3-Nitro-4-(propyl­amino)­benzonitrile

Liu, S.-L.; Jia, H.-S.

doi:10.1107/S1600536811045533

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3284

https://doi.org/10.1107/S1600536811045533

Open

access

3-Nitro-4-(propylamino)benzonitrile

Shang-Lian Liu ^a and Hong-Sheng Jia ^a ^*

^aDepartment of Biological and Chemical Engineering, Chien-shiung Institute of Technology, Taicang 215411, Suzhou, People's Republic of China
^*Correspondence e-mail: ntfenger@163.com

(Received 11 October 2011; accepted 30 October 2011; online 12 November 2011)

In the title compound, C₁₀H₁₁N₃O₂, the nitro group is essentially coplanar with the aromatic ring [dihedral angle = 1.3 (3)°] and forms an intramolecular amine–nitro N—H⋯O hydrogen bond. In the crystal, weak intermolecular aromatic C—H⋯O_nitro hydrogen bonds link the molecules. Weak aromatic ring π–π interactions [minimum ring centroid separation = 3.7744 (13) Å] are also present.

Related literature

For the synthesis of the title compound, see: Ates-Alagoz & Buyukbingol (2001 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₁N₃O₂
M_r = 205.22
Triclinic, $[P \overline 1]$
a = 7.6320 (15) Å
b = 7.9200 (16) Å
c = 9.2440 (18) Å
α = 109.30 (3)°
β = 91.28 (3)°
γ = 93.00 (3)°
V = 526.2 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 four-circle diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.982
2073 measured reflections
1918 independent reflections
1321 reflections with I > 2σ(I)
R_int = 0.017
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.165
S = 1.04
1918 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86	2.00	2.641 (2)	131
C9—H9A⋯O1ⁱ	0.93	2.42	3.331 (2)	165
Symmetry code: (i) x, y+1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1994 ); 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: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045533/zs2155sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045533/zs2155Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045533/zs2155Isup3.cml

checkCIF report

Comment top

We report herein the crystal structure of the title compound C₁₀H₁₁N₃O₂. In this molecule (Fig. 1), the bond lengths and angles (Allen et al., 1987) are within normal ranges. The nitro group is essentially coplanar with the aromatic ring forming a dihedral angle of 1.3 (3)° with the ring. The amine H atom forms an intramolecular hydrogen bond with a nitro O-acceptor (O2) (Table 1). In the crystal structure, a weak intermolecular aromatic C—H···O_nitro hydrogen bond links the molecules (Fig. 2) while also present are weak aromatic ring π–π interactions [minimum ring centroid separation, 3.7744 (13) Å].

Related literature top

For the synthesis of the title compound, see: Ates-Alagoz & Buyukbingol (2001). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was synthesized using the procedure of (Ates-Alagoz & Buyukbingol, 2001). 4-Chloro-3-nitrobenzonitrile (4.2 g, 0.023 mol) was refluxed in 25 ml of n-propylamine and 50 ml of tetrahydrofuran for 4 h. Then solvents were evaporated, water was added to give a precipitate which was collected by filtration and washed with cold ethanol (2 x 15 ml) to afford the yellow solid (4.2 g, 89%). The pure title compound was obtained by recrystallizing from ethanol, with crystals suitable for X-ray diffraction obtained by slow room-temperature evaporation of an ethanol solution.

Structure description top

For the synthesis of the title compound, see: Ates-Alagoz & Buyukbingol (2001). For standard bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell refinement: CAD-4 Software (Enraf–Nonius, 1994); 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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound, with intermolecular hydrogen bonds shown as dashed lines.

3-Nitro-4-(propylamino)benzonitrile top

Crystal data top

C₁₀H₁₁N₃O₂	Z = 2
M_r = 205.22	F(000) = 216
Triclinic, P1	D_x = 1.295 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6320 (15) Å	Cell parameters from 25 reflections
b = 7.9200 (16) Å	θ = 9–13°
c = 9.2440 (18) Å	µ = 0.09 mm⁻¹
α = 109.30 (3)°	T = 293 K
β = 91.28 (3)°	Block, yellow
γ = 93.00 (3)°	0.30 × 0.20 × 0.20 mm
V = 526.2 (2) Å³

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	1321 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.973, T_max = 0.982	l = −11→11
2073 measured reflections	3 standard reflections every 200 reflections
1918 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.10P)²0.002P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1918 reflections	Δρ_max = 0.18 e Å⁻³
137 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.22 (3)

Crystal data top

C₁₀H₁₁N₃O₂	γ = 93.00 (3)°
M_r = 205.22	V = 526.2 (2) Å³
Triclinic, P1	Z = 2
a = 7.6320 (15) Å	Mo Kα radiation
b = 7.9200 (16) Å	µ = 0.09 mm⁻¹
c = 9.2440 (18) Å	T = 293 K
α = 109.30 (3)°	0.30 × 0.20 × 0.20 mm
β = 91.28 (3)°

