1-Chloro­methyl-4-nitro­benzene

In the title compound, C₇H₆ClNO₂, the nitro group is almost coplanar with the aromatic ring [dihedral angle = 2.9 (2)°], but the Cl atom deviates from the ring plane by 1.129 (1) Å. In the crystal, mol­ecules are linked by weak C—H⋯O inter­actions to generate chains.

Related literature

For background on the toxicity of nitro-aromatic compounds, see: Moreno et al. (1986). For the synthesis of the title compound, see: Livermore & Sealock (1947). For bond-length data, see: Allen et al. (1987).

Experimental

Crystal data

• C₇H₆ClNO₂

• M_r = 171.58

• Orthorhombic, P 2₁ 2₁ 2₁

• a = 4.7434 (1) Å

• b = 6.4189 (2) Å

• c = 24.9413 (11) Å

• V = 759.40 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.45 mm⁻¹

• T = 296 K

• 0.35 × 0.11 × 0.10 mm

Data collection

• Bruker APEXII CCD diffractometer

• 4389 measured reflections

• 1816 independent reflections

• 1586 reflections with I > 2σ(I)

• R_int = 0.018

Refinement

• R[F² > 2σ(F²)] = 0.041

• wR(F²) = 0.103

• S = 1.04

• 1816 reflections

• 100 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

• Absolute structure: Flack (1983), 662 Freidel pairs

• Flack parameter: 0.02 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1^i	0.97	2.48	3.396 (3)	158
Symmetry code: (i) x-1, y+1, z.

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 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST (Nardelli, 1983) and PLATON (Spek, 2009).

Supporting information

S1. Comment

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 occurring. 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 × 103 s^-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)-4-nitrobenzene (p-nitrobenzyl chloride) might be helpful to carry out such studies on these nitroaromatic compounds in future.

The title molecule (I), (Fig. 1), is non-planar and the dihedral angle between the plane of the NO₂ group and benzene (C1–C6) ring is 2.9 (2)°, while the C5—C4—C7—Cl1 torsion angle is 83.8 (2)°. In (I), the bond lengths (Allen et al., 1987) and angles have values within the normal ranges.

In the crystal structure, there is no classic hydrogen bonds. A weak intermolecular C—H···O interaction contrubutes to the stability of the structure (Table 1, Fig. 2).

Related literature

For background on the toxicity of nitro-aromatic compounds, see: Moreno et al. (1986). For the synthesis of the title compound, see: Livermore & Sealock (1947). For bond-length data, see: Allen et al. (1987).

S2. Experimental

The title p-nitrobenzyl chloride was prepared by adding 5.3 ml of benzyl chloride slowly and with stirring to 27.5 ml of a mixture of equal parts of concentrated nitric and sulfuric acids cooled to 283 K. The temperature rose to 303 K during the 10 min required for the addition. The mixture was stirred for 30 min and then poured into 50 g of crushed ice. The crude material was recrystallized from ethanol. Product obtained was dissolved in ethanol and crystallized by slow evaporation of the solvent to yield colourless needles of (I) in an over-all yield of 46% (Livermore & Sealock, 1947).

S3. Refinement

H atoms were positioned geometrically (C—H = 0.93 and 0.97 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

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 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST (Nardelli, 1983) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title molecule, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing and the hydrogen bonding of (I) viewed down the a-axis. H-atoms not involved in hydrogen bonds have been omitted for clarity.

1-Chloromethyl-4-nitrobenzene

Crystal data

C7H6ClNO2	F(000) = 352
Mr = 171.58	Dx = 1.501 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1957 reflections
a = 4.7434 (1) Å	θ = 3.3–26.7°
b = 6.4189 (2) Å	µ = 0.45 mm^−1
c = 24.9413 (11) Å	T = 296 K
V = 759.40 (4) Å^3	Needle, colourless
Z = 4	0.35 × 0.11 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	1586 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.018
Graphite monochromator	θmax = 28.3°, θmin = 3.3°
ϕ and ω scans	h = −5→6
4389 measured reflections	k = −8→5
1816 independent reflections	l = −33→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.049P)^2 + 0.1709P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1816 reflections	Δρmax = 0.33 e Å^−3
100 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Absolute structure: Flack (1983), 662 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (11)

