organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-Iso­propyl­amino-3-nitro­benzo­nitrile

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 ππ 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[Ates-Alagoz, Z. & Buyukbingol, E. (2001). Heterocycl. Commun. 7, 455-460.]). For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C10H11N3O2

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.982, Tmax = 0.991

  • 2821 measured reflections

  • 1926 independent reflections

  • 1228 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.17 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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)[Enraf-Nonius (1994). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]; cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 ππ 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.

Refinement top

Hydrogen atoms were positioned geometrically, with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) or 0.96 Å (methyl) and N—H = 0.86 Å, an were allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(N, aromatic or methylene C) or 1.5Ueq(methyl C).

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
[Figure 1] Fig. 1. The molecular structure of the title compound showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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
C10H11N3O2F(000) = 432
Mr = 205.22Dx = 1.303 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 6.6640 (13) Åθ = 9–13°
b = 20.678 (4) ŵ = 0.09 mm1
c = 7.8900 (16) ÅT = 293 K
β = 105.74 (3)°Block, yellow
V = 1046.5 (4) Å30.20 × 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 tubeRint = 0.020
Graphite monochromatorθmax = 25.4°, θmin = 2.0°
ω/2θ scansh = 08
Absorption correction: ψ scan
(North et al., 1968)
k = 624
Tmin = 0.982, Tmax = 0.991l = 99
2821 measured reflections3 standard reflections every 200 reflections
1926 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.170 w = 1/[σ2(Fo2) + (0.10P)2 + 0.040P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1926 reflectionsΔρmax = 0.20 e Å3
137 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.038 (8)
Crystal data top
C10H11N3O2V = 1046.5 (4) Å3
Mr = 205.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.6640 (13) ŵ = 0.09 mm1
b = 20.678 (4) ÅT = 293 K
c = 7.8900 (16) Å0.20 × 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)
Rint = 0.020
Tmin = 0.982, Tmax = 0.9913 standard reflections every 200 reflections
2821 measured reflections intensity decay: 1%
1926 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.00Δρmax = 0.20 e Å3
1926 reflectionsΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
C10.3856 (4)0.06884 (12)0.1995 (3)0.0484 (6)
H1A0.34290.05820.08050.058*
O10.6054 (3)0.10761 (14)0.0153 (2)0.1029 (10)
N10.0699 (4)0.01652 (13)0.2024 (3)0.0764 (8)
O20.8456 (3)0.15107 (10)0.1884 (2)0.0683 (6)
N20.6789 (3)0.12211 (12)0.1391 (2)0.0578 (6)
C20.5671 (3)0.10375 (11)0.2650 (3)0.0440 (6)
N30.8123 (3)0.15551 (10)0.5144 (2)0.0526 (6)
H3A0.88800.16520.44540.063*
C30.6395 (3)0.12144 (11)0.4461 (3)0.0427 (6)
C40.5119 (4)0.10035 (12)0.5527 (3)0.0505 (7)
H4A0.55160.11070.67190.061*
C50.3355 (4)0.06600 (12)0.4889 (3)0.0532 (7)
H5A0.25760.05290.56440.064*
C60.2680 (3)0.04974 (12)0.3092 (3)0.0490 (6)
C70.0803 (4)0.01312 (14)0.2466 (3)0.0582 (7)
C80.8847 (4)0.17789 (13)0.6982 (3)0.0544 (7)
H8A0.86990.14220.77570.065*
C91.1128 (5)0.19404 (18)0.7342 (4)0.0861 (10)
H9A1.18730.15680.71130.129*
H9B1.16660.20670.85510.129*
H9C1.13000.22890.65910.129*
C100.7585 (5)0.23444 (15)0.7327 (4)0.0748 (9)
H10A0.61490.22190.70960.112*
H10B0.77040.26970.65700.112*
H10C0.80980.24760.85330.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0550 (14)0.0553 (15)0.0343 (11)0.0006 (12)0.0111 (10)0.0007 (10)
