organic compounds
2-Fluoro-5-nitroaniline
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
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.
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 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).
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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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 1829279
https://doi.org/10.1107/S241431461800425X/hb4212sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX2 (Bruker, 2004); cell
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).C6H5FN2O2 | F(000) = 320 |
Mr = 156.12 | Dx = 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 |
Bruker KappaCCD diffractometer | 1124 independent reflections |
Radiation source: fine-focus sealed tube | 731 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ω and φ scan | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −14→14 |
Tmin = 0.666, Tmax = 0.746 | k = −4→4 |
7982 measured reflections | l = −17→17 |
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(Fo2) + (0.0453P)2 + 0.1287P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1124 reflections | Δρmax = 0.15 e Å−3 |
108 parameters | Δρmin = −0.19 e Å−3 |
0 restraints |
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 Uiso(H) = 1.2Ueq(C). |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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.
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