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access2-Methyl-5-nitrobenzonitrile
aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: fudavid88@yahoo.com.cn
In the title compound, C8H6N2O2, the nitro group is rotated by 10.2 (2)° out of the plane of the benzene ring. The is stabilized by van der Waals interactions.
Related literature
For the chemistry of nitrile derivatives, see: Xiong et al. (2002![[Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800-3803.]](../../../../../../logos/arrows/e_arr.gif "Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800-3803.")
); Jin et al. (1994); Brewis et al. (2003); Dunica et al. (1991). For related literature, see: Fu & Zhao (2007).
![[Scheme 1]](bx2137scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; 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/S1600536808010982/bx2137sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808010982/bx2137Isup2.hkl
The title compound was purchased from Aldrich and was dissolved (3 mmol, 486.44 mg) in ethanol (20 ml) and evaporated in air affording colorless block crystals suitable for X-ray analysis.
Positional parameters of all the H atoms bonded to C atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded, with C—H = 0.93Å (aromatic) and with Uiso(H) = 1.2eq(C) or 0.96Å (methyl) and Uiso(H) = 1.5Ueq(C).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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]](./bx2137fig1thm.gif) | Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. |
| C8H6N2O2 | F(000) = 336 |
| Mr = 162.15 | Dx = 1.384 Mg m−3 |
| Monoclinic, P21/n | Melting point = 349–350 K |
| Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
| a = 3.8946 (8) Å | Cell parameters from 1763 reflections |
| b = 7.6350 (15) Å | θ = 3.1–27.7° |
| c = 26.180 (5) Å | µ = 0.10 mm−1 |
| β = 91.65 (3)° | T = 293 K |
| V = 778.1 (3) Å3 | Block, colourless |
| Z = 4 | 0.4 × 0.35 × 0.2 mm |
| Rigaku Mercury2 diffractometer | 1761 independent reflections |
| Radiation source: fine-focus sealed tube | 1273 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.039 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −5→4 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −9→9 |
| Tmin = 0.93, Tmax = 0.98 | l = −33→33 |
| 7390 measured reflections |
| 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.141 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0668P)2 + 0.1332P] where P = (Fo2 + 2Fc2)/3 |
| 1761 reflections | (Δ/σ)max < 0.001 |
| 109 parameters | Δρmax = 0.14 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C8H6N2O2 | V = 778.1 (3) Å3 |
| Mr = 162.15 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 3.8946 (8) Å | µ = 0.10 mm−1 |
| b = 7.6350 (15) Å | T = 293 K |
| c = 26.180 (5) Å | 0.4 × 0.35 × 0.2 mm |
| β = 91.65 (3)° |
| Rigaku Mercury2 diffractometer | 1761 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1273 reflections with I > 2σ(I) |
| Tmin = 0.93, Tmax = 0.98 | Rint = 0.039 |
