2-Ethyl-5-nitro­aniline

Chen, Y.; Fang, Z.; Wei, P.

doi:10.1107/S1600536809009878

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o827

doi:10.1107/S1600536809009878

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2-Ethyl-5-nitroaniline

Yan Chen,^a Zheng Fang ^a ^* and Ping Wei ^a

^aCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fzcpu@163.com

(Received 16 March 2009; accepted 17 March 2009; online 25 March 2009)

The molecule of the title compound, C₈H₁₀N₂O₂, is nearly planar [maximum deviation of 0.163 (3) Å for one of the O atoms of the NO₂ group]. In the crystal structure, weak intermolecular N—H⋯N and C—H⋯O hydrogen bonds link the molecules into chains, forming R₂²(10) ring motifs.

Related literature

For a related structure, see: Corwin (1955 ). For bond-length data, see: Allen et al. (1987 ). For ring motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₁₀N₂O₂
M_r = 166.18
Monoclinic, C 2/c
a = 23.037 (5) Å
b = 3.9540 (8) Å
c = 18.393 (4) Å
β = 104.51 (3)°
V = 1621.9 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.980, T_max = 0.990
2937 measured reflections
1474 independent reflections
906 reflections with I > 2σ(I)
R_int = 0.056
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.153
S = 1.01
1474 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N2ⁱ	0.86	2.62	3.423 (3)	156
C7—H7A⋯O1ⁱⁱ	0.93	2.60	3.417 (4)	147
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009878/hk2644sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009878/hk2644Isup2.hkl

checkCIF report

Comment top

Some derivatives of aniline are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C3-C8) is, of course, planar. Atoms C1, C2, N1, N2, O1 and O2 are -0.067 (3), -0.028 (2), -0.035 (3), -0.055 (3), 0.054 (3) and -0.163 (3) Å away from the ring plane of A, respectively.

In the crystal structure, weak intermolecular N-H···N and C-H···O hydrogen bonds (Table 1) link the molecules into chains, forming R₂²(10) ring motifs (Fig. 2) (Bernstein et al., 1995). in which they may be effective in the stabilization of the structure.

Related literature top

For a related structure, see: Corwin (1955). For bond-length data, see: Allen et al. (1987). For ring motifs, see: Bernstein et al. (1995).

Experimental top

For the preparation of the title compound, 2-ethylaniline (12.1 g) was dissolved in concentrated sulfuric acid (50 ml). The mixture was cooled to 273 K, and nitric acid (6.37 ml) was added in small portions. The mixture was stirred at 295 K for 0.5 h. Then, it was poured into a large volume of ice, used natrium hydroxydatum to neutralize excess acid, filtered, and dried. The compound was crystallized from cyclohexane (Corwin, 1955). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Ethyl-5-nitroaniline top

Crystal data top

C₈H₁₀N₂O₂	F(000) = 704
M_r = 166.18	D_x = 1.361 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 23.037 (5) Å	θ = 10–13°
b = 3.9540 (8) Å	µ = 0.10 mm⁻¹
c = 18.393 (4) Å	T = 298 K
β = 104.51 (3)°	Block, colorless
V = 1621.9 (6) Å³	0.20 × 0.10 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 25.3°, θ_min = 1.8°
ω/2θ scans	h = −27→27
Absorption correction: ψ scan (North et al., 1968)	k = 0→4
T_min = 0.980, T_max = 0.990	l = −22→22
2937 measured reflections	3 standard reflections every 120 min
1474 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)² + P] where P = (F_o² + 2F_c²)/3
1474 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₁₀N₂O₂	V = 1621.9 (6) Å³
M_r = 166.18	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.037 (5) Å	µ = 0.10 mm⁻¹
b = 3.9540 (8) Å	T = 298 K
c = 18.393 (4) Å	0.20 × 0.10 × 0.10 mm
β = 104.51 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	906 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.056
T_min = 0.980, T_max = 0.990	3 standard reflections every 120 min
2937 measured reflections	intensity decay: 1%
1474 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.01	Δρ_max = 0.23 e Å⁻³
1474 reflections	Δρ_min = −0.21 e Å⁻³
109 parameters

