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access1-Chloro-2-methyl-3-nitrobenzene
aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
*Correspondence e-mail: jotanski@vassar.edu
In the title compound, C7H6ClNO2, the chloro, methyl and nitro substituents are situated next to each other in this order on the benzene ring, with the mean plane of the nitro group twisted away from the mean plane of the benzene ring by 38.81 (5)°.
Related literature
For information on industrial chemicals, see: Chloronitrotoluenes (2010![[Chloronitrotoluenes (2010). Environment Agency. Environment Agency Wales, UK.]](../../../../../../logos/arrows/e_arr.gif "Chloronitrotoluenes (2010). Environment Agency. Environment Agency Wales, UK.")
). For the use of the title compound as a starting material in the synthesis of 7-chlorovasicine (pyrrolo[2,1-b]quinazolin-3-ol, 8-chloro-1,2,3,9-tetrahydro), see: Southwick & Cremer (1959). For the toxic effects of the title compound on D. magna, see: Ramos et al. (2001) and on T. pyriformis, see: Schultz (1999); Katritzky et al. (2003). For a related structure, see: Liu & Du (2008).
![[Scheme 1]](jj2075scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811004466/jj2075sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811004466/jj2075Isup2.hkl
Crystalline1-chloro-2-methyl-3-nitrobenzene was purchase from Aldrich Chemical Company, USA.
All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on carbon were included in calculated positions and refined using a riding model at C–H = 0.95 or 0.98 Å and Uiso(H) = 1.2 or 1.5 × Ueq(C) of the aryl and methyl C-atoms, respectively. The extinction parameter (EXTI) refined to zero and was removed from the refinement.
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./jj2075fig1thm.gif) | Fig. 1. A view of the title compound, with displacement ellipsoids shown at the 50% probability level. |
| C7H6ClNO2 | F(000) = 704 |
| Mr = 171.58 | Dx = 1.536 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 9979 reflections |
| a = 7.3061 (5) Å | θ = 2.8–30.5° |
| b = 13.8392 (9) Å | µ = 0.46 mm−1 |
| c = 14.6799 (10) Å | T = 125 K |
| V = 1484.29 (17) Å3 | Block, colorless |
| Z = 8 | 0.32 × 0.20 × 0.10 mm |
| Bruker APEXII CCD diffractometer | 2271 independent reflections |
| Radiation source: fine-focus sealed tube | 1963 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.038 |
| ϕ and ω scans | θmax = 30.5°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −10→10 |
| Tmin = 0.868, Tmax = 0.956 | k = −19→19 |
| 22310 measured reflections | l = −20→20 |
| 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.4184P] where P = (Fo2 + 2Fc2)/3 |
| 2271 reflections | (Δ/σ)max = 0.001 |
| 101 parameters | Δρmax = 0.35 e Å−3 |
| 0 restraints | Δρmin = −0.38 e Å−3 |
| C7H6ClNO2 | V = 1484.29 (17) Å3 |
| Mr = 171.58 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 7.3061 (5) Å | µ = 0.46 mm−1 |
| b = 13.8392 (9) Å | T = 125 K |
| c = 14.6799 (10) Å | 0.32 × 0.20 × 0.10 mm |
| Bruker APEXII CCD diffractometer | 2271 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1963 reflections with I > 2σ(I) |
| Tmin = 0.868, Tmax = 0.956 | Rint = 0.038 |
| 22310 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.35 e Å−3 |
| 2271 reflections | Δρmin = −0.38 e Å−3 |
| 101 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 | ||
| Cl | 0.02248 (4) | 0.79411 (2) | 0.19541 (2) | 0.02921 (10) | |
| O1 | 0.18412 (16) | 0.46030 (7) | 0.46513 (7) | 0.0383 (2) | |
| O2 | 0.27741 (17) | 0.60583 (8) | 0.49519 (6) | 0.0414 (3) | |
| N | 0.21538 (15) | 0.54450 (7) | 0.44328 (7) | 0.0269 (2) | |
| C1 | 0.09994 (14) | 0.68212 (7) | 0.23325 (8) | 0.0200 (2) | |
| C2 | 0.11332 (14) | 0.66404 (7) | 0.32692 (7) | 0.0202 (2) | |
| C3 | 0.18229 (14) | 0.57217 (8) | 0.34792 (7) | 0.0198 (2) | |
| C4 | 0.22965 (15) | 0.50274 (8) | 0.28388 (8) | 0.0207 (2) | |
| H4A | 0.2734 | 0.4412 | 0.3026 | 0.025* | |
| C5 | 0.21212 (15) | 0.52466 (8) | 0.19236 (7) | 0.0218 (2) | |
| H5A | 0.2439 | 0.4783 | 0.1474 | 0.026* | |
| C6 | 0.14754 (15) | 0.61522 (8) | 0.16681 (7) | 0.0218 (2) | |
| H6A | 0.1360 | 0.6313 | 0.1041 | 0.026* | |
| C7 | 0.05257 (18) | 0.73682 (9) | 0.39679 (9) | 0.0294 (3) | |
| H7A | −0.0502 | 0.7744 | 0.3725 | 0.044* | |
| H7B | 0.1544 | 0.7804 | 0.4111 | 0.044* | |
| H7C | 0.0139 | 0.7032 | 0.4523 | 0.044* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl | 0.02669 (16) | 0.01774 (15) | 0.04320 (19) | −0.00006 (9) | −0.00430 (11) | 0.00518 (11) |
| O1 | 0.0576 (6) | 0.0269 (5) | 0.0303 (5) | −0.0020 (4) | 0.0027 (4) | 0.0077 (4) |
| O2 | 0.0613 (7) | 0.0399 (6) | 0.0232 (4) | −0.0141 (5) | −0.0070 (4) | −0.0023 (4) |
| N | 0.0321 (5) | 0.0269 (5) | 0.0218 (4) | −0.0029 (4) | 0.0012 (4) | 0.0015 (4) |
| C1 | 0.0176 (4) | 0.0150 (4) | 0.0274 (5) | −0.0011 (4) | −0.0013 (4) | 0.0010 (4) |
| C2 | 0.0185 (5) | 0.0174 (5) | 0.0248 (5) | −0.0030 (4) | 0.0024 (4) | −0.0032 (4) |
| C3 | 0.0208 (5) | 0.0197 (5) | 0.0189 (5) | −0.0033 (4) | 0.0009 (4) | 0.0007 (4) |
| C4 | 0.0207 (5) | 0.0159 (4) | 0.0256 (5) | −0.0006 (4) | 0.0003 (4) | −0.0015 (4) |
| C5 | 0.0221 (5) | 0.0202 (5) | 0.0232 (5) | −0.0012 (4) | 0.0013 (4) | −0.0054 (4) |
| C6 | 0.0222 (5) | 0.0226 (5) | 0.0207 (5) | −0.0027 (4) | −0.0013 (4) | −0.0003 (4) |
| C7 | 0.0326 (6) | 0.0234 (5) | 0.0324 (6) | −0.0011 (5) | 0.0074 (5) | −0.0095 (5) |
| Cl—C1 | 1.7410 (11) | C4—C5 | 1.3832 (16) |
| O1—N | 1.2300 (13) | C4—H4A | 0.9500 |
| O2—N | 1.2275 (14) | C5—C6 | 1.3907 (16) |
| N—C3 | 1.4713 (14) | C5—H5A | 0.9500 |
| C1—C6 | 1.3891 (15) | C6—H6A | 0.9500 |
| C1—C2 | 1.4010 (15) | C7—H7A | 0.9800 |
| C2—C3 | 1.4018 (15) | C7—H7B | 0.9800 |
| C2—C7 | 1.5045 (15) | C7—H7C | 0.9800 |
| C3—C4 | 1.3882 (15) | ||
| O2—N—O1 | 124.17 (11) | C3—C4—H4A | 120.6 |
| O2—N—C3 | 118.13 (10) | C4—C5—C6 | 119.41 (10) |
| O1—N—C3 | 117.66 (10) | C4—C5—H5A | 120.3 |
| C6—C1—C2 | 123.55 (10) | C6—C5—H5A | 120.3 |
| C6—C1—Cl | 116.78 (8) | C1—C6—C5 | 119.74 (10) |
| C2—C1—Cl | 119.66 (8) | C1—C6—H6A | 120.1 |
| C1—C2—C3 | 113.76 (10) | C5—C6—H6A | 120.1 |
| C1—C2—C7 | 121.93 (10) | C2—C7—H7A | 109.5 |
| C3—C2—C7 | 124.29 (10) | C2—C7—H7B | 109.5 |
| C4—C3—C2 | 124.64 (10) | H7A—C7—H7B | 109.5 |
| C4—C3—N | 115.04 (10) | C2—C7—H7C | 109.5 |
| C2—C3—N | 120.29 (10) | H7A—C7—H7C | 109.5 |
| C5—C4—C3 | 118.87 (10) | H7B—C7—H7C | 109.5 |
| C5—C4—H4A | 120.6 | ||
| C6—C1—C2—C3 | 0.94 (15) | O1—N—C3—C4 | −38.35 (15) |
| Cl—C1—C2—C3 | −178.30 (7) | O2—N—C3—C2 | −38.54 (16) |
| C6—C1—C2—C7 | −177.26 (11) | O1—N—C3—C2 | 143.61 (12) |
| Cl—C1—C2—C7 | 3.50 (15) | C2—C3—C4—C5 | 1.31 (17) |
| C1—C2—C3—C4 | −1.68 (15) | N—C3—C4—C5 | −176.63 (10) |
| C7—C2—C3—C4 | 176.46 (11) | C3—C4—C5—C6 | −0.09 (17) |
| C1—C2—C3—N | 176.17 (9) | C2—C1—C6—C5 | 0.13 (17) |
| C7—C2—C3—N | −5.69 (16) | Cl—C1—C6—C5 | 179.39 (8) |
| O2—N—C3—C4 | 139.50 (12) | C4—C5—C6—C1 | −0.59 (17) |
Experimental details
| Crystal data | |
| Chemical formula | C7H6ClNO2 |
| Mr | 171.58 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 125 |
| a, b, c (Å) | 7.3061 (5), 13.8392 (9), 14.6799 (10) |
| V (Å3) | 1484.29 (17) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.46 |
| Crystal size (mm) | 0.32 × 0.20 × 0.10 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
| Tmin, Tmax | 0.868, 0.956 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 22310, 2271, 1963 |
| Rint | 0.038 |
| (sin θ/λ)max (Å−1) | 0.713 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.090, 1.05 |
| No. of reflections | 2271 |
| No. of parameters | 101 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.35, −0.38 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (grant No. 0521237 to JMT).
References
Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chloronitrotoluenes (2010). Environment Agency. Environment Agency Wales, UK. Google Scholar
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Liu, H.-L. & Du, Z.-Q. (2008). Acta Cryst. E64, o536. Web of Science CSD CrossRef IUCr Journals Google Scholar
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The title compound, C7H6ClNO2, also known as 2-chloro-6-nitrotoluene, is a common intermediate in the synthesis of industrial chemicals (Chloronitrotoluenes, 2010), as well as in pharmaceuticals such as the bronchodilatory compound vasicine (Southwick et al., 1959). 1-chloro-2-methyl-3-nitrobenzene is relatively toxic to biological species such as the freashwater flea D. magna and freshwater protozoa T. pyriformis, which suggests that this compound could become a harmful pollutant (Katritzky et al., 2003; Schultz, 1999; Ramos et al., 2001; Chloronitrotoluenes, 2010).
C7H6ClNO2, (I), contains an aromatic ring with chloro, methyl and nitro substituents arranged in this order next to one another, The C—Cl and C—N bond lengths and angles in (I) are very close to those found in a similar structure (Liu & Du, 2008). The central methyl group interacts sterically with the neighboring chloro and nitro groups, as evidenced by the N—C3—C4 and Cl—C1—C6 angles of 115.0 (1)° and 116.78 (8)°, respectively. These angles are compressed from the ideal sp2 - hybridized carbon atom. The mean plane of the nitro group is twisted away from the mean plane of the aromatic ring by 38.81 (5)°.