| 7390 measured reflections |
| R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
| wR(F2) = 0.141 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.14 e Å−3 |
| 1761 reflections | Δρmin = −0.18 e Å−3 |
| 109 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 | ||
| N1 | 0.8171 (4) | 0.3298 (2) | 0.18614 (5) | 0.0590 (4) | |
| C3 | 0.8617 (4) | 0.6612 (2) | 0.08273 (6) | 0.0450 (4) | |
| C2 | 0.7935 (4) | 0.5051 (2) | 0.10776 (5) | 0.0451 (4) | |
| H2A | 0.6877 | 0.4120 | 0.0907 | 0.054* | |
| C7 | 0.7618 (5) | 0.6787 (2) | 0.02938 (6) | 0.0534 (4) | |
| C4 | 1.0183 (4) | 0.8045 (2) | 0.10793 (6) | 0.0489 (4) | |
| C1 | 0.8882 (4) | 0.4929 (2) | 0.15883 (6) | 0.0469 (4) | |
| N2 | 0.6808 (5) | 0.6958 (2) | −0.01239 (6) | 0.0745 (5) | |
| C5 | 1.1068 (4) | 0.7835 (2) | 0.15941 (7) | 0.0569 (5) | |
| H5A | 1.2101 | 0.8762 | 0.1770 | 0.068* | |
| O1 | 0.9413 (5) | 0.3114 (2) | 0.22899 (6) | 0.0954 (6) | |
| O2 | 0.6345 (4) | 0.2205 (2) | 0.16517 (6) | 0.0838 (5) | |
| C6 | 1.0461 (4) | 0.6299 (2) | 0.18501 (6) | 0.0550 (5) | |
| H6A | 1.1100 | 0.6182 | 0.2193 | 0.066* | |
| C8 | 1.0878 (5) | 0.9721 (2) | 0.08010 (7) | 0.0636 (5) | |
| H8A | 1.1998 | 1.0535 | 0.1030 | 0.095* | |
| H8B | 0.8748 | 1.0213 | 0.0676 | 0.095* | |
| H8C | 1.2333 | 0.9487 | 0.0519 | 0.095* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0639 (9) | 0.0679 (10) | 0.0450 (8) | 0.0035 (8) | −0.0017 (7) | 0.0075 (7) |
| C3 | 0.0453 (8) | 0.0507 (9) | 0.0387 (8) | −0.0026 (7) | −0.0039 (6) | −0.0050 (6) |
| C2 | 0.0460 (8) | 0.0481 (9) | 0.0407 (8) | −0.0017 (7) | −0.0045 (6) | −0.0051 (6) |
| C7 | 0.0660 (11) | 0.0465 (9) | 0.0473 (9) | −0.0131 (8) | −0.0079 (8) | −0.0006 (7) |
| C4 | 0.0438 (8) | 0.0519 (9) | 0.0509 (9) | −0.0024 (7) | −0.0011 (7) | −0.0091 (7) |
| C1 | 0.0445 (8) | 0.0559 (10) | 0.0401 (8) | 0.0037 (7) | −0.0011 (6) | −0.0006 (7) |
| N2 | 0.1069 (14) | 0.0667 (10) | 0.0486 (9) | −0.0268 (9) | −0.0196 (9) | 0.0072 (7) |
| C5 | 0.0547 (10) | 0.0629 (11) | 0.0525 (10) | −0.0062 (8) | −0.0072 (8) | −0.0186 (8) |
| O1 | 0.1169 (13) | 0.1119 (13) | 0.0559 (8) | −0.0133 (10) | −0.0234 (8) | 0.0294 (8) |
| O2 | 0.1135 (13) | 0.0681 (9) | 0.0688 (9) | −0.0226 (9) | −0.0121 (9) | 0.0108 (7) |
| C6 | 0.0540 (10) | 0.0721 (12) | 0.0385 (8) | 0.0022 (8) | −0.0078 (7) | −0.0093 (7) |
| C8 | 0.0640 (11) | 0.0545 (10) | 0.0721 (12) | −0.0136 (9) | −0.0039 (9) | −0.0046 (9) |
| N1—O2 | 1.217 (2) | C4—C5 | 1.391 (2) |
| N1—O1 | 1.2168 (19) | C4—C8 | 1.501 (2) |
| N1—C1 | 1.467 (2) | C1—C6 | 1.385 (2) |
| C3—C4 | 1.407 (2) | C5—C6 | 1.375 (3) |
| C3—C2 | 1.390 (2) | C5—H5A | 0.9300 |
| C3—C7 | 1.445 (2) | C6—H6A | 0.9300 |
| C2—C1 | 1.380 (2) | C8—H8A | 0.9600 |
| C2—H2A | 0.9300 | C8—H8B | 0.9600 |
| C7—N2 | 1.137 (2) | C8—H8C | 0.9600 |
| O2—N1—O1 | 123.27 (16) | C2—C1—N1 | 118.73 (14) |
| O2—N1—C1 | 118.58 (14) | C6—C1—N1 | 119.18 (14) |
| O1—N1—C1 | 118.15 (15) | C6—C5—C4 | 121.98 (15) |
| C4—C3—C2 | 122.14 (14) | C6—C5—H5A | 119.0 |