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	1321 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.017
T_min = 0.973, T_max = 0.982	3 standard reflections every 200 reflections
2073 measured reflections	intensity decay: 1%
1918 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
1918 reflections	Δρ_min = −0.17 e Å⁻³
137 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
N1	0.3192 (2)	0.1104 (2)	0.86877 (17)	0.0589 (5)
H1A	0.3558	0.0076	0.8175	0.071*
O1	0.2437 (2)	−0.30919 (19)	1.04167 (18)	0.0847 (6)
C1	0.4572 (4)	0.3339 (4)	0.5821 (3)	0.0877 (8)
H1B	0.5109	0.2853	0.4853	0.132*
H1C	0.5341	0.4277	0.6502	0.132*
H1D	0.3479	0.3816	0.5668	0.132*
O2	0.3393 (2)	−0.22529 (19)	0.85827 (19)	0.0779 (5)
N2	0.2712 (2)	−0.1930 (2)	0.98294 (19)	0.0586 (5)
C2	0.4237 (3)	0.1875 (3)	0.6512 (2)	0.0720 (7)
H2A	0.3477	0.0921	0.5811	0.086*
H2B	0.5342	0.1378	0.6641	0.086*
C3	0.3404 (3)	0.2542 (3)	0.8029 (2)	0.0631 (6)
H3A	0.4132	0.3533	0.8722	0.076*
H3B	0.2266	0.2975	0.7898	0.076*
N3	−0.0667 (3)	0.2255 (3)	1.5411 (2)	0.0880 (7)
C4	0.2472 (2)	0.1269 (2)	1.0023 (2)	0.0490 (5)
C5	0.2198 (2)	−0.0143 (2)	1.0637 (2)	0.0489 (5)
C6	0.1414 (2)	0.0104 (2)	1.2017 (2)	0.0539 (5)
H6A	0.1264	−0.0853	1.2384	0.065*
C7	0.0851 (3)	0.1755 (3)	1.2854 (2)	0.0547 (5)
C8	0.1124 (3)	0.3178 (3)	1.2288 (2)	0.0599 (6)
H8A	0.0770	0.4304	1.2853	0.072*
C9	0.1890 (3)	0.2953 (2)	1.0940 (2)	0.0581 (5)
H9A	0.2043	0.3931	1.0600	0.070*
C10	0.0000 (3)	0.2015 (3)	1.4274 (3)	0.0661 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0739 (11)	0.0428 (9)	0.0594 (10)	0.0047 (8)	0.0125 (8)	0.0154 (7)
O1	0.1188 (14)	0.0447 (8)	0.0985 (12)	0.0147 (8)	0.0172 (10)	0.0322 (8)
C1	0.105 (2)	0.0872 (17)	0.0765 (16)	−0.0142 (15)	0.0120 (14)	0.0368 (13)
O2	0.0994 (12)	0.0541 (9)	0.0783 (10)	0.0199 (8)	0.0273 (9)	0.0154 (7)
N2	0.0659 (11)	0.0401 (9)	0.0698 (11)	0.0078 (7)	0.0042 (8)	0.0175 (8)
C2	0.0830 (15)	0.0691 (14)	0.0656 (13)	0.0024 (12)	0.0124 (11)	0.0243 (11)
C3	0.0749 (14)	0.0539 (11)	0.0626 (13)	0.0001 (10)	0.0083 (10)	0.0222 (9)
N3	0.1119 (17)	0.0745 (13)	0.0812 (13)	0.0188 (12)	0.0356 (12)	0.0267 (10)
C4	0.0508 (11)	0.0416 (10)	0.0536 (11)	0.0000 (8)	0.0018 (8)	0.0149 (8)
C5	0.0497 (10)	0.0378 (10)	0.0575 (11)	0.0030 (8)	−0.0001 (8)	0.0136 (8)
C6	0.0583 (12)	0.0445 (10)	0.0620 (12)	−0.0004 (9)	0.0001 (9)	0.0226 (8)
C7	0.0566 (11)	0.0497 (11)	0.0566 (11)	0.0017 (9)	0.0055 (9)	0.0158 (8)
C8	0.0719 (13)	0.0414 (10)	0.0614 (12)	0.0063 (9)	0.0092 (10)	0.0098 (8)
C9	0.0702 (13)	0.0380 (10)	0.0669 (12)	0.0009 (9)	0.0059 (10)	0.0186 (9)
C10	0.0762 (14)	0.0556 (12)	0.0660 (14)	0.0056 (11)	0.0113 (11)	0.0186 (10)

Geometric parameters (Å, º) top

N1—C4	1.332 (2)	C3—H3A	0.9700
N1—C3	1.463 (2)	C3—H3B	0.9700
N1—H1A	0.8600	N3—C10	1.141 (2)
O1—N2	1.225 (2)	C4—C5	1.419 (2)
C1—C2	1.511 (3)	C4—C9	1.424 (3)
C1—H1B	0.9600	C5—C6	1.381 (2)
C1—H1C	0.9600	C6—C7	1.378 (3)
C1—H1D	0.9600	C6—H6A	0.9300
O2—N2	1.229 (2)	C7—C8	1.399 (3)
N2—C5	1.445 (2)	C7—C10	1.436 (3)
C2—C3	1.495 (3)	C8—C9	1.350 (3)
C2—H2A	0.9700	C8—H8A	0.9300
C2—H2B	0.9700	C9—H9A	0.9300

C4—N1—C3	124.78 (15)	C2—C3—H3B	109.6
C4—N1—H1A	117.6	H3A—C3—H3B	108.1
C3—N1—H1A	117.6	N1—C4—C5	124.93 (16)
C2—C1—H1B	109.5	N1—C4—C9	119.98 (16)
C2—C1—H1C	109.5	C5—C4—C9	115.09 (16)
H1B—C1—H1C	109.5	C6—C5—C4	122.25 (15)
C2—C1—H1D	109.5	C6—C5—N2	116.43 (15)
H1B—C1—H1D	109.5	C4—C5—N2	121.32 (16)
H1C—C1—H1D	109.5	C7—C6—C5	120.56 (16)
O1—N2—O2	121.83 (16)	C7—C6—H6A	119.7
O1—N2—C5	118.22 (16)	C5—C6—H6A	119.7
O2—N2—C5	119.95 (15)	C6—C7—C8	118.46 (17)
C3—C2—C1	112.3 (2)	C6—C7—C10	120.97 (17)
C3—C2—H2A	109.1	C8—C7—C10	120.57 (17)
C1—C2—H2A	109.1	C9—C8—C7	121.52 (17)
C3—C2—H2B	109.1	C9—C8—H8A	119.2
C1—C2—H2B	109.1	C7—C8—H8A	119.2
H2A—C2—H2B	107.9	C8—C9—C4	122.11 (17)
N1—C3—C2	110.26 (17)	C8—C9—H9A	118.9
N1—C3—H3A	109.6	C4—C9—H9A	118.9
C2—C3—H3A	109.6	N3—C10—C7	178.7 (2)
N1—C3—H3B	109.6

C4—N1—C3—C2	−179.22 (17)	O2—N2—C5—C4	−0.4 (3)
C1—C2—C3—N1	−177.02 (18)	C4—C5—C6—C7	0.4 (3)
C3—N1—C4—C5	177.27 (18)	N2—C5—C6—C7	−178.84 (17)
C3—N1—C4—C9	−1.8 (3)	C5—C6—C7—C8	−1.2 (3)
N1—C4—C5—C6	−178.73 (16)	C5—C6—C7—C10	178.64 (17)
C9—C4—C5—C6	0.4 (3)	C6—C7—C8—C9	1.2 (3)
N1—C4—C5—N2	0.5 (3)	C10—C7—C8—C9	−178.65 (18)
C9—C4—C5—N2	179.62 (16)	C7—C8—C9—C4	−0.4 (3)
O1—N2—C5—C6	−0.5 (3)	N1—C4—C9—C8	178.75 (17)
O2—N2—C5—C6	178.87 (16)	C5—C4—C9—C8	−0.4 (3)
O1—N2—C5—C4	−179.81 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.00	2.641 (2)	131
N1—H1A···N2	0.86	2.61	2.937 (2)	104
C6—H6A···O1	0.93	2.32	2.644 (2)	100
C9—H9A···O1ⁱ	0.93	2.42	3.331 (2)	165

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁N₃O₂
M_r	205.22
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.6320 (15), 7.9200 (16), 9.2440 (18)
α, β, γ (°)	109.30 (3), 91.28 (3), 93.00 (3)
V (Å³)	526.2 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 four-circle
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	2073, 1918, 1321
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.165, 1.04
No. of reflections	1918
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: CAD-4 Software (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	2.00	2.641 (2)	131
C9—H9A···O1ⁱ	0.93	2.42	3.331 (2)	165

Symmetry code: (i) x, y+1, z.

Acknowledgements

The authors thank Liu Bo Nian from Nanjing University of Technology for useful discussions and the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19 CrossRef Google Scholar
Ates-Alagoz, Z. & Buyukbingol, E. (2001). Heterocycl. Commun. 7, 455–460. CAS Google Scholar
Enraf–Nonius (1994). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar