1,3-Bis(bromo­meth­yl)-2-nitro­benzene

Arshad, M.N.; Edson, K.Z.; Mough, S.T.; Holman, K.T.

doi:10.1107/S160053681000718X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o834

doi:10.1107/S160053681000718X

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1,3-Bis(bromomethyl)-2-nitrobenzene

Muhammad Nadeem Arshad,^a ‡ Katheryne Zumberge Edson,^b Scott T. Mough ^b and K. Travis Holman ^b ^*

^aDepartment of Chemistry, GC University Lahore 54000, Pakistan, and ^bDepartment of Chemistry, Georgetown University, 37th and O St NW, Washington, DC 20057, USA
^*Correspondence e-mail: kth7@georgetown.edu

(Received 4 February 2010; accepted 24 February 2010; online 13 March 2010)

In the title compound, C₈H₇Br₂NO₂, an intermediate for the synthesis of macrocycles, the NO₂ group makes a dihedral angle of 65.07 (19)° with the arene ring, and the bromomethyl substituents adopt a trans conformation about the ring such that the molecule closely approximates C2 symmetry.

Related literature

For related structures, see: Li et al. (2006 ); Qin et al. (2005 ). For related compounds, see: Raatikainen et al. (2008 ); Mough et al. (2004 ). For the synthesis, see: Boeckmann & Vögtle (1981 ).

Experimental

Crystal data

C₈H₇Br₂NO₂
M_r = 308.97
Monoclinic, P 2₁ /n
a = 7.7837 (13) Å
b = 7.7573 (13) Å
c = 15.938 (3) Å
β = 90.933 (3)°
V = 962.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 8.39 mm⁻¹
T = 185 K
0.20 × 0.20 × 0.08 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.285, T_max = 0.553
8228 measured reflections
2259 independent reflections
1812 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.083
S = 1.06
2259 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 1.35 e Å⁻³
Δρ_min = −1.31 e Å⁻³

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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 ), PLATON (Spek, 2009 ) and X-SEED (Barbour, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681000718X/ng2729sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000718X/ng2729Isup2.hkl

checkCIF report

Comment top

Derivatives of 1,3-bis(bromomethyl)benzene have been widely used to synthesize macrocycles via S_N2 reactions. For recent examples, see Raatikainen et al., 2008 and Mough et al., 2004.

The crystal structure of the title compound is in comparison with the already reported 1,3-bis(bromomethyl)benzene (II) (Li et al., 2006) and 2,3-bis(bromomethyl)-1-methoxy-4-nitrobenzene (III) (Qin et al., 2005). The nitro group of I is oriented at a dihedral angle of 65.07(0.19)° to the arene ring. The bromomethyl groups (C7/Br1 and C8/Br2) are oriented anti to each other and exhibit almost identical dihedral angles with respect to arene ring carbons atoms (80.34(0.27)° and 80.99(0.28)°, respectively). The molecules therefore closely approximate C2 point group symmetry in the crystal.

Related literature top

For related structures, see: Li et al. (2006); Qin et al. (2005). For related compounds, see: Raatikainen et al. (2008); Mough et al. (2004). For the synthesis, see: Boeckmann & Vögtle (1981).

Experimental top

The title compound was prepared following the method reported by Boeckmann and Vögtle et al., 1981.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009) and X-SEED (Barbour, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The labelled thermal ellipsoid plot of (I) at the 50% probability level.
	Fig. 2. The unit cell packing diagram of (I) as viewed down the b axis.

1,3-Bis(bromomethyl)-2-nitrobenzene top

Crystal data top

C₈H₇Br₂NO₂	F(000) = 592
M_r = 308.97	D_x = 2.133 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1024 reflections
a = 7.7837 (13) Å	θ = 2.6–28.0°
b = 7.7573 (13) Å	µ = 8.39 mm⁻¹
c = 15.938 (3) Å	T = 185 K
β = 90.933 (3)°	Needles, colorless
V = 962.2 (3) Å³	0.20 × 0.20 × 0.08 mm
Z = 4

Data collection top

Bruker SMART 1K diffractometer	2259 independent reflections
Radiation source: fine-focus sealed tube	1812 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω scan	θ_max = 28.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.285, T_max = 0.553	k = −10→10
8228 measured reflections	l = −21→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0289P)² + 1.9462P] where P = (F_o² + 2F_c²)/3
2259 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 1.35 e Å⁻³
0 restraints	Δρ_min = −1.31 e Å⁻³

