organic compounds
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
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
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell 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
10.1107/S1600536811051737/zs2168sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811051737/zs2168Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811051737/zs2168Isup3.cml
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.
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).
Data collection: CAD-4 Software (Enraf–Nonius, 1994); cell
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.C10H11N3O2 | F(000) = 432 |
Mr = 205.22 | Dx = 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 |
Enraf–Nonius CAD-4 four-circle diffractometer | 1228 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.4°, θmin = 2.0° |
ω/2θ scans | h = 0→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −6→24 |
Tmin = 0.982, Tmax = 0.991 | l = −9→9 |
2821 measured reflections | 3 standard reflections every 200 reflections |
1926 independent reflections | intensity decay: 1% |
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(Fo2) + (0.10P)2 + 0.040P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1926 reflections | Δρmax = 0.20 e Å−3 |
137 parameters | Δρmin = −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) |
C10H11N3O2 | V = 1046.5 (4) Å3 |
Mr = 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)° |
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 = 0.991 | 3 standard reflections every 200 reflections |
2821 measured reflections | intensity decay: 1% |
1926 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.170 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.20 e Å−3 |
1926 reflections | Δρmin = −0.17 e Å−3 |
137 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.982, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2821, 1926, 1228 |
Rint | 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 |
Δρmax, Δρmin (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.
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
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 Web of Science 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
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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].