4-Fluoro-N-methyl-N-nitro­aniline

Gajda, K.; Dziuk, B.; Daszkiewicz, Z.

doi:10.1107/S2414314616014462

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161446

doi:10.1107/S2414314616014462

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4-Fluoro-N-methyl-N-nitroaniline

Katarzyna Gajda,^a ^* Błażej Dziuk ^a and Zdzisław Daszkiewicz ^a

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: katarzyna.gajda@uni.opole.pl

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 8 September 2016; accepted 12 September 2016; online 16 September 2016)

Molecules of the title compound, C₇H₇FN₂O₂, are composed of a nitramine group which is twisted with the respect to the aromatic ring, with an N—N—C—C torsion angle of −117.38 (12)°. In the molecule, the N—N bond length [1.3510 (15) Å] indicates some double-bond character, while the angle between the aromatic ring and the nitramine group rules out further delocalization in the molecule. In the crystal, C—H⋯F hydrogen bonds connect the molecules into C¹₁(6) chains along the a axis. C—H⋯O hydrogen bonds form, which feature R²₂(12) loops and further connect these chains.

Keywords: nitramines; crystal structure; intermolecular bonds.

CCDC reference: 1504022

Structure description

Nitroamines find applications in rocket fuels and explosive devices (Williams, 1982 ). As a result of the unusual properties of the N—N bond, N-nitroamines are very active in photochemical reactions (Mialocq & Stephenson, 1986 ).

In the molecule (Fig. 1), the nitramine group is twisted with the respect to the aromatic ring, with an N1—N2—C1—C2 torsion angle of −117.38 (12)°. The N2—N3 bond length is notably shorter [1.3510 (15) Å] than a typical N—N single bond (1.42 Å; Allen, 2002 ), but longer than the distance characteristic for an N=N double bond (1.24 Å; Allen, 2002), indicating partial double-bond character. The geometry of the nitroamine group is normal, and corresponds well those in with similar compounds (Ejsmont et al., 1998 ; Zarychta et al., 2005a ,b , 2011 ).

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

In the crystal, weak C6—H6⋯F1 hydrogen bonds (Fig. 2 and Table 1) connect the molecules into C₁¹(6) chains along the a axis. C—H⋯O contacts further connect the molecules into chains featuring R₂²(12) loops.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯F1ⁱ	0.958 (15)	2.366 (15)	3.1730 (15)	141.7 (12)
C6—H6⋯O2ⁱⁱ	0.958 (15)	2.623 (15)	3.3298 (15)	131.0 (11)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+2, -y, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the a axis. The C—H⋯F hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

The title compound was obtained by a previously reported nitration reaction (Daszkiewicz et al., 1994 ). The crude product was crystallized from a mixture of diethyl ether with n-hexane (1:4) in 79% yield, m.p. 137–138°C.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₇FN₂O₂
M_r	170.15
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	13.1126 (5), 6.8916 (3), 16.1831 (6)
V (Å³)	1462.41 (10)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.05 × 0.05 × 0.04

Data collection
Diffractometer	Oxford Diffraction Xcalibur
No. of measured, independent and observed [I > 2σ(I)] reflections	9125, 1434, 1245
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.04
No. of reflections	1434
No. of parameters	138
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.16
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2014/7 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014/7 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1504022

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616014462/bt4026sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014462/bt4026Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014462/bt4026Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

4-Fluoro-N-methyl-N-nitroaniline top

Crystal data top

C₇H₇FN₂O₂	D_x = 1.546 Mg m⁻³
M_r = 170.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9125 reflections
a = 13.1126 (5) Å	θ = 3.0–26.0°
b = 6.8916 (3) Å	µ = 0.13 mm⁻¹
c = 16.1831 (6) Å	T = 100 K
V = 1462.41 (10) Å³	Plate, colourless
Z = 8	0.05 × 0.05 × 0.04 mm
F(000) = 704

Data collection top

Oxford Diffraction Xcalibur diffractometer	1245 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
ω scans	h = −16→16
9125 measured reflections	k = −8→5
1434 independent reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0481P)² + 0.3197P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.085	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.20 e Å⁻³
1434 reflections	Δρ_min = −0.16 e Å⁻³
138 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0142 (14)

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.