Crystal data top

C₈H₇Br₂NO₂	V = 962.2 (3) Å³
M_r = 308.97	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7837 (13) Å	µ = 8.39 mm⁻¹
b = 7.7573 (13) Å	T = 185 K
c = 15.938 (3) Å	0.20 × 0.20 × 0.08 mm
β = 90.933 (3)°

Data collection top

Bruker SMART 1K diffractometer	2259 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1812 reflections with I > 2σ(I)
T_min = 0.285, T_max = 0.553	R_int = 0.041
8228 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.06	Δρ_max = 1.35 e Å⁻³
2259 reflections	Δρ_min = −1.31 e Å⁻³
118 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br1	0.20766 (5)	0.59088 (5)	0.74548 (2)	0.03326 (13)
Br2	0.26732 (6)	0.86865 (6)	0.32665 (3)	0.04186 (15)
C1	0.2474 (4)	0.6504 (4)	0.5246 (2)	0.0211 (7)
N1	0.2391 (4)	0.8324 (4)	0.55227 (19)	0.0245 (7)
C2	0.1776 (4)	0.6087 (4)	0.4461 (2)	0.0203 (7)
C3	0.1891 (5)	0.4378 (5)	0.4212 (2)	0.0238 (8)
H3	0.1450	0.4051	0.3676	0.029*
O1	0.3753 (4)	0.9089 (4)	0.5617 (2)	0.0434 (8)
C6	0.3228 (4)	0.5301 (5)	0.5786 (2)	0.0205 (7)
C5	0.3295 (5)	0.3604 (5)	0.5504 (2)	0.0249 (8)
H5	0.3807	0.2750	0.5855	0.030*
C7	0.3935 (5)	0.5748 (5)	0.6637 (2)	0.0281 (8)
H7A	0.4550	0.6864	0.6610	0.034*
H7B	0.4768	0.4854	0.6820	0.034*
O2	0.0993 (4)	0.8953 (4)	0.5634 (2)	0.0426 (8)
C4	0.2638 (5)	0.3131 (5)	0.4729 (2)	0.0260 (8)
H4	0.2695	0.1965	0.4550	0.031*
C8	0.0943 (5)	0.7371 (5)	0.3889 (2)	0.0259 (8)
H8A	0.0239	0.8174	0.4222	0.031*
H8B	0.0170	0.6766	0.3487	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0391 (2)	0.0396 (2)	0.0212 (2)	−0.00245 (18)	0.00494 (16)	−0.00610 (16)
Br2	0.0346 (2)	0.0541 (3)	0.0370 (3)	−0.0017 (2)	0.00213 (18)	0.0232 (2)
C1	0.0198 (17)	0.0187 (17)	0.0247 (18)	−0.0006 (14)	0.0027 (14)	−0.0005 (14)
N1	0.0324 (18)	0.0223 (16)	0.0188 (15)	0.0027 (13)	−0.0022 (13)	0.0000 (12)
C2	0.0161 (16)	0.0231 (18)	0.0218 (18)	−0.0003 (14)	0.0033 (14)	0.0018 (14)
C3	0.0227 (18)	0.030 (2)	0.0190 (18)	−0.0043 (15)	0.0030 (15)	−0.0041 (15)
O1	0.0381 (17)	0.0343 (16)	0.058 (2)	−0.0126 (14)	0.0095 (15)	−0.0141 (15)
C6	0.0153 (16)	0.0287 (18)	0.0175 (17)	−0.0005 (14)	0.0020 (14)	0.0005 (14)
C5	0.0254 (19)	0.0218 (17)	0.028 (2)	0.0038 (15)	0.0060 (16)	0.0076 (15)
C7	0.0247 (19)	0.038 (2)	0.0215 (19)	0.0002 (16)	−0.0013 (15)	0.0014 (16)
O2	0.0310 (16)	0.0359 (16)	0.061 (2)	0.0146 (13)	−0.0064 (15)	−0.0158 (15)
C4	0.0258 (19)	0.0215 (18)	0.031 (2)	−0.0022 (15)	0.0074 (16)	−0.0021 (15)
C8	0.0228 (19)	0.031 (2)	0.0236 (19)	−0.0007 (16)	0.0001 (15)	0.0058 (15)

