3-Chloro-4-fluoro­anilinium picrate

Balladka K Sarojini; Badiadka Narayana; Hemmige S Yathirajan; Thomas Gerber; Benjamin van Brecht; Richard Betz

doi:10.1107/S1600536813000718

. 2013 Jan 16;69(Pt 2):o240. doi: 10.1107/S1600536813000718

3-Chloro-4-fluoroanilinium picrate

Balladka K Sarojini ^a, Badiadka Narayana ^b, Hemmige S Yathirajan ^c, Thomas Gerber ^d, Benjamin van Brecht ^d, Richard Betz ^d,^*

PMCID: PMC3569773 PMID: 23424519

Abstract

In the title picrate salt of a dihalogenated aniline derivative, C₆H₆ClF⁺·C₆H₂N₃O₇ ⁻, the intracyclic C—C—C angles in the picrate anion cover a broad range [111.95 (12)–125.38 (13)°], while those in the aromatic cation span a much narrower range [118.25 (14)–122.33 (13)°]. In the crystal, classical N—H⋯O hydrogen bonds, as well as C—H⋯O contacts, connect the ions into layers parallel to (001).

Related literature

For related structures, see: Jin et al. (2011 ▶); Wang (2011 ▶); Betz et al. (2011 ▶); Dutkiewicz et al. (2011 ▶); Jasinski et al. (2010a ▶,b ▶, 2011 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). graphic file with name e-69-0o240-scheme1.jpg

Experimental

Crystal data

C₆H₆ClF⁺·C₆H₂N₃O₇ ⁻
M _r = 374.67
Triclinic,
a = 4.4054 (2) Å
b = 11.9881 (5) Å
c = 13.7010 (5) Å
α = 90.057 (1)°
β = 91.803 (1)°
γ = 97.743 (1)°
V = 716.62 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 200 K
0.53 × 0.32 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.907, T _max = 1.000
12360 measured reflections
3525 independent reflections
2947 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.06
3525 reflections
238 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(22.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000718/bg2490sup1.cif

e-69-0o240-sup1.cif^{(22.5KB, cif)}

Click here for additional data file.^{(3.1KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813000718/bg2490Isup2.cdx

Click here for additional data file.^{(172.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000718/bg2490Isup3.hkl

e-69-0o240-Isup3.hkl^{(172.8KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000718/bg2490Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯O1ⁱ	0.91 (2)	1.85 (2)	2.7324 (17)	165 (2)
N4—H42⋯O12ⁱⁱ	0.89 (2)	2.40 (2)	3.0599 (18)	131.2 (16)
N4—H42⋯O11ⁱⁱ	0.89 (2)	2.60 (2)	3.3425 (17)	141.8 (16)
N4—H43⋯O1	0.96 (2)	1.81 (2)	2.7579 (16)	172.7 (18)
C13—H13⋯O21ⁱⁱⁱ	0.95	2.47	3.3152 (19)	148
C26—H26⋯O32	0.95	2.49	3.378 (2)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals.

supplementary crystallographic information

Comment

2,4,6-Trinitrophenol (picric acid) was and is primarily used to manufacture explosives. I has also found widespread use as an intermediate in the production of dyes. As a strong organic acid, picric acid forms salts with a large variety of N-containing organic bases. The crystal structures of some picrates have been reported (Jin et al., 2011; Wang, 2011; Betz et al., 2011; Dutkiewicz et al., 2011; Jasinski et al., 2011; Jasinski et al., 2010a; Jasinski et al., 2010b). In continuation of our studies of structural aspects of simple organic salts of amine bases, the title compound was synthesized.

Intracyclic C–C–C angles in the picrate anion markedly deviate from the ideal value by covering a range of 111.95 (12)–125.38 (13) ° where the smallest angle is found on the carbon atome bearing the deprotonated hydroxy group and the largest angle on one of the carbon atoms in ortho position to the former one. The cationic part demonstrates a relatively smaller distortion of its aromatic system in terms of intracyclic C–C–C angles, the latter ones found in between 118.25 (14) ° and 122.33 (13) °. The smallest angle in the cation appears on the unsubstituted carbon atom in between the protonated amine group and the chloro substituent while the largest angle is present on the carbon atom bearing the protonated amine group. The tilting of the nitro groups of the picrate anion with respect to the aromatic system they are bonded to varies significantly, the respective O–N–C–C dihedral angles being 13.5 (2) °, -25.4 (2) ° and 42.61 (19) °. The least-squares planes defined by the individual carbon atoms of both aromatic systems subtend an angle of 16.92 (7) ° (Fig. 1).

In the crystal, classical hydrogen bonds of the N–H···O type are observed, as well as C–H···O contacts whose range falls by more than 0.2 Å below the sum of van-der-Waals radii of the participating. atoms. The latter contacts are supported by carbon-bound hydrogen atoms on the cation as well as the anion and invariably have oxygen atoms on nitro groups as acceptors. Two of the nitrogen-bonded hydrogen atoms form hydrogen bonds to the oxygen atom of the deprotonated hydroxyl group while the third nitrogen-bonded hydrogen atom forms a hydrogen bond to a nitro group. The latter hydrogen bond shows bifurcation. Metrical parameters as well as information about the symmetry of these contacts are summarized in Table 1. In total, the N–H···O type hydrogen bonds connect the entities of the crystal structure to columnar arrays along the crystallographic a axis that are further connected to layers parallel ab by the C–H···O contacts. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the C–H···O contacts is DR²₂(10) on the unary level while the classical hydrogen bonds necessitate a DDDDD descriptor on the same level (Fig. 2).

The packing of the title compound in the crystal structure is shown in Figure 3.

Experimental

3-Chloro-4-fluoroaniline (1.45 g, 0.01 mol) and picric acid (2.29 g, 0.01 mol) were individually dissolved in water (60 mL). The solutions were mixed and HCl (5 M, 2 mL) was added under stirring in a few minutes. The product formed was filtered and dried. Yellow crystals of the title compound were obtained by slow evaporation of a solution of the compound in ethanol at room temperature.