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

	x	y	z	U_iso*/U_eq
F1	0.62328 (5)	0.21268 (11)	0.47654 (5)	0.0324 (2)
O1	1.16296 (7)	0.15293 (15)	0.32855 (6)	0.0335 (3)
O2	1.03374 (7)	−0.03829 (12)	0.35186 (5)	0.0291 (3)
N1	1.01031 (8)	0.28024 (14)	0.34758 (7)	0.0255 (3)
N2	1.07221 (8)	0.12384 (15)	0.34329 (6)	0.0236 (3)
C1	0.90945 (9)	0.25393 (17)	0.38054 (8)	0.0218 (3)
C2	0.82638 (10)	0.28901 (17)	0.33025 (8)	0.0244 (3)
H2	0.8369 (11)	0.324 (2)	0.2744 (10)	0.028 (4)*
C3	0.72915 (10)	0.27567 (17)	0.36275 (9)	0.0244 (3)
H3	0.6743 (12)	0.302 (2)	0.3304 (9)	0.029 (4)*
C4	0.71891 (9)	0.22704 (17)	0.44471 (9)	0.0236 (3)
C5	0.80010 (10)	0.19109 (18)	0.49632 (8)	0.0242 (3)
H5	0.7867 (11)	0.156 (2)	0.5526 (10)	0.030 (4)*
C6	0.89695 (10)	0.20558 (17)	0.46345 (8)	0.0229 (3)
H6	0.9547 (11)	0.181 (2)	0.4981 (10)	0.029 (4)*
C7	1.05729 (12)	0.4711 (2)	0.34364 (9)	0.0294 (3)
H7A	1.0971 (13)	0.483 (2)	0.2957 (12)	0.050 (5)*
H7B	1.0990 (13)	0.491 (3)	0.3897 (12)	0.052 (5)*
H7C	1.0042 (15)	0.562 (3)	0.3432 (10)	0.050 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0206 (4)	0.0365 (5)	0.0401 (5)	0.0010 (3)	0.0042 (3)	0.0017 (3)
O1	0.0247 (5)	0.0407 (6)	0.0351 (6)	0.0014 (4)	0.0086 (4)	−0.0007 (4)
O2	0.0358 (5)	0.0203 (5)	0.0312 (5)	0.0008 (4)	0.0035 (4)	0.0002 (4)
N1	0.0264 (6)	0.0195 (5)	0.0306 (6)	−0.0001 (4)	0.0041 (5)	0.0009 (4)
N2	0.0272 (6)	0.0264 (6)	0.0173 (5)	0.0017 (5)	0.0015 (4)	−0.0011 (4)
C1	0.0237 (6)	0.0161 (5)	0.0256 (7)	−0.0006 (5)	0.0019 (5)	−0.0022 (5)
C2	0.0341 (8)	0.0173 (6)	0.0218 (7)	0.0013 (5)	−0.0019 (5)	0.0007 (5)
C3	0.0260 (7)	0.0184 (6)	0.0287 (7)	0.0021 (5)	−0.0071 (5)	−0.0008 (5)
C4	0.0219 (6)	0.0179 (6)	0.0311 (7)	0.0004 (5)	0.0021 (5)	−0.0036 (5)
C5	0.0281 (7)	0.0226 (6)	0.0219 (7)	−0.0006 (5)	0.0003 (5)	−0.0005 (5)
C6	0.0230 (7)	0.0216 (7)	0.0242 (7)	−0.0003 (5)	−0.0037 (5)	−0.0012 (5)
C7	0.0337 (8)	0.0240 (7)	0.0305 (8)	−0.0052 (6)	0.0047 (6)	0.0013 (5)

Geometric parameters (Å, º) top

F1—C4	1.3593 (14)	C3—C4	1.375 (2)
O1—N2	1.2301 (14)	C3—H3	0.908 (15)
O2—N2	1.2337 (14)	C4—C5	1.3756 (18)
N1—N2	1.3510 (15)	C5—C6	1.3805 (18)
N1—C1	1.4376 (16)	C5—H5	0.959 (15)
N1—C7	1.4537 (16)	C6—H6	0.958 (15)
C1—C2	1.3811 (18)	C7—H7A	0.939 (19)
C1—C6	1.3922 (18)	C7—H7B	0.935 (19)
C2—C3	1.3822 (19)	C7—H7C	0.938 (19)
C2—H2	0.944 (16)

N2—N1—C1	118.11 (10)	F1—C4—C3	118.26 (12)
N2—N1—C7	117.71 (11)	F1—C4—C5	118.09 (12)
C1—N1—C7	121.35 (10)	C3—C4—C5	123.65 (12)
O1—N2—O2	124.40 (11)	C4—C5—C6	117.71 (12)
O1—N2—N1	117.46 (10)	C4—C5—H5	118.7 (9)
O2—N2—N1	118.11 (10)	C6—C5—H5	123.5 (9)
C2—C1—C6	121.14 (12)	C5—C6—C1	119.79 (12)
C2—C1—N1	119.00 (11)	C5—C6—H6	119.2 (9)
C6—C1—N1	119.74 (11)	C1—C6—H6	121.0 (9)
C1—C2—C3	119.44 (12)	N1—C7—H7A	110.6 (10)
C1—C2—H2	119.5 (9)	N1—C7—H7B	110.1 (11)
C3—C2—H2	121.0 (9)	H7A—C7—H7B	108.8 (16)
C4—C3—C2	118.27 (12)	N1—C7—H7C	107.0 (11)
C4—C3—H3	121.8 (9)	H7A—C7—H7C	110.3 (14)
C2—C3—H3	119.9 (9)	H7B—C7—H7C	110.0 (15)

C1—N1—N2—O1	−167.89 (10)	N1—C1—C2—C3	−176.06 (11)
C7—N1—N2—O1	−6.67 (15)	C1—C2—C3—C4	−0.15 (18)
C1—N1—N2—O2	14.26 (15)	C2—C3—C4—F1	−179.58 (10)
C7—N1—N2—O2	175.47 (11)	C2—C3—C4—C5	0.09 (19)
N2—N1—C1—C2	−117.38 (12)	F1—C4—C5—C6	179.86 (10)
C7—N1—C1—C2	82.13 (15)	C3—C4—C5—C6	0.20 (18)
N2—N1—C1—C6	66.58 (15)	C4—C5—C6—C1	−0.42 (18)
C7—N1—C1—C6	−93.91 (15)	C2—C1—C6—C5	0.37 (18)
C6—C1—C2—C3	−0.08 (18)	N1—C1—C6—C5	176.33 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F1ⁱ	0.958 (15)	2.366 (15)	3.1730 (15)	141.7 (12)
C6—H6···O2ⁱⁱ	0.958 (15)	2.623 (15)	3.3298 (15)	131.0 (11)

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

References

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