Geometric parameters (Å, º) top

Br1—C7	1.967 (4)	C3—H3	0.9500
Br2—C8	1.971 (4)	C6—C5	1.392 (5)
C1—C6	1.392 (5)	C6—C7	1.497 (5)
C1—C2	1.395 (5)	C5—C4	1.379 (5)
C1—N1	1.480 (5)	C5—H5	0.9500
N1—O2	1.209 (4)	C7—H7A	0.9900
N1—O1	1.222 (4)	C7—H7B	0.9900
C2—C3	1.387 (5)	C4—H4	0.9500
C2—C8	1.491 (5)	C8—H8A	0.9900
C3—C4	1.392 (5)	C8—H8B	0.9900

C6—C1—C2	123.6 (3)	C6—C5—H5	119.2
C6—C1—N1	118.4 (3)	C6—C7—Br1	110.6 (2)
C2—C1—N1	118.0 (3)	C6—C7—H7A	109.5
O2—N1—O1	124.5 (3)	Br1—C7—H7A	109.5
O2—N1—C1	118.2 (3)	C6—C7—H7B	109.5
O1—N1—C1	117.3 (3)	Br1—C7—H7B	109.5
C3—C2—C1	116.9 (3)	H7A—C7—H7B	108.1
C3—C2—C8	119.6 (3)	C5—C4—C3	119.4 (3)
C1—C2—C8	123.5 (3)	C5—C4—H4	120.3
C2—C3—C4	121.6 (3)	C3—C4—H4	120.3
C2—C3—H3	119.2	C2—C8—Br2	111.1 (2)
C4—C3—H3	119.2	C2—C8—H8A	109.4
C1—C6—C5	116.9 (3)	Br2—C8—H8A	109.4
C1—C6—C7	123.3 (3)	C2—C8—H8B	109.4
C5—C6—C7	119.7 (3)	Br2—C8—H8B	109.4
C4—C5—C6	121.7 (3)	H8A—C8—H8B	108.0
C4—C5—H5	119.2

C6—C1—N1—O2	−115.0 (4)	N1—C1—C6—C5	−179.6 (3)
C2—C1—N1—O2	64.5 (5)	C2—C1—C6—C7	−178.4 (3)
C6—C1—N1—O1	65.5 (5)	N1—C1—C6—C7	1.0 (5)
C2—C1—N1—O1	−115.1 (4)	C1—C6—C5—C4	−0.3 (5)
C6—C1—C2—C3	−1.5 (5)	C7—C6—C5—C4	179.1 (3)
N1—C1—C2—C3	179.1 (3)	C1—C6—C7—Br1	80.1 (4)
C6—C1—C2—C8	179.0 (3)	C5—C6—C7—Br1	−99.3 (3)
N1—C1—C2—C8	−0.4 (5)	C6—C5—C4—C3	0.2 (5)
C1—C2—C3—C4	1.2 (5)	C2—C3—C4—C5	−0.6 (5)
C8—C2—C3—C4	−179.2 (3)	C3—C2—C8—Br2	−98.9 (3)
C2—C1—C6—C5	1.0 (5)	C1—C2—C8—Br2	80.6 (4)

Experimental details

Crystal data
Chemical formula	C₈H₇Br₂NO₂
M_r	308.97
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	185
a, b, c (Å)	7.7837 (13), 7.7573 (13), 15.938 (3)
β (°)	90.933 (3)
V (Å³)	962.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.39
Crystal size (mm)	0.20 × 0.20 × 0.08

Data collection
Diffractometer	Bruker SMART 1K diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.285, 0.553
No. of measured, independent and observed [I > 2σ(I)] reflections	8228, 2259, 1812
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.083, 1.06
No. of reflections	2259
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.35, −1.31

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009) and X-SEED (Barbour, 2001), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Footnotes

‡Current address: Department of Chemistry, Georgetown University, 37th and O St NW, Washington, DC 20057 USA.

Acknowledgements

The authors acknowledge Higher Education Commission of Pakistan for providing a fellowship to MNA under the International Research Support Initiative Programme (IRSIP). KTH acknowledges grant support from the National Science Foundation (DMR-0349316).

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