PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3358.
Published online 2010 November 30. doi:  10.1107/S1600536810049226
PMCID: PMC3011469

1-[2-(2-Bromo­phen­yl)eth­yl]-4-chloro-2-nitro­benzene

Abstract

In the title mol­ecule, C14H11BrClNO2, the dihedral angle between the mean planes of the bromo-substitued benzene and the chloro-substituted benzene rings is 1.8 (4) °. The nitro group is twisted by 15.8 (6)° from the mean plane of the benzene ring to which it is attached. The crystal packing is influenced by weak inter­molecular C—H(...)O inter­actions and weak π–π stacking inter­actions [centroid–centroid distances = 3.903 (2), 3.596 (2) and 3.903 (2) Å].

Related literature

For background and a related structure, see: Post & Horn (1977 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3358-scheme1.jpg

Experimental

Crystal data

  • C14H11BrClNO2
  • M r = 340.60
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3358-efi1.jpg
  • a = 15.7756 (4) Å
  • b = 7.3795 (2) Å
  • c = 11.5236 (3) Å
  • V = 1341.53 (6) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 5.99 mm−1
  • T = 150 K
  • 0.47 × 0.35 × 0.12 mm

Data collection

  • Oxford Diffraction Xcalibur Ruby Gemini diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 [triangle]) T min = 0.655, T max = 1.000
  • 3043 measured reflections
  • 1901 independent reflections
  • 1839 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.084
  • S = 1.08
  • 1901 reflections
  • 172 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.51 e Å−3
  • Δρmin = −0.36 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 472 Friedel pairs
  • Flack parameter: 0.04 (2)

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810049226/lh5167sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049226/lh5167Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

MSS thanks R. L. Fine Chem. Bangalore, for the gift sample of the title compound and HSY thanks the University of Mysore for the sanction of sabbatical leave. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

1-(4-Chloro-2-nitrophenethyl)-2-bromobenzene is an intermediate in the synthesis of 10,11–dihydro-5H-dibenzo[b,f]azepine derivatives. It has also been used successfully in the preparation of a number of biologically active compounds and drugs; e.g. the antidepressants imipramine, chloripramine are among the most commonly known. The crystal and molecular structure of the tricyclic antidepressant chlorimipramine hydrochloride is reported (Post & Horn, 1977). In view of the importance of the title compound as a pharmaceutical intermediate, this paper reports its crystal structure.

In the crystal structure of the title compound, C14H11BrClNO2, the dihedral angle between the mean planes of 1-bromo benzene and 2-nitro, 4-chloro benzene rings is 1.8 (4)Å (Fig. 1). The nitro group is twisted 15.8 (6)° from the mean plane of the 2-nitro, 4-chloro benzene ring. Bond angles and distances (Allen et al., 1987) are in normal ranges. Crystal packing is influenced by weak C—H···O intermolecular interactions (Table 2) and weak π–π stacking interactions (Fig. 2).

Experimental

1-[2(2-Bromo-phenylethyl]-4-chloro-2-nitrobenzene was obtained as a gift sample from RL Fine Chem, Bangalore. The compound was recrystallized from dichloromethane (m.p.: 361–363 K).

Refinement

All of the H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.95Å (CH) and 0.99Å (CH2). Isotropic displacement parameters for these atoms were set to 1.18–1.21 (CH), or 1.18 (CH2) times Ueq of the parent atom.

Figures

Fig. 1.
Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
Fig. 2.
Packing diagram of the title compound viewed along the c axis.

Crystal data

C14H11BrClNO2F(000) = 680
Mr = 340.60Dx = 1.686 Mg m3
Orthorhombic, Pna21Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2c -2nCell parameters from 2576 reflections
a = 15.7756 (4) Åθ = 4.8–73.8°
b = 7.3795 (2) ŵ = 5.99 mm1
c = 11.5236 (3) ÅT = 150 K
V = 1341.53 (6) Å3Plate, pale yellow
Z = 40.47 × 0.35 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer1901 independent reflections
Radiation source: Enhance (Cu) X-ray Source1839 reflections with I > 2σ(I)
graphiteRint = 0.021
Detector resolution: 10.5081 pixels mm-1θmax = 74.0°, θmin = 5.6°
ω scansh = −13→19
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)k = −8→8
Tmin = 0.655, Tmax = 1.000l = −11→13
3043 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.084w = 1/[σ2(Fo2) + (0.060P)2 + 0.3149P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
1901 reflectionsΔρmax = 0.51 e Å3
172 parametersΔρmin = −0.36 e Å3
1 restraintAbsolute structure: Flack (1983), 472 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (2)

Special details

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)

xyzUiso*/Ueq
Br0.18735 (2)0.86647 (5)−0.24466 (4)0.03870 (15)
Cl0.01563 (7)0.92827 (15)0.48765 (11)0.0500 (3)
O10.36114 (15)0.8900 (4)0.2328 (3)0.0367 (7)
O20.3344 (2)0.8808 (4)0.4162 (3)0.0452 (7)
N10.31207 (17)0.8805 (4)0.3146 (4)0.0272 (7)
C10.3270 (2)0.9177 (5)−0.0882 (4)0.0258 (7)
C20.3041 (2)0.8721 (5)−0.2013 (4)0.0283 (8)
C30.3634 (3)0.8310 (5)−0.2862 (4)0.0366 (9)
H3A0.34580.8004−0.36260.044*
C40.4477 (3)0.8353 (5)−0.2583 (5)0.0419 (11)
H4A0.48900.8085−0.31570.050*
C50.4730 (3)0.8786 (5)−0.1466 (4)0.0379 (10)
H5A0.53150.8804−0.12750.046*
C60.4135 (2)0.9190 (5)−0.0635 (4)0.0315 (8)
H6A0.43170.94860.01270.038*
C70.2645 (2)0.9579 (4)0.0073 (3)0.0270 (7)
H7A0.21261.0118−0.02640.032*
H7B0.28941.04680.06180.032*
C80.2413 (2)0.7822 (4)0.0736 (3)0.0244 (6)
H8A0.20900.70100.02150.029*
H8B0.29410.71860.09630.029*
C90.18952 (19)0.8201 (5)0.1804 (3)0.0226 (7)
C100.2198 (2)0.8680 (4)0.2905 (3)0.0203 (6)
C110.1674 (2)0.9012 (5)0.3857 (3)0.0268 (7)
H11A0.19050.93170.45930.032*
C120.0819 (3)0.8884 (5)0.3697 (4)0.0309 (8)
C130.0477 (2)0.8412 (4)0.2638 (6)0.0353 (8)
H13A−0.01200.83210.25430.042*
C140.1010 (2)0.8078 (5)0.1726 (3)0.0285 (7)
H14A0.07670.77450.10020.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0430 (2)0.0377 (2)0.0354 (2)−0.00382 (15)−0.0082 (2)0.0031 (2)
Cl0.0498 (6)0.0514 (5)0.0486 (6)0.0055 (5)0.0305 (5)0.0064 (5)
O10.0212 (10)0.0559 (15)0.0331 (18)0.0000 (10)0.0030 (11)−0.0015 (12)
O20.0398 (14)0.066 (2)0.0297 (16)−0.0066 (13)−0.0109 (14)0.0040 (14)
N10.0258 (16)0.0237 (15)0.032 (2)−0.0007 (11)−0.0051 (13)0.0018 (13)
C10.0401 (17)0.0139 (14)0.0234 (18)−0.0017 (12)0.0040 (14)−0.0001 (13)
C20.0379 (19)0.0214 (17)0.0256 (18)−0.0019 (13)0.0027 (14)0.0008 (12)
C30.062 (3)0.0214 (15)0.0261 (18)−0.0024 (16)0.0109 (17)0.0031 (14)
C40.050 (2)0.0329 (17)0.042 (3)0.0008 (15)0.024 (2)0.0017 (19)
C50.036 (2)0.0307 (19)0.047 (3)−0.0015 (14)0.0067 (18)0.0013 (17)
C60.0378 (18)0.0233 (15)0.033 (2)−0.0034 (14)0.0025 (15)0.0012 (15)
C70.0364 (16)0.0208 (14)0.0238 (17)0.0064 (13)0.0037 (14)−0.0006 (12)
C80.0289 (16)0.0196 (14)0.0247 (15)0.0023 (12)0.0003 (12)−0.0021 (12)
C90.0267 (18)0.0149 (14)0.0262 (19)0.0006 (11)0.0007 (13)−0.0024 (14)
C100.0262 (16)0.0136 (14)0.0210 (17)−0.0002 (11)0.0004 (12)0.0021 (9)
C110.0349 (18)0.0198 (15)0.0257 (19)0.0010 (13)0.0029 (15)0.0018 (14)
C120.0359 (19)0.0255 (17)0.0312 (19)0.0023 (13)0.0181 (16)0.0054 (14)
C130.0232 (14)0.0319 (17)0.051 (2)−0.0028 (12)0.003 (2)0.005 (2)
C140.0261 (16)0.0273 (16)0.0322 (19)−0.0031 (13)−0.0055 (14)−0.0010 (15)

Geometric parameters (Å, °)

