4-Chloro-3-nitro­benzamide

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

doi:10.1107/S1600536808041342

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o80

doi:10.1107/S1600536808041342

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4-Chloro-3-nitrobenzamide

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 crystal of the title compound, C₇H₅ClN₂O₃, the molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds. The π–π contact between the benzene rings, [centroid–centroid distance = 3.803 (3) Å] may further stabilize the structure.

Related literature

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

Experimental

Crystal data

C₇H₅ClN₂O₃
M_r = 200.58
Monoclinic, P 2₁ /n
a = 8.8490 (18) Å
b = 7.5470 (15) Å
c = 12.374 (3) Å
β = 101.18 (3)°
V = 810.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.44 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 = 0.879, T_max = 0.957
1555 measured reflections
1459 independent reflections
1085 reflections with I > 2σ(I)
R_int = 0.061
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.198
S = 1.01
1459 reflections
112 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O3ⁱ	0.86	2.10	2.958 (6)	177
N2—H2C⋯O2ⁱⁱ	0.86	2.26	3.067 (6)	155
C2—H2A⋯O3ⁱⁱⁱ	0.93	2.42	3.331 (6)	166
Symmetry codes: (i) -x+3, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536808041342/hk2596sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041342/hk2596Isup2.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, N1 and C7 are 0.021 (3), 0.029 (3) and -0.001 (3) Å away from the plane of the benzene ring. The intramolecular C-H···O hydrogen bond results in the formation of a five-membered ring B (O2/N1/C5/C6/H5A), having envelope conformation with O2 atom displaced by 0.278 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular N-H···O and C-H···O 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) -x, -y, 1 - z, where Cg1 is centroid of the ring A (C1-C6)] may further stabilize the structure, with centroid-centroid distance of 3.803 (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-nitrobenzoic acid (60.3 g, 0.32 mol) was suspended in thionyl chloride (180 ml) and heated at reflux for 5 h, then concentrated in vacuum as far as possible, the oily substance obtained. Added ice ammonia water (300 ml) to the oil, cooling to room temperature, a precipitate formed, which was collected by filtration and washed with water. Pure title compound was obtained by crystallizing from methanol (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. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

4-Chloro-3-nitrobenzamide top

Crystal data top

C₇H₅ClN₂O₃	F(000) = 408
M_r = 200.58	D_x = 1.643 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.8490 (18) Å	θ = 10–13°
b = 7.5470 (15) Å	µ = 0.44 mm⁻¹
c = 12.374 (3) Å	T = 294 K
β = 101.18 (3)°	Block, colorless
V = 810.7 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1085 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.061
Graphite monochromator	θ_max = 25.3°, θ_min = 2.6°
ω/2θ scans	h = −10→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.879, T_max = 0.957	l = 0→14
1555 measured reflections	3 standard reflections every 120 min
1459 independent reflections	intensity decay: none

Refinement top

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)] = 0.078	H-atom parameters constrained
wR(F²) = 0.198	w = 1/[σ²(F_o²) + (0.060P)² + 4.5P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1459 reflections	Δρ_max = 0.41 e Å⁻³
112 parameters	Δρ_min = −0.51 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₇H₅ClN₂O₃	V = 810.7 (3) Å³
M_r = 200.58	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8490 (18) Å	µ = 0.44 mm⁻¹
b = 7.5470 (15) Å	T = 294 K
c = 12.374 (3) Å	0.30 × 0.20 × 0.10 mm
β = 101.18 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1085 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.061
T_min = 0.879, T_max = 0.957	3 standard reflections every 120 min
1555 measured reflections	intensity decay: none
1459 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	112 parameters
wR(F²) = 0.198	H-atom parameters constrained
S = 1.01	Δρ_max = 0.41 e Å⁻³
1459 reflections	Δρ_min = −0.51 e Å⁻³

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	0.65545 (17)	0.0416 (2)	0.36001 (13)	0.0618 (5)
O1	0.7053 (5)	0.1130 (7)	0.5888 (4)	0.0749 (14)
O2	0.8610 (5)	0.3068 (6)	0.6677 (3)	0.0554 (11)
O3	1.3178 (4)	0.4669 (5)	0.5500 (2)	0.0390 (9)
N1	0.8103 (5)	0.2076 (5)	0.5896 (3)	0.0385 (10)
N2	1.3809 (5)	0.3507 (7)	0.3985 (4)	0.0502 (12)
H2B	1.4701	0.4002	0.4120	0.060*
H2C	1.3546	0.2856	0.3409	0.060*
C1	0.8373 (6)	0.1359 (7)	0.3967 (4)	0.0378 (11)
C2	0.9221 (6)	0.1454 (7)	0.3143 (4)	0.0401 (12)
H2A	0.8819	0.1004	0.2448	0.048*
C3	1.0637 (6)	0.2201 (7)	0.3346 (4)	0.0424 (12)
H3A	1.1188	0.2260	0.2779	0.051*
C4	1.1312 (5)	0.2902 (6)	0.4397 (3)	0.0295 (10)
C5	1.0412 (5)	0.2840 (6)	0.5196 (3)	0.0316 (10)
H5A	1.0790	0.3319	0.5888	0.038*
C6	0.8958 (5)	0.2076 (6)	0.4985 (4)	0.0308 (10)
C7	1.2837 (6)	0.3746 (7)	0.4668 (4)	0.0435 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0584 (9)	0.0679 (10)	0.0626 (10)	−0.0058 (7)	0.0208 (7)	−0.0114 (8)
O1	0.079 (3)	0.088 (3)	0.074 (3)	−0.027 (3)	0.057 (3)	−0.007 (3)
O2	0.072 (3)	0.068 (3)	0.035 (2)	−0.016 (2)	0.0311 (18)	−0.007 (2)
O3	0.0454 (18)	0.052 (2)	0.0267 (16)	−0.0091 (16)	0.0254 (14)	−0.0091 (15)
N1	0.054 (2)	0.038 (2)	0.036 (2)	0.000 (2)	0.0375 (19)	0.0044 (19)
N2	0.051 (2)	0.070 (3)	0.042 (2)	−0.007 (2)	0.038 (2)	−0.018 (2)
C1	0.049 (3)	0.035 (3)	0.035 (2)	0.008 (2)	0.020 (2)	0.004 (2)
C2	0.063 (3)	0.042 (3)	0.019 (2)	0.001 (2)	0.018 (2)	−0.004 (2)
C3	0.068 (3)	0.044 (3)	0.024 (2)	0.002 (2)	0.031 (2)	0.002 (2)
C4	0.043 (2)	0.030 (2)	0.022 (2)	−0.0015 (19)	0.0245 (18)	−0.0009 (18)
C5	0.050 (3)	0.032 (2)	0.020 (2)	0.002 (2)	0.0234 (18)	−0.0002 (18)
C6	0.046 (2)	0.028 (2)	0.027 (2)	0.0066 (19)	0.0275 (19)	0.0056 (18)
C7	0.061 (2)	0.038 (2)	0.038 (2)	0.009 (19)	0.034 (19)	0.006 (18)

