4-Isopropyl­amino-3-nitro­benzonitrile

Jia, H.

doi:10.1107/S1600536811051737

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o183

doi:10.1107/S1600536811051737

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4-Isopropylamino-3-nitrobenzonitrile

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 20 November 2011; accepted 1 December 2011; online 21 December 2011)

In the title compound, C₁₀H₁₁N₃O₂, the nitro group is essentially coplanar with the aromatic ring [dihedral angle = 3.4 (3)°] and forms an intramolecular N—H⋯O hydrogen bond with the amine group. In the crystal, weak aromatic C—H⋯O and C—H⋯N hydrogen bonds link the molecules. Weak aromatic ring π–π interactions [minimum ring centroid–centroid separation = 3.9841 (16) Å] are also present.

Related literature

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

Experimental

Crystal data

C₁₀H₁₁N₃O₂
M_r = 205.22
Monoclinic, P 2₁ /n
a = 6.6640 (13) Å
b = 20.678 (4) Å
c = 7.8900 (16) Å
β = 105.74 (3)°
V = 1046.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 four-circle diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.982, T_max = 0.991
2821 measured reflections
1926 independent reflections
1228 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.170
S = 1.00
1926 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.20 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
N3—H3A⋯O2	0.86	1.99	2.643 (2)	132
C1—H1A⋯N1ⁱ	0.93	2.61	3.469 (3)	153
C4—H4A⋯O1ⁱⁱ	0.93	2.40	3.298 (3)	163
C5—H5A⋯N1ⁱⁱⁱ	0.93	2.60	3.529 (4)	175
Symmetry codes: (i) -x, -y, -z; (ii) x, y, z+1; (iii) -x, -y, -z+1.

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: 10.1107/S1600536811051737/zs2168sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051737/zs2168Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051737/zs2168Isup3.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 3.4 (3)° with the ring. The amine H atom forms an intramolecular hydrogen bond with a nitro O-atom acceptor (O2) (Table 1). In the crystal structure, intermolecular aromatic C—H···O and C—H···N hydrogen bonds link the molecules (Fig. 2) while also present are weak aromatic ring π–π interactions [minimum ring centroid separation, 3.9841 (16) Å].

Related literature top

For the synthesis of the title compound, see: Ates-Alagoz & Buyukbingol (2001). For bond-length data, 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 t-propylamine and 50 ml of tetrahydrofuran for 4 h. The solvent was then evaporated and water was added to give a precipitate which was collected by filtration and washed with cold ethanol (2 × 15 ml) to afford the yellow solid (4.2 g, 89%). The pure title compound was obtained by crystallizing from ethanol, with crystals suitable for X-ray diffraction obtained by slow room-temperature evaporation of an ethanol solution.

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.

4-Isopropylamino-3-nitrobenzonitrile top

Crystal data top

C₁₀H₁₁N₃O₂	F(000) = 432
M_r = 205.22	D_x = 1.303 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 6.6640 (13) Å	θ = 9–13°
b = 20.678 (4) Å	µ = 0.09 mm⁻¹
c = 7.8900 (16) Å	T = 293 K
β = 105.74 (3)°	Block, yellow
V = 1046.5 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	1228 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 25.4°, θ_min = 2.0°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = −6→24
T_min = 0.982, T_max = 0.991	l = −9→9
2821 measured reflections	3 standard reflections every 200 reflections
1926 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)] = 0.050	H-atom parameters constrained
wR(F²) = 0.170	w = 1/[σ²(F_o²) + (0.10P)² + 0.040P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1926 reflections	Δρ_max = 0.20 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: 0.038 (8)

Crystal data top

C₁₀H₁₁N₃O₂	V = 1046.5 (4) Å³
M_r = 205.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.6640 (13) Å	µ = 0.09 mm⁻¹
b = 20.678 (4) Å	T = 293 K
c = 7.8900 (16) Å	0.20 × 0.10 × 0.10 mm
β = 105.74 (3)°