| C4—C3—C7 | 118.83 (14) | C4—C5—H5A | 119.0 |
| C2—C3—C7 | 119.02 (13) | C5—C6—C1 | 118.89 (15) |
| C1—C2—C3 | 117.73 (14) | C5—C6—H6A | 120.6 |
| C1—C2—H2A | 121.1 | C1—C6—H6A | 120.6 |
| C3—C2—H2A | 121.1 | C4—C8—H8A | 109.5 |
| N2—C7—C3 | 178.63 (19) | C4—C8—H8B | 109.5 |
| C5—C4—C3 | 117.16 (15) | H8A—C8—H8B | 109.5 |
| C5—C4—C8 | 121.71 (15) | C4—C8—H8C | 109.5 |
| C3—C4—C8 | 121.12 (15) | H8A—C8—H8C | 109.5 |
| C2—C1—C6 | 122.09 (15) | H8B—C8—H8C | 109.5 |
| C4—C3—C2—C1 | −0.7 (2) | O1—N1—C1—C2 | 170.40 (16) |
| C7—C3—C2—C1 | −179.26 (14) | O2—N1—C1—C6 | 169.28 (16) |
| C2—C3—C4—C5 | 0.6 (2) | O1—N1—C1—C6 | −9.9 (2) |
| C7—C3—C4—C5 | 179.19 (15) | C3—C4—C5—C6 | 0.2 (2) |
| C2—C3—C4—C8 | −179.73 (15) | C8—C4—C5—C6 | −179.50 (16) |
| C7—C3—C4—C8 | −1.1 (2) | C4—C5—C6—C1 | −0.8 (3) |
| C3—C2—C1—C6 | 0.0 (2) | C2—C1—C6—C5 | 0.7 (3) |
| C3—C2—C1—N1 | 179.64 (13) | N1—C1—C6—C5 | −178.91 (15) |
| O2—N1—C1—C2 | −10.4 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C8H6N2O2 |
| Mr | 162.15 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 293 |
| a, b, c (Å) | 3.8946 (8), 7.6350 (15), 26.180 (5) |
| β (°) | 91.65 (3) |
| V (Å3) | 778.1 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.4 × 0.35 × 0.2 |
| Data collection | |
| Diffractometer | Rigaku Mercury2 diffractometer |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.93, 0.98 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7390, 1761, 1273 |
| Rint | 0.039 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.141, 1.04 |
| No. of reflections | 1761 |
| No. of parameters | 109 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.14, −0.18 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.
References
Brewis, M., Helliwell, M. & McKeown, N. B. (2003). Tetrahedron, 59, 3863–3872. Web of Science CSD CrossRef CAS Google Scholar
Dunica, J. V., Pierce, M. E. & Santella, J. B. (1991). J. Org. Chem. 56, 2395–2400. Google Scholar
Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800–3803. Web of Science CrossRef CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Nitrile derivatives have found wide range of applications in industry and coordination chemistry as ligands. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (Brewis et al., 2003). And nitrile compounds are the precursor of tetrazole complexes (Dunica et al., 1991), which we have focused on for the design of noncentrosymmetric bulk materials, based on axial-chiral ligand 5-(3-methyl-4-nitrophenyl)-2H-tetrazole (Xiong et al., 2002). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007). As an extension of our work on the structural characterization, we report here the crystal structure of title compound. The crystal data show that in the title compound, the benzene ring and the nitro group are nearly planar, they are only twisted to each other by a torsion angles of O2—N1—C1—C2 (-10.4 (2)°) and O1—N1—C1—C6 (-9.9 (2)°), the nitrile group C7—N2 bond length of 1.137 (2)Å is within the normal range (Fig.1).