Br—C21.909 (4)C7—C81.549 (4)
Cl—C121.739 (4)C7—H7A0.9900
O1—N11.222 (5)C7—H7B0.9900
O2—N11.222 (6)C8—C91.503 (5)
N1—C101.485 (4)C8—H8A0.9900
C1—C21.393 (6)C8—H8B0.9900
C1—C61.393 (5)C9—C101.401 (5)
C1—C71.507 (5)C9—C141.403 (4)
C2—C31.388 (6)C10—C111.395 (5)
C3—C41.368 (6)C11—C121.365 (6)
C3—H3A0.9500C11—H11A0.9500
C4—C51.385 (8)C12—C131.379 (8)
C4—H4A0.9500C13—C141.368 (6)
C5—C61.374 (6)C13—H13A0.9500
C5—H5A0.9500C14—H14A0.9500
C6—H6A0.9500
O1—N1—O2123.8 (3)H7A—C7—H7B108.1
O1—N1—C10118.7 (3)C9—C8—C7112.1 (3)
O2—N1—C10117.5 (3)C9—C8—H8A109.2
C2—C1—C6116.6 (4)C7—C8—H8A109.2
C2—C1—C7124.1 (3)C9—C8—H8B109.2
C6—C1—C7119.3 (3)C7—C8—H8B109.2
C3—C2—C1122.5 (4)H8A—C8—H8B107.9
C3—C2—Br117.5 (4)C10—C9—C14114.4 (3)
C1—C2—Br120.0 (3)C10—C9—C8127.1 (3)
C4—C3—C2119.0 (4)C14—C9—C8118.5 (3)
C4—C3—H3A120.5C11—C10—C9123.7 (3)
C2—C3—H3A120.5C11—C10—N1115.0 (3)
C3—C4—C5120.3 (4)C9—C10—N1121.3 (3)
C3—C4—H4A119.9C12—C11—C10117.9 (4)
C5—C4—H4A119.9C12—C11—H11A121.1
C6—C5—C4120.1 (4)C10—C11—H11A121.1
C6—C5—H5A120.0C11—C12—C13121.5 (4)
C4—C5—H5A120.0C11—C12—Cl118.5 (4)
C5—C6—C1121.6 (4)C13—C12—Cl120.0 (3)
C5—C6—H6A119.2C14—C13—C12119.0 (3)
C1—C6—H6A119.2C14—C13—H13A120.5
C1—C7—C8110.5 (3)C12—C13—H13A120.5
C1—C7—H7A109.6C13—C14—C9123.5 (4)
C8—C7—H7A109.6C13—C14—H14A118.3
C1—C7—H7B109.6C9—C14—H14A118.3
C8—C7—H7B109.6
C6—C1—C2—C3−0.4 (5)C8—C9—C10—C11180.0 (3)
C7—C1—C2—C3−178.2 (3)C14—C9—C10—N1177.8 (3)
C6—C1—C2—Br−179.9 (2)C8—C9—C10—N1−2.2 (5)
C7—C1—C2—Br2.4 (5)O1—N1—C10—C11−165.3 (3)
C1—C2—C3—C40.0 (6)O2—N1—C10—C1114.7 (5)
Br—C2—C3—C4179.4 (3)O1—N1—C10—C916.7 (5)
C2—C3—C4—C50.5 (6)O2—N1—C10—C9−163.3 (3)
C3—C4—C5—C6−0.6 (6)C9—C10—C11—C12−0.9 (5)
C4—C5—C6—C10.1 (6)N1—C10—C11—C12−178.8 (3)
C2—C1—C6—C50.4 (5)C10—C11—C12—C131.1 (6)
C7—C1—C6—C5178.3 (3)C10—C11—C12—Cl179.7 (3)
C2—C1—C7—C890.2 (4)C11—C12—C13—C14−0.4 (6)
C6—C1—C7—C8−87.5 (4)Cl—C12—C13—C14−179.0 (3)
C1—C7—C8—C9171.4 (3)C12—C13—C14—C9−0.5 (6)
C7—C8—C9—C10−84.5 (4)C10—C9—C14—C130.7 (5)
C7—C8—C9—C1495.5 (4)C8—C9—C14—C13−179.3 (3)
C14—C9—C10—C110.0 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.952.623.479 (6)150
C13—H13A···O1ii0.952.603.421 (4)145

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

Table 2 Cg···Cg π-stacking interactions, Cg1 and Cg2 are the centroids of rings C1-C6 and C9-C14. [Symmetry codes: (i) 1/2-x, -1/2+y, -1/2+z; (ii) 1/2-x, 1/2+y, -1/2+z; (iii) 1/2-x, -1/2+y,1/2+z; (iv) 1/2-x, 1/2+y,1/2+z].

CgX···CgY (Å)CgX···Perp (Å)CgY···Perp (Å)
Cg1···Cg2i3.903 (2)3.5875 (15)-3.5830 (14)
Cg1···Cg2ii3.596 (2)-3.5429 (15)3.5404 (14)
Cg2···Cg1iii3.596 (2)3.5404 (14)-3.5430 (15)
Cg2···Cg1iv3.903 (2)-3.5830 (14)3.5875 (15)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH5167).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED Oxford Diffraction Ltd, Abingdon, England.
  • Post, M. L. & Horn, A. S. (1977). Acta Cryst. B33, 2590–2595.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography