2-Methyl-5-nitro­benzonitrile

Abstract

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 ▶); Jin et al. (1994 ▶); Brewis et al. (2003 ▶); Dunica et al. (1991 ▶). For related literature, see: Fu & Zhao (2007 ▶).

Experimental

Crystal data

• C₈H₆N₂O₂

• M _r = 162.15

• Monoclinic,

• a = 3.8946 (8) Å

• b = 7.6350 (15) Å

• c = 26.180 (5) Å

• β = 91.65 (3)°

• V = 778.1 (3) ų

• 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 ▶) T _min = 0.93, T _max = 0.98

• 7390 measured reflections

• 1761 independent reflections

• 1273 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.141

• S = 1.04

• 1761 reflections

• 109 parameters

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

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

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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

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 U_iso(H) = 1.2_eq(C) or 0.96Å (methyl) and U_iso(H) = 1.5U_eq(C).

Figures

Fig. 1.

A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Crystal data

C8H6N2O2	F000 = 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 = 3.1–27.7º
c = 26.180 (5) Å	µ = 0.10 mm−1
β = 91.65 (3)º	T = 293 (2) K
V = 778.1 (3) Å3	Block, colourless
Z = 4	0.4 × 0.35 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer	1761 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.039
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5º
T = 293(2) K	θmin = 3.1º
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

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) = 0.141	w = 1/[σ2(Fo2) + (0.0668P)2 + 0.1332P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1761 reflections	Δρmax = 0.14 e Å−3
109 parameters	Δρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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)