4-Chloro-3-nitro­benzonitrile

Liu, B.-N.; Tang, S.-G.; Li, H.-Y.; Guo, C.

doi:10.1107/S1600536808041330

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o92

doi:10.1107/S1600536808041330

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4-Chloro-3-nitrobenzonitrile

Bo-Nian Liu,^a Shi-Gui Tang,^b Hao-Yuan Li ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China, and ^bCollege of Life Sciences and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 4 December 2008; accepted 7 December 2008; online 10 December 2008)

In the title compound, C₇H₃ClN₂O₂, the Cl, C and N atoms are coplanar with the aromatic ring. In the crystal structure, weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds link the molecules. The π–π contact between the benzene rings, [centroid–centroid distances = 3.912 (3) Å] may further stabilize the structure.

Related literature

For a related structure, see: Sun & Wang (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₃ClN₂O₂
M_r = 182.56
Triclinic, $[P \overline 1]$
a = 7.2260 (14) Å
b = 7.7610 (16) Å
c = 7.7970 (16) Å
α = 110.27 (3)°
β = 91.86 (3)°
γ = 107.22 (3)°
V = 387.32 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.878, T_max = 0.957
1540 measured reflections
1418 independent reflections
1000 reflections with I > 2σ(I)
R_int = 0.052
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.182
S = 1.00
1418 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.48	3.288 (7)	145
C5—H5A⋯N2ⁱⁱ	0.93	2.61	3.497 (7)	159
Symmetry codes: (i) x, y+1, z; (ii) -x+2, -y+1, -z+2.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: 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: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041330/hk2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041330/hk2597Isup2.hkl

checkCIF report

Comment top

Some derivatives of pyridine are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. Atoms Cl, C7, N1 and N2 are -0.040 (3), -0.049 (3), 0.005 (3) and 0.036 (3) Å away from the plane of the benzene ring.

In the crystal structure, weak intermolecular C-H···O and C-H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the benzene rings, Cg1—Cg1ⁱ [symmetry code: (i) 1 - x, 1 - y, -z, where Cg1 is centroid of the ring A (C1-C6)] may further stabilize the structure, with centroid-centroid distance of 3.912 (3) Å.

Related literature top

For a related structure, see: Sun et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 4-chloro-3-nitrobenzamide (33.9 g, 0.17 mol) was suspended in phosphorus oxychloride (150 ml). The temperature was controlled at 333 K for 6 h, and then it was put into ice water (500 ml). It was filtered and the colorless precipitate was washed (yield; 28.2 g) (Sun et al., 2006). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003.

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

4-Chloro-3-nitrobenzonitrile top

Crystal data top

C₇H₃ClN₂O₂	Z = 2
M_r = 182.56	F(000) = 184
Triclinic, P1	D_x = 1.565 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2260 (14) Å	Cell parameters from 25 reflections
b = 7.7610 (16) Å	θ = 9–12°
c = 7.7970 (16) Å	µ = 0.45 mm⁻¹
α = 110.27 (3)°	T = 294 K
β = 91.86 (3)°	Block, colorless
γ = 107.22 (3)°	0.30 × 0.20 × 0.10 mm
V = 387.32 (18) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1000 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 25.3°, θ_min = 2.8°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = −9→8
T_min = 0.878, T_max = 0.957	l = 0→9
1540 measured reflections	3 standard reflections every 120 min
1418 independent reflections	intensity decay: none

Refinement top

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.060P)² + 0.880P] where P = (F_o² + 2F_c²)/3
1418 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₇H₃ClN₂O₂	γ = 107.22 (3)°
M_r = 182.56	V = 387.32 (18) Å³
Triclinic, P1	Z = 2
a = 7.2260 (14) Å	Mo Kα radiation
b = 7.7610 (16) Å	µ = 0.45 mm⁻¹
c = 7.7970 (16) Å	T = 294 K
α = 110.27 (3)°	0.30 × 0.20 × 0.10 mm
β = 91.86 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1000 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.052
T_min = 0.878, T_max = 0.957	3 standard reflections every 120 min
1540 measured reflections	intensity decay: none
1418 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
1418 reflections	Δρ_min = −0.33 e Å⁻³
103 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

	x	y	z	U_iso*/U_eq
Cl	0.08801 (17)	0.32257 (19)	0.5711 (2)	0.0767 (5)
O1	0.3498 (8)	0.0413 (6)	0.7577 (7)	0.1159 (19)
O2	0.2991 (5)	0.0203 (5)	0.4775 (6)	0.0819 (12)
N1	0.3567 (5)	0.1130 (5)	0.6413 (6)	0.0590 (10)
N2	1.0736 (7)	0.7724 (7)	1.0090 (8)	0.0942 (17)
C1	0.6103 (7)	0.7170 (6)	0.8157 (7)	0.0652 (12)
H1A	0.6681	0.8512	0.8556	0.077*
C2	0.4139 (6)	0.6306 (6)	0.7290 (7)	0.0602 (12)
H2A	0.3418	0.7057	0.7106	0.072*
C3	0.3307 (6)	0.4305 (6)	0.6717 (6)	0.0560 (12)
C4	0.4384 (6)	0.3252 (6)	0.7025 (6)	0.0502 (11)
C5	0.6290 (6)	0.4094 (6)	0.7883 (6)	0.0581 (12)
H5A	0.7001	0.3352	0.8108	0.070*
C6	0.7137 (6)	0.6118 (6)	0.8413 (6)	0.0478 (10)
C7	0.9133 (7)	0.7033 (7)	0.9310 (8)	0.0718 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0388 (6)	0.0651 (8)	0.1075 (11)	0.0117 (5)	0.0161 (6)	0.0143 (7)
O1	0.187 (5)	0.048 (2)	0.111 (4)	0.028 (3)	0.076 (3)	0.031 (2)
O2	0.064 (2)	0.047 (2)	0.098 (3)	0.0060 (16)	0.015 (2)	−0.007 (2)
N1	0.046 (2)	0.038 (2)	0.078 (3)	0.0103 (16)	0.027 (2)	0.005 (2)
N2	0.059 (3)	0.068 (3)	0.110 (4)	−0.004 (2)	−0.001 (3)	−0.001 (3)
C1	0.062 (2)	0.034 (3)	0.078 (3)	0.005 (2)	0.031 (2)	0.004 (2)
C2	0.046 (2)	0.048 (3)	0.079 (3)	0.018 (2)	0.022 (2)	0.011 (2)
C3	0.037 (2)	0.047 (2)	0.068 (3)	0.0102 (19)	0.027 (2)	0.003 (2)
C4	0.044 (2)	0.032 (2)	0.065 (3)	0.0098 (17)	0.033 (2)	0.0069 (19)
C5	0.043 (2)	0.042 (2)	0.071 (3)	0.0143 (19)	0.020 (2)	−0.001 (2)
C6	0.047 (2)	0.039 (2)	0.053 (2)	0.0128 (18)	0.0204 (19)	0.0112 (18)
C7	0.050 (3)	0.048 (3)	0.088 (4)	0.004 (2)	0.016 (3)	0.001 (3)

Geometric parameters (Å, º) top

Cl—C3	1.726 (4)	C4—C3	1.354 (6)
N1—O1	1.213 (6)	C4—C5	1.370 (6)
N1—O2	1.214 (5)	C5—C6	1.406 (6)
C1—H1A	0.9300	C5—H5A	0.9300
C2—C1	1.407 (7)	C6—C1	1.316 (6)
C2—C3	1.386 (6)	C6—C7	1.434 (7)
C2—H2A	0.9300	C7—N2	1.166 (6)
C4—N1	1.466 (5)

O1—N1—O2	124.2 (4)	C2—C3—Cl	118.9 (4)
O1—N1—C4	117.9 (4)	C4—C3—Cl	121.5 (3)
O2—N1—C4	117.9 (4)	C4—C3—C2	119.5 (4)
C1—C2—H2A	120.9	C3—C4—N1	121.1 (4)
C1—C6—C5	120.8 (4)	C3—C4—C5	122.2 (4)
C1—C6—C7	120.3 (4)	C5—C4—N1	116.6 (4)
C2—C1—H1A	119.4	C4—C5—C6	117.8 (4)
C6—C1—C2	121.3 (4)	C4—C5—H5A	121.1
C6—C1—H1A	119.4	C6—C5—H5A	121.1
C3—C2—C1	118.3 (4)	C5—C6—C7	118.8 (4)
C3—C2—H2A	120.9	N2—C7—C6	176.8 (6)

C3—C2—C1—C6	0.4 (7)	C5—C4—C3—Cl	−177.5 (4)
C1—C2—C3—C4	0.9 (7)	N1—C4—C3—Cl	3.8 (6)
C1—C2—C3—Cl	178.2 (4)	C3—C4—C5—C6	−1.4 (7)
C3—C4—N1—O1	−120.7 (5)	N1—C4—C5—C6	177.3 (4)
C5—C4—N1—O1	60.6 (6)	C4—C5—C6—C1	2.6 (7)
C3—C4—N1—O2	58.9 (5)	C4—C5—C6—C7	−179.8 (4)
C5—C4—N1—O2	−119.8 (5)	C5—C6—C1—C2	−2.1 (7)
C5—C4—C3—C2	−0.3 (7)	C7—C6—C1—C2	−179.6 (5)
N1—C4—C3—C2	−179.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.93	2.48	3.288 (7)	145
C5—H5A···N2ⁱⁱ	0.93	2.61	3.497 (7)	159

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₇H₃ClN₂O₂
M_r	182.56
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.2260 (14), 7.7610 (16), 7.7970 (16)
α, β, γ (°)	110.27 (3), 91.86 (3), 107.22 (3)
V (Å³)	387.32 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.878, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	1540, 1418, 1000
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.182, 1.00
No. of reflections	1418
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.33

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.9300	2.4800	3.288 (7)	145.00
C5—H5A···N2ⁱⁱ	0.9300	2.6100	3.497 (7)	159.00

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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