Data collection top

Enraf–Nonius CAD-4 four-circle diffractometer	1228 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.020
T_min = 0.982, T_max = 0.991	3 standard reflections every 200 reflections
2821 measured reflections	intensity decay: 1%
1926 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.170	H-atom parameters constrained
S = 1.00	Δρ_max = 0.20 e Å⁻³
1926 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
C1	0.3856 (4)	0.06884 (12)	0.1995 (3)	0.0484 (6)
H1A	0.3429	0.0582	0.0805	0.058*
O1	0.6054 (3)	0.10761 (14)	−0.0153 (2)	0.1029 (10)
N1	−0.0699 (4)	−0.01652 (13)	0.2024 (3)	0.0764 (8)
O2	0.8456 (3)	0.15107 (10)	0.1884 (2)	0.0683 (6)
N2	0.6789 (3)	0.12211 (12)	0.1391 (2)	0.0578 (6)
C2	0.5671 (3)	0.10375 (11)	0.2650 (3)	0.0440 (6)
N3	0.8123 (3)	0.15551 (10)	0.5144 (2)	0.0526 (6)
H3A	0.8880	0.1652	0.4454	0.063*
C3	0.6395 (3)	0.12144 (11)	0.4461 (3)	0.0427 (6)
C4	0.5119 (4)	0.10035 (12)	0.5527 (3)	0.0505 (7)
H4A	0.5516	0.1107	0.6719	0.061*
C5	0.3355 (4)	0.06600 (12)	0.4889 (3)	0.0532 (7)
H5A	0.2576	0.0529	0.5644	0.064*
C6	0.2680 (3)	0.04974 (12)	0.3092 (3)	0.0490 (6)
C7	0.0803 (4)	0.01312 (14)	0.2466 (3)	0.0582 (7)
C8	0.8847 (4)	0.17789 (13)	0.6982 (3)	0.0544 (7)
H8A	0.8699	0.1422	0.7757	0.065*
C9	1.1128 (5)	0.19404 (18)	0.7342 (4)	0.0861 (10)
H9A	1.1873	0.1568	0.7113	0.129*
H9B	1.1666	0.2067	0.8551	0.129*
H9C	1.1300	0.2289	0.6591	0.129*
C10	0.7585 (5)	0.23444 (15)	0.7327 (4)	0.0748 (9)
H10A	0.6149	0.2219	0.7096	0.112*
H10B	0.7704	0.2697	0.6570	0.112*
H10C	0.8098	0.2476	0.8533	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0550 (14)	0.0553 (15)	0.0343 (11)	0.0006 (12)	0.0111 (10)	0.0007 (10)
O1	0.1008 (16)	0.178 (3)	0.0316 (10)	−0.0490 (16)	0.0207 (10)	−0.0053 (13)
N1	0.0729 (16)	0.0899 (19)	0.0677 (15)	−0.0259 (15)	0.0211 (12)	−0.0044 (14)
O2	0.0723 (13)	0.0866 (14)	0.0533 (10)	−0.0266 (11)	0.0294 (9)	−0.0077 (10)
N2	0.0632 (14)	0.0774 (16)	0.0359 (11)	−0.0117 (12)	0.0185 (9)	0.0019 (10)
C2	0.0502 (13)	0.0511 (14)	0.0323 (11)	−0.0016 (11)	0.0137 (9)	0.0039 (10)
N3	0.0573 (12)	0.0644 (13)	0.0384 (10)	−0.0135 (11)	0.0168 (9)	−0.0083 (9)
C3	0.0488 (13)	0.0452 (13)	0.0349 (11)	0.0013 (11)	0.0128 (10)	0.0009 (10)
C4	0.0603 (15)	0.0625 (16)	0.0313 (11)	−0.0063 (13)	0.0167 (10)	−0.0043 (11)
C5	0.0613 (16)	0.0611 (16)	0.0434 (13)	−0.0030 (13)	0.0245 (11)	0.0034 (11)
C6	0.0484 (14)	0.0523 (15)	0.0464 (13)	−0.0027 (12)	0.0133 (11)	0.0008 (11)
C7	0.0610 (16)	0.0653 (17)	0.0497 (14)	−0.0064 (15)	0.0174 (12)	0.0020 (13)
C8	0.0634 (16)	0.0613 (16)	0.0371 (12)	−0.0052 (13)	0.0112 (11)	−0.0126 (11)
C9	0.073 (2)	0.109 (3)	0.074 (2)	−0.0228 (19)	0.0156 (16)	−0.0385 (19)
C10	0.090 (2)	0.072 (2)	0.0614 (16)	0.0019 (17)	0.0199 (15)	−0.0147 (15)

