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ISSN: 2056-9890

2-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

(Received 31 March 2008; accepted 19 April 2008; online 3 May 2008)

In the title compound, C8H6N2O2, the nitro group is rotated by 10.2 (2)° out of the plane of the benzene ring. The crystal structure 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.]); Jin et al. (1994[Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205-212.]); Brewis et al. (2003[Brewis, M., Helliwell, M. & McKeown, N. B. (2003). Tetrahedron, 59, 3863-3872.]); Dunica et al. (1991[Dunica, J. V., Pierce, M. E. & Santella, J. B. (1991). J. Org. Chem. 56, 2395-2400.]). For related literature, see: Fu & Zhao (2007[Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6N2O2

  • Mr = 162.15

  • Monoclinic, P 21 /n

  • a = 3.8946 (8) Å

  • b = 7.6350 (15) Å

  • c = 26.180 (5) Å

  • β = 91.65 (3)°

  • V = 778.1 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 293 (2) K

  • 0.4 × 0.35 × 0.2 mm

Data collection
  • Rigaku Mercury2 diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.93, Tmax = 0.98

  • 7390 measured reflections

  • 1761 independent reflections

  • 1273 reflections with I > 2σ(I)

  • Rint = 0.038

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.141

  • S = 1.04

  • 1761 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005[Rigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

For the chemistry of Nitrile derivatives, see: Xiong et al. (2002); Jin et al. (1994); Brewis et al. (2003); Dunica et al. (1991). For related literature, see: Fu & Zhao (2007).

Experimental top

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.

Refinement top

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).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
2-Methyl-5-nitrobenzonitrile top
Crystal data top
C8H6N2O2F(000) = 336
Mr = 162.15Dx = 1.384 Mg m3
Monoclinic, P21/nMelting point = 349–350 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 3.8946 (8) ÅCell parameters from 1763 reflections
b = 7.6350 (15) Åθ = 3.1–27.7°
c = 26.180 (5) ŵ = 0.10 mm1
β = 91.65 (3)°T = 293 K
V = 778.1 (3) Å3Block, colourless
Z = 40.4 × 0.35 × 0.2 mm
Data collection top
Rigaku Mercury2
diffractometer
1761 independent reflections
Radiation source: fine-focus sealed tube1273 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 54
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 99
Tmin = 0.93, Tmax = 0.98l = 3333
7390 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-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 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C8H6N2O2V = 778.1 (3) Å3
Mr = 162.15Z = 4
Monoclinic, P21/nMo Kα radiation
a = 3.8946 (8) ŵ = 0.10 mm1
b = 7.6350 (15) ÅT = 293 K
c = 26.180 (5) Å0.4 × 0.35 × 0.2 mm
β = 91.65 (3)°
Data collection top
Rigaku Mercury2
diffractometer
1761 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
1273 reflections with I > 2σ(I)
Tmin = 0.93, Tmax = 0.98Rint = 0.039
7390 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.04Δρmax = 0.14 e Å3
1761 reflectionsΔρmin = 0.18 e Å3
109 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
N10.8171 (4)0.3298 (2)0.18614 (5)0.0590 (4)
C30.8617 (4)0.6612 (2)0.08273 (6)0.0450 (4)
C20.7935 (4)0.5051 (2)0.10776 (5)0.0451 (4)
H2A0.68770.41200.09070.054*
C70.7618 (5)0.6787 (2)0.02938 (6)0.0534 (4)
C41.0183 (4)0.8045 (2)0.10793 (6)0.0489 (4)
C10.8882 (4)0.4929 (2)0.15883 (6)0.0469 (4)
N20.6808 (5)0.6958 (2)0.01239 (6)0.0745 (5)
C51.1068 (4)0.7835 (2)0.15941 (7)0.0569 (5)
H5A1.21010.87620.17700.068*
O10.9413 (5)0.3114 (2)0.22899 (6)0.0954 (6)
O20.6345 (4)0.2205 (2)0.16517 (6)0.0838 (5)
C61.0461 (4)0.6299 (2)0.18501 (6)0.0550 (5)
H6A1.11000.61820.21930.066*
C81.0878 (5)0.9721 (2)0.08010 (7)0.0636 (5)
H8A1.19981.05350.10300.095*
H8B0.87481.02130.06760.095*
H8C1.23330.94870.05190.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0639 (9)0.0679 (10)0.0450 (8)0.0035 (8)0.0017 (7)0.0075 (7)
C30.0453 (8)0.0507 (9)0.0387 (8)0.0026 (7)0.0039 (6)0.0050 (6)
C20.0460 (8)0.0481 (9)0.0407 (8)0.0017 (7)0.0045 (6)0.0051 (6)
C70.0660 (11)0.0465 (9)0.0473 (9)0.0131 (8)0.0079 (8)0.0006 (7)
C40.0438 (8)0.0519 (9)0.0509 (9)0.0024 (7)0.0011 (7)0.0091 (7)
C10.0445 (8)0.0559 (10)0.0401 (8)0.0037 (7)0.0011 (6)0.0006 (7)
N20.1069 (14)0.0667 (10)0.0486 (9)0.0268 (9)0.0196 (9)0.0072 (7)
C50.0547 (10)0.0629 (11)0.0525 (10)0.0062 (8)0.0072 (8)0.0186 (8)
O10.1169 (13)0.1119 (13)0.0559 (8)0.0133 (10)0.0234 (8)0.0294 (8)
O20.1135 (13)0.0681 (9)0.0688 (9)0.0226 (9)0.0121 (9)0.0108 (7)
C60.0540 (10)0.0721 (12)0.0385 (8)0.0022 (8)0.0078 (7)0.0093 (7)
C80.0640 (11)0.0545 (10)0.0721 (12)0.0136 (9)0.0039 (9)0.0046 (9)
Geometric parameters (Å, º) top
N1—O21.217 (2)C4—C51.391 (2)
N1—O11.2168 (19)C4—C81.501 (2)
N1—C11.467 (2)C1—C61.385 (2)
C3—C41.407 (2)C5—C61.375 (3)
C3—C21.390 (2)C5—H5A0.9300
C3—C71.445 (2)C6—H6A0.9300
C2—C11.380 (2)C8—H8A0.9600
C2—H2A0.9300C8—H8B0.9600
C7—N21.137 (2)C8—H8C0.9600
O2—N1—O1123.27 (16)C2—C1—N1118.73 (14)
O2—N1—C1118.58 (14)C6—C1—N1119.18 (14)
O1—N1—C1118.15 (15)C6—C5—C4121.98 (15)
C4—C3—C2122.14 (14)C6—C5—H5A119.0
C4—C3—C7118.83 (14)C4—C5—H5A119.0
C2—C3—C7119.02 (13)C5—C6—C1118.89 (15)
C1—C2—C3117.73 (14)C5—C6—H6A120.6
C1—C2—H2A121.1C1—C6—H6A120.6
C3—C2—H2A121.1C4—C8—H8A109.5
N2—C7—C3178.63 (19)C4—C8—H8B109.5
C5—C4—C3117.16 (15)H8A—C8—H8B109.5
C5—C4—C8121.71 (15)C4—C8—H8C109.5
C3—C4—C8121.12 (15)H8A—C8—H8C109.5
C2—C1—C6122.09 (15)H8B—C8—H8C109.5
C4—C3—C2—C10.7 (2)O1—N1—C1—C2170.40 (16)
C7—C3—C2—C1179.26 (14)O2—N1—C1—C6169.28 (16)
C2—C3—C4—C50.6 (2)O1—N1—C1—C69.9 (2)
C7—C3—C4—C5179.19 (15)C3—C4—C5—C60.2 (2)
C2—C3—C4—C8179.73 (15)C8—C4—C5—C6179.50 (16)
C7—C3—C4—C81.1 (2)C4—C5—C6—C10.8 (3)
C3—C2—C1—C60.0 (2)C2—C1—C6—C50.7 (3)
C3—C2—C1—N1179.64 (13)N1—C1—C6—C5178.91 (15)
O2—N1—C1—C210.4 (2)

Experimental details

Crystal data
Chemical formulaC8H6N2O2
Mr162.15
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)3.8946 (8), 7.6350 (15), 26.180 (5)
β (°) 91.65 (3)
V3)778.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.4 × 0.35 × 0.2
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2005)
Tmin, Tmax0.93, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
7390, 1761, 1273
Rint0.039
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.141, 1.04
No. of reflections1761
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBrewis, M., Helliwell, M. & McKeown, N. B. (2003). Tetrahedron, 59, 3863–3872.  Web of Science CSD CrossRef CAS
First citationDunica, J. V., Pierce, M. E. & Santella, J. B. (1991). J. Org. Chem. 56, 2395–2400.
First citationFu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206.  Web of Science CSD CrossRef IUCr Journals
First citationJin, 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
First citationRigaku/MSC (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationXiong, 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

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ISSN: 2056-9890
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