1-Chloro­meth­yl-3-nitro­benzene

Abbasi, M.A.; Jahangir, M.; Akkurt, M.; Aziz-ur-Rehman; Khan, I.U.; Sharif, S.

doi:10.1107/S1600536810005076

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o608

doi:10.1107/S1600536810005076

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1-Chloromethyl-3-nitrobenzene

Muhammad Athar Abbasi,^a ‡ Muhammad Jahangir,^a Mehmet Akkurt,^b ^* Aziz-ur-Rehman,^a Islam Ullah Khan ^a and Shahzad Sharif ^a

^aDepartment of Chemistry, Government College University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 4 February 2010; accepted 8 February 2010; online 13 February 2010)

In the title molecule, C₇H₆ClNO₂, the plane of the nitro group and the direction of the chloromethyl group are twisted away from the benzene ring, forming dihedral angles of 8.2 (3) and 67.55 (12)°, respectively. In the crystal structure, weak intermolecular C—H⋯O interactions link the molecules into corrugated sheets parallel to the bc plane.

Related literature

For the characteristics of nitroaromatic compounds, see: Moreno et al. (1986 ). For details of the synthesis, see: Livermore & Sealock (1947 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₆ClNO₂
M_r = 171.58
Monoclinic, P 2₁ /c
a = 12.1219 (10) Å
b = 4.5104 (4) Å
c = 15.1219 (11) Å
β = 112.709 (2)°
V = 762.69 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 296 K
0.34 × 0.18 × 0.11 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
8475 measured reflections
1903 independent reflections
1350 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.03
1903 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.67	3.583 (3)	166
C6—H6⋯O2ⁱⁱ	0.93	2.67	3.374 (3)	133
Symmetry codes: (i) -x+2, -y+3, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005076/cv2694sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810005076/cv2694Isup2.hkl

checkCIF report

Comment top

The irreversible binding of the reductive intermediates of nitroaromatic compounds to protein and DNA is thought to be responsible for the carcinogenicity and mutagenicity of this class of compounds. Several studies revealed that some nitro radical metabolites with special features are expected to decompose to form neutral carbon-centered free radicals with not net reduction of the nitro group occuring. The radicals anions of p-and o-nitrobenzyl chloride are known to expel chloride to form the corresponding carbon-centered nitrobenzyl radicals with rate constants of 1 × 10⁴ and 4 × 10³s^-1. Such species are highly reactive and could account for the unusual cytotoxicity of these nitrocompounds (Moreno et al., 1986). This structural report on 1-(chloromethyl)-3-nitrobenzene (m-nitrobenzyl chloride) might be helpful to carry out such studies on these nitroaromatic compounds in future.

The molecule of the title compound has normal bond lengths (Allen et al., 1987). The benzene ring (C1-C6) forms dihedral angles of 8.2 (3) and 67.55 (12)°, with the plane of the nitro group (N1/O1/O2) and with the direction of the chloromethyl group (C7/Cl1), respectively.

In the crystal structure, there is no classic hydrogen bonds. Weak intermolecular C—H···O interactions (Table 1) link molecules into corrugated sheets parallel to bc plane.

Related literature top

For the characteristics of nitroaromatic compounds, see: Moreno et al. (1986). For details of the synthesis, see: Livermore & Sealock (1947). For reference bond lengths, see: Allen et al. (1987).

Experimental top

1-(Chloromethyl)-3-nitrobenzene (m-nitrobenzyl chloride) was prepared from the m-nitrobenzyl alcohol, 5 g; being refluxed with 25 ml of concentrated hydrochloric acid on a boiling water bath for 1.5 h. The ether was washed with water and sodium carbonate and dried with sodium sulfate. Evaporation of ether yielded an oily residue which crystallized on cooling. A 70 per cent yield of the crude compound was obtained. Recrystallization from petroleum ether gave a product melting at 317-319 K (Livermore and Sealock, 1947). m-Nitrobenzyl alcohol was purchased from Sigma Aldrich while all other chemicals involved were obtained from Merk, Germany.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

1-Chloromethyl-3-nitrobenzene top

Crystal data top

C₇H₆ClNO₂	F(000) = 352
M_r = 171.58	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2610 reflections
a = 12.1219 (10) Å	θ = 2.8–26.9°
b = 4.5104 (4) Å	µ = 0.44 mm⁻¹
c = 15.1219 (11) Å	T = 296 K
β = 112.709 (2)°	Slab, pale yellow
V = 762.69 (11) Å³	0.34 × 0.18 × 0.11 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	1350 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 28.4°, θ_min = 1.8°
ϕ and ω scans	h = −16→16
8475 measured reflections	k = −6→5
1903 independent reflections	l = −19→20

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0443P)² + 0.2569P] where P = (F_o² + 2F_c²)/3
1903 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₆ClNO₂	V = 762.69 (11) Å³
M_r = 171.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1219 (10) Å	µ = 0.44 mm⁻¹
b = 4.5104 (4) Å	T = 296 K
c = 15.1219 (11) Å	0.34 × 0.18 × 0.11 mm
β = 112.709 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	1350 reflections with I > 2σ(I)
8475 measured reflections	R_int = 0.023
1903 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
1903 reflections	Δρ_min = −0.26 e Å⁻³
100 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl1	0.46056 (5)	0.88735 (16)	0.10489 (5)	0.0856 (2)
O1	0.91285 (17)	1.2499 (5)	0.51307 (11)	0.0999 (7)
O2	0.78454 (18)	0.9074 (5)	0.49378 (12)	0.1009 (8)
N1	0.83972 (16)	1.0739 (5)	0.46346 (11)	0.0666 (6)
C1	0.86599 (17)	1.2052 (5)	0.23036 (13)	0.0593 (6)
C2	0.88908 (16)	1.2205 (5)	0.32703 (13)	0.0559 (6)
C3	0.81640 (15)	1.0604 (4)	0.36006 (11)	0.0499 (5)
C4	0.72367 (16)	0.8898 (4)	0.30166 (13)	0.0540 (6)
C5	0.70089 (15)	0.8763 (4)	0.20455 (13)	0.0526 (6)
C6	0.77357 (17)	1.0351 (4)	0.17013 (12)	0.0559 (6)
C7	0.60014 (19)	0.6926 (5)	0.13890 (17)	0.0738 (8)
H1	0.91350	1.31120	0.20570	0.0710*
H2	0.95160	1.33500	0.36830	0.0670*
H4	0.67650	0.78420	0.32670	0.0650*
H6	0.75960	1.02650	0.10520	0.0670*
H7A	0.59560	0.50880	0.17070	0.0890*
H7B	0.61490	0.64360	0.08200	0.0890*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0538 (3)	0.1001 (5)	0.0947 (4)	−0.0057 (3)	0.0195 (3)	−0.0148 (3)
O1	0.1089 (13)	0.1307 (16)	0.0585 (9)	−0.0134 (13)	0.0306 (9)	−0.0266 (10)
O2	0.1138 (14)	0.1320 (17)	0.0669 (10)	0.0001 (12)	0.0459 (10)	0.0313 (10)
N1	0.0684 (10)	0.0841 (13)	0.0505 (9)	0.0193 (10)	0.0265 (8)	0.0092 (9)
C1	0.0587 (10)	0.0689 (12)	0.0572 (10)	−0.0008 (9)	0.0300 (9)	0.0060 (9)
C2	0.0500 (9)	0.0607 (11)	0.0548 (10)	0.0006 (9)	0.0179 (8)	−0.0025 (9)
C3	0.0518 (9)	0.0558 (11)	0.0436 (8)	0.0127 (8)	0.0200 (7)	0.0054 (7)
C4	0.0546 (9)	0.0498 (10)	0.0624 (10)	0.0059 (8)	0.0278 (8)	0.0097 (8)
C5	0.0517 (9)	0.0445 (10)	0.0583 (10)	0.0084 (8)	0.0175 (8)	−0.0027 (8)
C6	0.0593 (10)	0.0640 (12)	0.0471 (9)	0.0104 (9)	0.0236 (8)	0.0004 (8)
C7	0.0683 (13)	0.0587 (12)	0.0863 (15)	0.0003 (10)	0.0210 (11)	−0.0148 (11)

Geometric parameters (Å, º) top

Cl1—C7	1.796 (3)	C5—C6	1.384 (3)
O1—N1	1.211 (3)	C5—C7	1.493 (3)
O2—N1	1.208 (3)	C1—H1	0.9300
N1—C3	1.479 (2)	C2—H2	0.9300
C1—C2	1.380 (3)	C4—H4	0.9300
C1—C6	1.373 (3)	C6—H6	0.9300
C2—C3	1.374 (3)	C7—H7A	0.9700
C3—C4	1.367 (3)	C7—H7B	0.9700
C4—C5	1.387 (3)