Geometric parameters (Å, º) top

Cl—C1	1.737 (5)	C1—C6	1.377 (7)
O3—C7	1.231 (6)	C2—C3	1.352 (7)
N1—O1	1.170 (6)	C2—H2A	0.9300
N1—O2	1.236 (5)	C3—C4	1.424 (7)
N1—C6	1.474 (5)	C3—H3A	0.9300
N2—C7	1.329 (6)	C4—C5	1.386 (6)
N2—H2B	0.8600	C4—C7	1.471 (7)
N2—H2C	0.8600	C5—C6	1.388 (7)
C1—C2	1.380 (6)	C5—H5A	0.9300

O1—N1—O2	122.9 (4)	C4—C3—H3A	118.9
O1—N1—C6	121.2 (4)	C3—C4—C7	124.9 (4)
O2—N1—C6	115.8 (4)	C5—C4—C3	116.2 (4)
C7—N2—H2B	120.0	C5—C4—C7	118.8 (4)
C7—N2—H2C	120.0	C4—C5—C6	121.3 (4)
H2B—N2—H2C	120.0	C4—C5—H5A	119.3
C2—C1—Cl	115.9 (4)	C6—C5—H5A	119.3
C6—C1—Cl	124.4 (4)	C1—C6—C5	120.4 (4)
C6—C1—C2	119.6 (5)	C1—C6—N1	122.8 (4)
C1—C2—H2A	119.9	C5—C6—N1	116.8 (4)
C3—C2—C1	120.1 (5)	O3—C7—N2	121.7 (5)
C3—C2—H2A	119.9	O3—C7—C4	120.0 (4)
C2—C3—C4	122.3 (4)	N2—C7—C4	118.3 (5)
C2—C3—H3A	118.9

O1—N1—C6—C1	17.6 (7)	C2—C3—C4—C5	−2.5 (7)
O2—N1—C6—C1	−165.6 (5)	C2—C3—C4—C7	−179.3 (5)
O1—N1—C6—C5	−162.2 (5)	C3—C4—C5—C6	2.3 (7)
O2—N1—C6—C5	14.6 (6)	C7—C4—C5—C6	179.3 (4)
C6—C1—C2—C3	2.0 (8)	C5—C4—C7—O3	−13.8 (7)
Cl—C1—C2—C3	178.6 (4)	C3—C4—C7—O3	163.0 (5)
C2—C1—C6—C5	−2.2 (7)	C5—C4—C7—N2	167.3 (5)
Cl—C1—C6—C5	−178.5 (4)	C3—C4—C7—N2	−15.9 (8)
C2—C1—C6—N1	178.1 (4)	C4—C5—C6—C1	0.0 (7)
Cl—C1—C6—N1	1.8 (7)	C4—C5—C6—N1	179.7 (4)
C1—C2—C3—C4	0.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3ⁱ	0.86	2.10	2.958 (6)	177
N2—H2C···O2ⁱⁱ	0.86	2.26	3.067 (6)	155
C2—H2A···O3ⁱⁱⁱ	0.93	2.42	3.331 (6)	166
C5—H5A···O2	0.93	2.33	2.658 (6)	100

Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₇H₅ClN₂O₃
M_r	200.58
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	8.8490 (18), 7.5470 (15), 12.374 (3)
β (°)	101.18 (3)
V (Å³)	810.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
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	0.879, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	1555, 1459, 1085
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.198, 1.01
No. of reflections	1459
No. of parameters	112
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.51

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
N2—H2B···O3ⁱ	0.86	2.10	2.958 (6)	177.00
N2—H2C···O2ⁱⁱ	0.86	2.26	3.067 (6)	155.00
C2—H2A···O3ⁱⁱⁱ	0.93	2.42	3.331 (6)	166.00
C5—H5A···O2	0.93	2.33	2.658 (6)	100.00

Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

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

References

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