O10.1008 (16)0.178 (3)0.0316 (10)0.0490 (16)0.0207 (10)0.0053 (13)
N10.0729 (16)0.0899 (19)0.0677 (15)0.0259 (15)0.0211 (12)0.0044 (14)
O20.0723 (13)0.0866 (14)0.0533 (10)0.0266 (11)0.0294 (9)0.0077 (10)
N20.0632 (14)0.0774 (16)0.0359 (11)0.0117 (12)0.0185 (9)0.0019 (10)
C20.0502 (13)0.0511 (14)0.0323 (11)0.0016 (11)0.0137 (9)0.0039 (10)
N30.0573 (12)0.0644 (13)0.0384 (10)0.0135 (11)0.0168 (9)0.0083 (9)
C30.0488 (13)0.0452 (13)0.0349 (11)0.0013 (11)0.0128 (10)0.0009 (10)
C40.0603 (15)0.0625 (16)0.0313 (11)0.0063 (13)0.0167 (10)0.0043 (11)
C50.0613 (16)0.0611 (16)0.0434 (13)0.0030 (13)0.0245 (11)0.0034 (11)
C60.0484 (14)0.0523 (15)0.0464 (13)0.0027 (12)0.0133 (11)0.0008 (11)
C70.0610 (16)0.0653 (17)0.0497 (14)0.0064 (15)0.0174 (12)0.0020 (13)
C80.0634 (16)0.0613 (16)0.0371 (12)0.0052 (13)0.0112 (11)0.0126 (11)
C90.073 (2)0.109 (3)0.074 (2)0.0228 (19)0.0156 (16)0.0385 (19)
C100.090 (2)0.072 (2)0.0614 (16)0.0019 (17)0.0199 (15)0.0147 (15)
Geometric parameters (Å, º) top
C1—C61.374 (3)C4—H4A0.9300
C1—C21.383 (3)C5—C61.407 (3)
C1—H1A0.9300C5—H5A0.9300
O1—N21.221 (2)C6—C71.430 (4)
N1—C71.144 (3)C8—C91.506 (4)
O2—N21.229 (3)C8—C101.507 (4)
N2—C21.445 (3)C8—H8A0.9800
C2—C31.426 (3)C9—H9A0.9600
N3—C31.333 (3)C9—H9B0.9600
N3—C81.473 (3)C9—H9C0.9600
N3—H3A0.8600C10—H10A0.9600
C3—C41.417 (3)C10—H10B0.9600
C4—C51.349 (3)C10—H10C0.9600
C6—C1—C2120.3 (2)C1—C6—C7122.0 (2)
C6—C1—H1A119.8C5—C6—C7119.0 (2)
C2—C1—H1A119.8N1—C7—C6177.7 (3)
O1—N2—O2121.3 (2)N3—C8—C9107.4 (2)
O1—N2—C2118.7 (2)N3—C8—C10111.8 (2)
O2—N2—C2120.05 (18)C9—C8—C10112.2 (2)
C1—C2—C3122.2 (2)N3—C8—H8A108.4
C1—C2—N2116.20 (19)C9—C8—H8A108.4
C3—C2—N2121.6 (2)C10—C8—H8A108.4
C3—N3—C8125.47 (19)C8—C9—H9A109.5
C3—N3—H3A117.3C8—C9—H9B109.5
C8—N3—H3A117.3H9A—C9—H9B109.5
N3—C3—C4120.94 (19)C8—C9—H9C109.5
N3—C3—C2124.1 (2)H9A—C9—H9C109.5
C4—C3—C2114.9 (2)H9B—C9—H9C109.5
C5—C4—C3122.9 (2)C8—C10—H10A109.5
C5—C4—H4A118.6C8—C10—H10B109.5
C3—C4—H4A118.6H10A—C10—H10B109.5
C4—C5—C6120.7 (2)C8—C10—H10C109.5
C4—C5—H5A119.7H10A—C10—H10C109.5
C6—C5—H5A119.7H10B—C10—H10C109.5
C1—C6—C5119.0 (2)
C6—C1—C2—C30.2 (4)N2—C2—C3—C4179.5 (2)
C6—C1—C2—N2179.4 (2)N3—C3—C4—C5179.8 (2)
O1—N2—C2—C11.9 (4)C2—C3—C4—C50.1 (4)
O2—N2—C2—C1177.3 (2)C3—C4—C5—C60.6 (4)
O1—N2—C2—C3177.4 (3)C2—C1—C6—C50.3 (4)
O2—N2—C2—C33.5 (4)C2—C1—C6—C7179.4 (2)
C8—N3—C3—C43.4 (4)C4—C5—C6—C10.6 (4)
C8—N3—C3—C2176.1 (2)C4—C5—C6—C7179.8 (2)
C1—C2—C3—N3179.4 (2)C3—N3—C8—C9161.5 (3)
N2—C2—C3—N30.1 (4)C3—N3—C8—C1075.0 (3)
C1—C2—C3—C40.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···O20.861.992.643 (2)132
C1—H1A···N1i0.932.613.469 (3)153
C4—H4A···O1ii0.932.403.298 (3)163
C5—H5A···N1iii0.932.603.529 (4)175
Symmetry codes: (i) x, y, z; (ii) x, y, z+1; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC10H11N3O2
Mr205.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.6640 (13), 20.678 (4), 7.8900 (16)
β (°) 105.74 (3)
V3)1046.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.10 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4 four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.982, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
2821, 1926, 1228
Rint0.020
(sin θ/λ)max1)0.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.170, 1.00
No. of reflections1926
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N3—H3A···O20.86001.99002.643 (2)132.00
C1—H1A···N1i0.93002.61003.469 (3)153.00
C4—H4A···O1ii0.93002.40003.298 (3)163.00
C5—H5A···N1iii0.93002.60003.529 (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

First citationAllen, 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 Web of Science
First citationAtes-Alagoz, Z. & Buyukbingol, E. (2001). Heterocycl. Commun. 7, 455–460.  CAS
First citationEnraf–Nonius (1994). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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