7982, 1124, 731
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.106, 1.09
No. of reflections	1124
No. of parameters	108
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.19
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXT2014 (Sheldrick, 2015a ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ), SHELXL2014 (Sheldrick, 2015b ), WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1829279

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461800425X/hb4212sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461800425X/hb4212Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461800425X/hb4212Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

2-Fluoro-5-nitroaniline top

Crystal data top

C₆H₅FN₂O₂	F(000) = 320
M_r = 156.12	D_x = 1.602 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.1967 (9) Å	Cell parameters from 2057 reflections
b = 3.7559 (2) Å	θ = 2.5–28.0°
c = 14.4539 (10) Å	µ = 0.14 mm⁻¹
β = 102.143 (3)°	T = 296 K
V = 647.31 (7) Å³	Block, brown
Z = 4	0.25 × 0.20 × 0.15 mm

Data collection top

Bruker KappaCCD diffractometer	1124 independent reflections
Radiation source: fine-focus sealed tube	731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and φ scan	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
T_min = 0.666, T_max = 0.746	k = −4→4
7982 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.106	w = 1/[σ²(F_o²) + (0.0453P)² + 0.1287P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1124 reflections	Δρ_max = 0.15 e Å⁻³
108 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The N-bound H atoms were located in a difference Fourier map and refined with distance restraints: N—H = 0.89 (2) Å. The C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.24514 (17)	1.0767 (5)	0.94448 (14)	0.0370 (5)
C2	0.16370 (17)	0.9076 (5)	0.98328 (16)	0.0423 (6)
C3	0.17626 (19)	0.8268 (5)	1.07728 (16)	0.0430 (6)
H3	0.1187	0.7157	1.0995	0.052*
C4	0.27553 (18)	0.9127 (5)	1.13846 (15)	0.0402 (6)
H4	0.2869	0.8600	1.2026	0.048*
C5	0.35721 (17)	1.0787 (5)	1.10151 (13)	0.0327 (5)
C6	0.34464 (17)	1.1593 (5)	1.00692 (13)	0.0343 (5)
H6	0.4027	1.2687	0.9850	0.041*
N1	0.46159 (16)	1.1836 (4)	1.16606 (12)	0.0439 (5)
N2	0.2278 (2)	1.1426 (7)	0.84863 (14)	0.0563 (6)
O1	0.47362 (16)	1.1064 (6)	1.24921 (11)	0.0826 (7)
O2	0.53201 (14)	1.3472 (5)	1.13505 (11)	0.0627 (5)
F1	0.06598 (11)	0.8233 (4)	0.92311 (10)	0.0660 (5)
H2B	0.158 (2)	1.155 (7)	0.8230 (19)	0.074 (9)*
H2A	0.271 (2)	1.293 (7)	0.830 (2)	0.083 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0376 (13)	0.0370 (12)	0.0353 (11)	0.0103 (11)	0.0055 (10)	−0.0004 (10)
C2	0.0295 (13)	0.0389 (12)	0.0552 (14)	0.0049 (10)	0.0015 (11)	−0.0096 (11)
C3	0.0391 (14)	0.0358 (12)	0.0597 (15)	−0.0010 (11)	0.0231 (12)	−0.0013 (10)
C4	0.0499 (15)	0.0358 (12)	0.0380 (11)	0.0044 (11)	0.0164 (11)	0.0006 (10)
C5	0.0341 (12)	0.0294 (10)	0.0345 (11)	0.0040 (9)	0.0067 (9)	−0.0024 (9)
C6	0.0343 (12)	0.0341 (11)	0.0364 (11)	0.0040 (10)	0.0117 (10)	−0.0001 (9)
N1	0.0433 (12)	0.0475 (11)	0.0387 (11)	0.0041 (10)	0.0035 (9)	−0.0031 (9)
N2	0.0491 (15)	0.0750 (16)	0.0400 (12)	0.0034 (14)	−0.0016 (11)	0.0038 (11)
O1	0.0832 (15)	0.1230 (16)	0.0340 (10)	−0.0218 (12)	−0.0053 (9)	0.0090 (11)
O2	0.0414 (10)	0.0848 (12)	0.0595 (11)	−0.0144 (10)	0.0056 (9)	0.0022 (9)
F1	0.0375 (8)	0.0796 (10)	0.0755 (10)	−0.0046 (7)	−0.0001 (7)	−0.0135 (8)

Geometric parameters (Å, º) top

C1—N2	1.379 (3)	C4—H4	0.9300
C1—C6	1.387 (3)	C5—C6	1.377 (3)
C1—C2	1.392 (3)	C5—N1	1.465 (3)
C2—F1	1.357 (2)	C6—H6	0.9300
C2—C3	1.369 (3)	N1—O1	1.215 (2)
C3—C4	1.379 (3)	N1—O2	1.216 (2)
C3—H3	0.9300	N2—H2B	0.85 (3)
C4—C5	1.375 (3)	N2—H2A	0.85 (3)

N2—C1—C6	122.8 (2)	C4—C5—C6	123.2 (2)
N2—C1—C2	121.0 (2)	C4—C5—N1	118.56 (18)
C6—C1—C2	116.15 (19)	C6—C5—N1	118.27 (18)
F1—C2—C3	119.0 (2)	C5—C6—C1	119.77 (19)
F1—C2—C1	116.9 (2)	C5—C6—H6	120.1
C3—C2—C1	124.1 (2)	C1—C6—H6	120.1
C2—C3—C4	119.0 (2)	O1—N1—O2	122.5 (2)
C2—C3—H3	120.5	O1—N1—C5	118.28 (19)
C4—C3—H3	120.5	O2—N1—C5	119.18 (18)
C5—C4—C3	117.85 (19)	C1—N2—H2B	111.9 (18)
C5—C4—H4	121.1	C1—N2—H2A	117 (2)
C3—C4—H4	121.1	H2B—N2—H2A	117 (3)

N2—C1—C2—F1	−2.2 (3)	C4—C5—C6—C1	1.0 (3)
C6—C1—C2—F1	−179.70 (16)	N1—C5—C6—C1	−177.43 (16)
N2—C1—C2—C3	178.47 (19)	N2—C1—C6—C5	−178.51 (18)
C6—C1—C2—C3	1.0 (3)	C2—C1—C6—C5	−1.1 (3)
F1—C2—C3—C4	−179.95 (17)	C4—C5—N1—O1	3.0 (3)
C1—C2—C3—C4	−0.7 (3)	C6—C5—N1—O1	−178.58 (19)
C2—C3—C4—C5	0.4 (3)	C4—C5—N1—O2	−176.16 (18)
C3—C4—C5—C6	−0.6 (3)	C6—C5—N1—O2	2.3 (3)
C3—C4—C5—N1	177.80 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···F1	0.85 (3)	2.37 (3)	2.718 (3)	105 (2)
N2—H2B···O1ⁱ	0.85 (3)	2.45 (3)	3.270 (3)	162 (2)
C6—H6···O2ⁱⁱ	0.93	2.51	3.348 (3)	150

Symmetry codes: (i) x−1/2, −y+5/2, z−1/2; (ii) −x+1, −y+3, −z+2.

Acknowledgements

The authors are grateful to the SAIF, IIT, Madras, India, for the data collection.

References

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