Cl1···H4ⁱ	2.8900	C6···C7^vi	3.560 (3)
O1···N1ⁱⁱ	3.230 (3)	C6···O2^viii	3.374 (3)
O1···O1ⁱⁱ	3.217 (3)	C7···C6^vii	3.560 (3)
O1···O1ⁱⁱⁱ	3.218 (3)	C1···H1^ix	3.0400
O1···C2ⁱⁱ	3.410 (3)	C5···H7A^vi	3.0900
O1···C3ⁱⁱ	3.399 (3)	C6···H7A^vi	3.0400
O2···C6^iv	3.374 (3)	H1···C1^x	3.0400
O1···H2	2.4400	H2···O1	2.4400
O1···H6^v	2.9000	H2···O1ⁱⁱⁱ	2.6700
O1···H2ⁱⁱⁱ	2.6700	H4···O2	2.4200
O2···H4	2.4200	H4···H7A	2.5100
O2···H6^iv	2.6700	H4···Cl1^xi	2.8900
O2···H7B^iv	2.8600	H6···H7B	2.3900
N1···O1ⁱⁱ	3.230 (3)	H6···O1^xii	2.9000
C1···C5^vi	3.566 (3)	H6···O2^viii	2.6700
C2···C4^vi	3.562 (3)	H7A···C5^vii	3.0900
C2···O1ⁱⁱ	3.410 (3)	H7A···C6^vii	3.0400
C3···O1ⁱⁱ	3.399 (3)	H7A···H4	2.5100
C4···C2^vii	3.562 (3)	H7B···H6	2.3900
C5···C1^vii	3.566 (3)	H7B···O2^viii	2.8600

O1—N1—O2	123.57 (18)	C2—C1—H1	120.00
O1—N1—C3	118.53 (19)	C6—C1—H1	120.00
O2—N1—C3	117.90 (18)	C1—C2—H2	121.00
C2—C1—C6	120.7 (2)	C3—C2—H2	121.00
C1—C2—C3	117.56 (18)	C3—C4—H4	120.00
N1—C3—C2	118.37 (17)	C5—C4—H4	120.00
N1—C3—C4	118.69 (17)	C1—C6—H6	120.00
C2—C3—C4	122.94 (16)	C5—C6—H6	120.00
C3—C4—C5	119.12 (18)	Cl1—C7—H7A	109.00
C4—C5—C6	118.70 (17)	Cl1—C7—H7B	109.00
C4—C5—C7	120.40 (18)	C5—C7—H7A	109.00
C6—C5—C7	120.90 (17)	C5—C7—H7B	109.00
C1—C6—C5	120.98 (17)	H7A—C7—H7B	108.00
Cl1—C7—C5	110.94 (15)

O1—N1—C3—C2	8.1 (3)	N1—C3—C4—C5	179.84 (18)
O1—N1—C3—C4	−171.9 (2)	C2—C3—C4—C5	−0.1 (3)
O2—N1—C3—C2	−171.8 (2)	C3—C4—C5—C6	0.4 (3)
O2—N1—C3—C4	8.3 (3)	C3—C4—C5—C7	−179.86 (18)
C6—C1—C2—C3	−0.1 (3)	C4—C5—C6—C1	−0.5 (3)
C2—C1—C6—C5	0.4 (3)	C7—C5—C6—C1	179.7 (2)
C1—C2—C3—N1	180.0 (2)	C4—C5—C7—Cl1	81.5 (2)
C1—C2—C3—C4	−0.1 (3)	C6—C5—C7—Cl1	−98.7 (2)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+3, −z+1; (iv) x, −y+3/2, z+1/2; (v) x, −y+5/2, z+1/2; (vi) x, y+1, z; (vii) x, y−1, z; (viii) x, −y+3/2, z−1/2; (ix) −x+2, y−1/2, −z+1/2; (x) −x+2, y+1/2, −z+1/2; (xi) −x+1, y−1/2, −z+1/2; (xii) x, −y+5/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱⁱⁱ	0.93	2.67	3.583 (3)	166
C6—H6···O2^viii	0.93	2.67	3.374 (3)	133

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

Experimental details

Crystal data
Chemical formula	C₇H₆ClNO₂
M_r	171.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.1219 (10), 4.5104 (4), 15.1219 (11)
β (°)	112.709 (2)
V (Å³)	762.69 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.34 × 0.18 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8475, 1903, 1350
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.03
No. of reflections	1903
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.67	3.583 (3)	166.0
C6—H6···O2ⁱⁱ	0.93	2.67	3.374 (3)	133.0

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

Footnotes

‡Additional corresponding author: atrabbasi@yahoo.com.

Acknowledgements

The authors are grateful to the Higher Education Commission of Pakistan for financial support.

References

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