Special details

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 e.s.d.'s 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.75015 (18)	0.45250 (12)	0.22343 (3)	0.0812 (3)
O1	1.4188 (4)	−0.3381 (3)	0.07002 (7)	0.0621 (6)
O2	1.4761 (4)	−0.0854 (3)	0.01453 (7)	0.0601 (6)
N1	1.3647 (3)	−0.1634 (3)	0.05351 (7)	0.0434 (5)
C1	1.1532 (4)	−0.0398 (3)	0.08269 (7)	0.0364 (5)
C2	1.0829 (4)	0.1540 (3)	0.06377 (7)	0.0421 (6)
C3	0.8901 (4)	0.2704 (3)	0.09215 (8)	0.0437 (6)
C4	0.7690 (4)	0.1928 (3)	0.13883 (7)	0.0393 (5)
C5	0.8402 (5)	−0.0046 (3)	0.15629 (8)	0.0472 (6)
C6	1.0341 (5)	−0.1235 (3)	0.12836 (8)	0.0459 (6)
C7	0.5663 (5)	0.3213 (4)	0.17034 (8)	0.0533 (7)
H2	1.16370	0.20560	0.03250	0.0510*
H3	0.84040	0.40230	0.08000	0.0520*
H5	0.75690	−0.05800	0.18710	0.0570*
H6	1.08280	−0.25630	0.14000	0.0550*
H7A	0.42040	0.23280	0.18530	0.0640*
H7B	0.47710	0.42290	0.14710	0.0640*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0957 (5)	0.0831 (5)	0.0647 (4)	0.0041 (4)	0.0047 (4)	−0.0299 (3)
O1	0.0677 (11)	0.0514 (9)	0.0671 (10)	0.0222 (8)	−0.0024 (8)	0.0041 (8)
O2	0.0584 (10)	0.0629 (11)	0.0591 (9)	0.0072 (8)	0.0175 (8)	0.0010 (8)
N1	0.0412 (8)	0.0450 (9)	0.0440 (8)	0.0046 (8)	−0.0047 (7)	−0.0051 (7)
C1	0.0336 (8)	0.0382 (9)	0.0374 (8)	0.0008 (7)	−0.0048 (7)	−0.0001 (7)
C2	0.0446 (10)	0.0451 (11)	0.0366 (9)	0.0024 (9)	0.0012 (7)	0.0076 (8)
C3	0.0496 (11)	0.0409 (10)	0.0406 (9)	0.0079 (9)	−0.0016 (8)	0.0079 (8)
C4	0.0362 (9)	0.0460 (10)	0.0357 (8)	0.0024 (9)	−0.0033 (7)	−0.0008 (7)
C5	0.0526 (11)	0.0495 (12)	0.0394 (9)	−0.0012 (9)	0.0046 (8)	0.0080 (8)
C6	0.0500 (11)	0.0405 (10)	0.0471 (10)	0.0015 (9)	0.0001 (9)	0.0084 (8)
C7	0.0510 (12)	0.0613 (13)	0.0475 (11)	0.0111 (12)	0.0033 (9)	−0.0004 (10)

Geometric parameters (Å, º)

Cl1—C7	1.795 (2)	C4—C7	1.491 (3)
O1—N1	1.222 (3)	C5—C6	1.383 (3)
O2—N1	1.215 (2)	C2—H2	0.9300
N1—C1	1.472 (3)	C3—H3	0.9300
C1—C2	1.372 (3)	C5—H5	0.9300
C1—C6	1.380 (3)	C6—H6	0.9300
C2—C3	1.377 (3)	C7—H7A	0.9700
C3—C4	1.391 (3)	C7—H7B	0.9700
C4—C5	1.382 (3)
O1—N1—O2	123.83 (19)	C1—C2—H2	121.00
O1—N1—C1	118.12 (17)	C3—C2—H2	121.00
O2—N1—C1	118.05 (18)	C2—C3—H3	120.00
N1—C1—C2	118.98 (16)	C4—C3—H3	120.00
N1—C1—C6	118.51 (17)	C4—C5—H5	120.00
C2—C1—C6	122.51 (18)	C6—C5—H5	120.00
C1—C2—C3	118.48 (17)	C1—C6—H6	121.00
C2—C3—C4	120.69 (18)	C5—C6—H6	121.00
C3—C4—C5	119.43 (18)	Cl1—C7—H7A	110.00
C3—C4—C7	120.64 (18)	Cl1—C7—H7B	110.00
C5—C4—C7	119.93 (18)	C4—C7—H7A	110.00
C4—C5—C6	120.65 (18)	C4—C7—H7B	110.00
C1—C6—C5	118.22 (18)	H7A—C7—H7B	108.00
Cl1—C7—C4	109.58 (16)
O1—N1—C1—C2	−177.90 (18)	C1—C2—C3—C4	−0.2 (3)
O1—N1—C1—C6	2.4 (3)	C2—C3—C4—C5	−1.0 (3)
O2—N1—C1—C2	2.4 (3)	C2—C3—C4—C7	178.30 (19)
O2—N1—C1—C6	−177.28 (19)	C3—C4—C5—C6	1.2 (3)
N1—C1—C2—C3	−178.37 (17)	C7—C4—C5—C6	−178.1 (2)
C6—C1—C2—C3	1.3 (3)	C3—C4—C7—Cl1	−95.5 (2)
N1—C1—C6—C5	178.55 (18)	C5—C4—C7—Cl1	83.8 (2)
C2—C1—C6—C5	−1.1 (3)	C4—C5—C6—C1	−0.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1^i	0.97	2.48	3.396 (3)	158

Symmetry code: (i) x−1, y+1, z.

 

Footnotes

‡Additional corresponding author, e-mail: [e-mail].