Special details top

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
O1	0.18034 (10)	0.6924 (7)	−0.09151 (11)	0.0931 (9)
O2	0.08462 (10)	0.6656 (7)	−0.12713 (11)	0.0921 (8)
N1	0.13189 (12)	0.6134 (7)	−0.08113 (12)	0.0598 (6)
N2	0.23320 (8)	0.2602 (7)	0.17155 (11)	0.0643 (8)
H2A	0.2663	0.3390	0.1651	0.077*
H2B	0.2322	0.1704	0.2138	0.077*
C1	0.06424 (11)	−0.1027 (8)	0.20919 (14)	0.0592 (8)
H1A	0.0687	−0.1949	0.2586	0.089*
H1B	0.0479	−0.2721	0.1723	0.089*
H1C	0.0377	0.0881	0.2025	0.089*
C2	0.12500 (10)	0.0091 (7)	0.19996 (12)	0.0489 (7)
H2C	0.1413	0.1738	0.2388	0.059*
H2D	0.1515	−0.1852	0.2087	0.059*
C3	0.12627 (10)	0.1609 (6)	0.12529 (12)	0.0406 (6)
C4	0.07514 (10)	0.1952 (7)	0.06693 (13)	0.0458 (6)
H4A	0.0388	0.1174	0.0738	0.055*
C5	0.07620 (11)	0.3397 (7)	−0.00061 (13)	0.0479 (7)
H5A	0.0413	0.3608	−0.0389	0.058*
C6	0.13008 (10)	0.4519 (7)	−0.01007 (12)	0.0445 (6)
C7	0.18252 (10)	0.4228 (7)	0.04537 (13)	0.0476 (7)
H7A	0.2185	0.4993	0.0372	0.057*
C8	0.18102 (10)	0.2780 (7)	0.11353 (12)	0.0442 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0812 (15)	0.132 (2)	0.0759 (14)	−0.0154 (16)	0.0390 (12)	0.0189 (15)
O2	0.0889 (15)	0.121 (2)	0.0588 (12)	−0.0001 (15)	0.0045 (11)	0.0277 (14)
N1	0.0728 (16)	0.0621 (16)	0.0473 (12)	−0.0051 (14)	0.0201 (12)	−0.0025 (12)
N2	0.0382 (11)	0.101 (2)	0.0502 (12)	−0.0073 (13)	0.0052 (9)	−0.0046 (14)
C1	0.0702 (18)	0.0533 (18)	0.0597 (16)	−0.0030 (15)	0.0266 (13)	0.0046 (14)
C2	0.0550 (15)	0.0431 (16)	0.0493 (14)	0.0009 (12)	0.0142 (12)	−0.0057 (12)
C3	0.0433 (13)	0.0346 (14)	0.0441 (13)	0.0014 (11)	0.0115 (10)	−0.0080 (11)
C4	0.0402 (13)	0.0443 (16)	0.0529 (14)	−0.0059 (12)	0.0117 (11)	−0.0044 (13)
C5	0.0455 (14)	0.0474 (16)	0.0471 (14)	−0.0007 (13)	0.0044 (11)	−0.0016 (13)
C6	0.0526 (14)	0.0411 (15)	0.0415 (13)	0.0020 (12)	0.0148 (11)	−0.0082 (12)
C7	0.0438 (13)	0.0515 (17)	0.0519 (14)	−0.0063 (13)	0.0202 (11)	−0.0094 (13)
C8	0.0394 (13)	0.0479 (16)	0.0448 (13)	0.0022 (12)	0.0097 (10)	−0.0105 (12)

Geometric parameters (Å, º) top

O1—N1	1.219 (3)	C2—H2C	0.9700
O2—N1	1.218 (3)	C2—H2D	0.9700
N1—C6	1.465 (3)	C3—C4	1.387 (3)
N2—C8	1.395 (3)	C3—C8	1.410 (3)
N2—H2A	0.8600	C4—C5	1.373 (3)
N2—H2B	0.8600	C4—H4A	0.9300
C1—C2	1.517 (3)	C5—C6	1.370 (3)
C1—H1A	0.9600	C5—H5A	0.9300
C1—H1B	0.9600	C6—C7	1.377 (3)
C1—H1C	0.9600	C7—C8	1.387 (3)
C2—C3	1.506 (3)	C7—H7A	0.9300

O2—N1—O1	122.8 (2)	C4—C3—C8	117.9 (2)
O2—N1—C6	118.3 (2)	C4—C3—C2	122.5 (2)
O1—N1—C6	118.9 (2)	C8—C3—C2	119.56 (19)
C8—N2—H2A	120.0	C5—C4—C3	122.5 (2)
C8—N2—H2B	120.0	C5—C4—H4A	118.8
H2A—N2—H2B	120.0	C3—C4—H4A	118.8
C2—C1—H1A	109.5	C6—C5—C4	118.2 (2)
C2—C1—H1B	109.5	C6—C5—H5A	120.9
H1A—C1—H1B	109.5	C4—C5—H5A	120.9
C2—C1—H1C	109.5	C5—C6—C7	122.3 (2)
H1A—C1—H1C	109.5	C5—C6—N1	118.9 (2)
H1B—C1—H1C	109.5	C7—C6—N1	118.8 (2)
C3—C2—C1	116.59 (19)	C6—C7—C8	119.2 (2)
C3—C2—H2C	108.1	C6—C7—H7A	120.4
C1—C2—H2C	108.1	C8—C7—H7A	120.4
C3—C2—H2D	108.1	C7—C8—N2	120.0 (2)
C1—C2—H2D	108.1	C7—C8—C3	120.0 (2)
H2C—C2—H2D	107.3	N2—C8—C3	119.9 (2)

C1—C2—C3—C4	−0.7 (4)	O1—N1—C6—C7	5.9 (4)
C1—C2—C3—C8	178.4 (2)	C5—C6—C7—C8	−0.6 (4)
C8—C3—C4—C5	−0.5 (4)	N1—C6—C7—C8	178.4 (2)
C2—C3—C4—C5	178.7 (3)	C6—C7—C8—N2	−177.1 (2)
C3—C4—C5—C6	0.3 (4)	C6—C7—C8—C3	0.4 (4)
C4—C5—C6—C7	0.3 (4)	C4—C3—C8—C7	0.1 (3)
C4—C5—C6—N1	−178.7 (2)	C2—C3—C8—C7	−179.0 (2)
O2—N1—C6—C5	5.6 (4)	C4—C3—C8—N2	177.6 (2)
O1—N1—C6—C5	−175.1 (3)	C2—C3—C8—N2	−1.5 (4)
O2—N1—C6—C7	−173.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N2ⁱ	0.86	2.62	3.423 (3)	156
C7—H7A···O1ⁱⁱ	0.93	2.60	3.417 (4)	147

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O₂
M_r	166.18
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	23.037 (5), 3.9540 (8), 18.393 (4)
β (°)	104.51 (3)
V (Å³)	1621.9 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.980, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2937, 1474, 906
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.153, 1.01
No. of reflections	1474
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N2ⁱ	0.86	2.62	3.423 (3)	156
C7—H7A···O1ⁱⁱ	0.93	2.60	3.417 (4)	147

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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