Geometric parameters (Å, º) top

C1—C6	1.374 (3)	C4—H4A	0.9300
C1—C2	1.383 (3)	C5—C6	1.407 (3)
C1—H1A	0.9300	C5—H5A	0.9300
O1—N2	1.221 (2)	C6—C7	1.430 (4)
N1—C7	1.144 (3)	C8—C9	1.506 (4)
O2—N2	1.229 (3)	C8—C10	1.507 (4)
N2—C2	1.445 (3)	C8—H8A	0.9800
C2—C3	1.426 (3)	C9—H9A	0.9600
N3—C3	1.333 (3)	C9—H9B	0.9600
N3—C8	1.473 (3)	C9—H9C	0.9600
N3—H3A	0.8600	C10—H10A	0.9600
C3—C4	1.417 (3)	C10—H10B	0.9600
C4—C5	1.349 (3)	C10—H10C	0.9600

C6—C1—C2	120.3 (2)	C1—C6—C7	122.0 (2)
C6—C1—H1A	119.8	C5—C6—C7	119.0 (2)
C2—C1—H1A	119.8	N1—C7—C6	177.7 (3)
O1—N2—O2	121.3 (2)	N3—C8—C9	107.4 (2)
O1—N2—C2	118.7 (2)	N3—C8—C10	111.8 (2)
O2—N2—C2	120.05 (18)	C9—C8—C10	112.2 (2)
C1—C2—C3	122.2 (2)	N3—C8—H8A	108.4
C1—C2—N2	116.20 (19)	C9—C8—H8A	108.4
C3—C2—N2	121.6 (2)	C10—C8—H8A	108.4
C3—N3—C8	125.47 (19)	C8—C9—H9A	109.5
C3—N3—H3A	117.3	C8—C9—H9B	109.5
C8—N3—H3A	117.3	H9A—C9—H9B	109.5
N3—C3—C4	120.94 (19)	C8—C9—H9C	109.5
N3—C3—C2	124.1 (2)	H9A—C9—H9C	109.5
C4—C3—C2	114.9 (2)	H9B—C9—H9C	109.5
C5—C4—C3	122.9 (2)	C8—C10—H10A	109.5
C5—C4—H4A	118.6	C8—C10—H10B	109.5
C3—C4—H4A	118.6	H10A—C10—H10B	109.5
C4—C5—C6	120.7 (2)	C8—C10—H10C	109.5
C4—C5—H5A	119.7	H10A—C10—H10C	109.5
C6—C5—H5A	119.7	H10B—C10—H10C	109.5
C1—C6—C5	119.0 (2)

C6—C1—C2—C3	−0.2 (4)	N2—C2—C3—C4	179.5 (2)
C6—C1—C2—N2	−179.4 (2)	N3—C3—C4—C5	179.8 (2)
O1—N2—C2—C1	1.9 (4)	C2—C3—C4—C5	0.1 (4)
O2—N2—C2—C1	−177.3 (2)	C3—C4—C5—C6	−0.6 (4)
O1—N2—C2—C3	−177.4 (3)	C2—C1—C6—C5	−0.3 (4)
O2—N2—C2—C3	3.5 (4)	C2—C1—C6—C7	−179.4 (2)
C8—N3—C3—C4	−3.4 (4)	C4—C5—C6—C1	0.6 (4)
C8—N3—C3—C2	176.1 (2)	C4—C5—C6—C7	179.8 (2)
C1—C2—C3—N3	−179.4 (2)	C3—N3—C8—C9	161.5 (3)
N2—C2—C3—N3	−0.1 (4)	C3—N3—C8—C10	−75.0 (3)
C1—C2—C3—C4	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2	0.86	1.99	2.643 (2)	132
C1—H1A···N1ⁱ	0.93	2.61	3.469 (3)	153
C4—H4A···O1ⁱⁱ	0.93	2.40	3.298 (3)	163
C5—H5A···N1ⁱⁱⁱ	0.93	2.60	3.529 (4)	175

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁N₃O₂
M_r	205.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.6640 (13), 20.678 (4), 7.8900 (16)
β (°)	105.74 (3)
V (Å³)	1046.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 four-circle diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2821, 1926, 1228
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.170, 1.00
No. of reflections	1926
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2	0.8600	1.9900	2.643 (2)	132.00
C1—H1A···N1ⁱ	0.9300	2.6100	3.469 (3)	153.00
C4—H4A···O1ⁱⁱ	0.9300	2.4000	3.298 (3)	163.00
C5—H5A···N1ⁱⁱⁱ	0.9300	2.6000	3.529 (4)	175.00

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

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

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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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