PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1304.
Published online 2008 June 19. doi:  10.1107/S1600536808018175
PMCID: PMC2961808

3,9-Dibromo-5,7-dihydro­dibenzo[c,e]oxepine

Abstract

The title compound, C14H10Br2O, is a biphenyl derivative containing a –CH2—O—CH2– bridge in the 2,2′-position. The compound displays a twisted conformation with the two benzene rings making a dihedral angle of 45.02 (5)°, while the central seven-membered ring is in a boat conformation. The mol­ecule lies on a crystallographic twofold axis of symmetry passing through the O atom and bis­ecting the 1,1′ C—C bond.

Related literature

For a previous synthesis of related biphenyl mol­ecules, see: Mislow & Glass (1961 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1304-scheme1.jpg

Experimental

Crystal data

  • C14H10Br2O
  • M r = 354.04
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1304-efi1.jpg
  • a = 16.5965 (3) Å
  • b = 10.2476 (6) Å
  • c = 7.2626 (14) Å
  • V = 1235.2 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.54 mm−1
  • T = 291 (2) K
  • 0.14 × 0.14 × 0.12 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.457, T max = 0.498 (expected range = 0.419–0.456)
  • 2468 measured reflections
  • 1371 independent reflections
  • 896 reflections with I > 2σ(I)
  • R int = 0.014

Refinement

  • R[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.042
  • S = 1.05
  • 1371 reflections
  • 78 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018175/bv2098sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018175/bv2098Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the National Science Foundation of China (20125421, 90101026, 50303007 and 60207003) and the Ministry of Science and Technology of China (2002CB6134003 and 2003CB3147032).

supplementary crystallographic information

Comment

The dibenzo[c,e]oxepine derivatives were studied due to their optical activity as discussed in a previous article (Mislow & Glass, 1961). Introducing functional groups such as Br on the benzene ring of the dibenzo[c,e]oxepine can expand the range of their applications, such as photoluminescence, electro-luminescence devices and nonlinear optics. Herein we present the crystal structure of the title compound. In orthorhombic (space group Pbcn) crystals of 3,9-dibromo-5,7-dihydro-dibenzo[c,e]oxepine, there are four molecules in the unit cell. The molecule lies on a crystallographic 2-fold axis of symmetry passing through the O and bisecting the C4-C4a bond. The compound exhibits twisted conformation between two phenyl rings with a dihedral angle of 45.02 (5)°, while central 7-member ring is in a boat conformation.

Experimental

The four-step reaction to prepare 3,9-dibromo-5,7 -dihydro dibenzo [c,e] oxepin is described as follows: (1) 2,7-Dibromo-phenanthrenequinone was obtained by directly brominating phenanthrenequinone in presence N-bromosuccinamide (NBS) in H2SO4. (2) This was followed by oxidation of 2,7-dibromophenanthrenequinone in the presence of pure oxygen and Cu(I)Cl to give 4,4-dibromodiphenic acid. (3). The reduction of 4,4-dibromodiphenic acid using NaBH4 gave 4,4'-dibromo-2,2'-bis-(hydroxymethyl)-biphenyl. (4) The final production was obtained by ring closure of 4,4'-dibromo-2,2'-bis-(hydroxymethyl)-biphenyl in the presence of HBr acid. Single-crystals of X-ray diffraction quality were grown by slow evaporation of a ethanol solution.

Refinement

C-bound H atoms were geometrically positioned with C—H = 0.97 Å, Uiso(H) = 1.5Ueq(C) for methyl and C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) for carbon atoms.

Figures

Fig. 1.
The structure of the title compound, with the atom-labelling Displacement ellipsoids are drawn at the 30% probability level of arbitrary radii.
Fig. 2.
The synthesis route for the preparation of 3,9-dibromo-5,7-dihydro-dibenzo[c,e]oxepine.

Crystal data

C14H10Br2OF000 = 688
Mr = 354.04Dx = 1.904 Mg m3
Orthorhombic, PbcnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 10356 reflections
a = 16.5965 (3) Åθ = 2.5–54.9º
b = 10.2476 (6) ŵ = 6.54 mm1
c = 7.2626 (14) ÅT = 291 (2) K
V = 1235.2 (2) Å3Block, colorless
Z = 40.14 × 0.14 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer1371 independent reflections
Radiation source: fine-focus sealed tube896 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.014
T = 291(2) Kθmax = 27.5º
ω scansθmin = 2.3º
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)h = −21→21
Tmin = 0.457, Tmax = 0.498k = −13→12
2468 measured reflectionsl = −9→9

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.042  w = 1/[σ2(Fo2) + (0.0103P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1371 reflectionsΔρmax = 0.28 e Å3
78 parametersΔρmin = −0.46 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
Br10.677363 (15)0.36711 (3)0.14224 (4)0.04966 (11)
O11.00000.0746 (2)0.25000.0401 (7)
C10.79077 (14)0.3698 (3)0.1813 (3)0.0333 (6)
C60.82561 (17)0.4814 (3)0.2538 (3)0.0392 (7)
H6A0.79430.55340.28460.047*
C30.91882 (13)0.2642 (2)0.1600 (3)0.0251 (5)
C70.96934 (14)0.1504 (2)0.1017 (3)0.0342 (6)
H7A0.93730.09440.02280.041*
H7B1.01430.18250.02930.041*
C40.95561 (13)0.3761 (2)0.2353 (3)0.0273 (5)
C20.83600 (13)0.2626 (2)0.1339 (3)0.0295 (6)
H2A0.81120.18910.08450.035*
C50.90852 (16)0.4830 (3)0.2793 (3)0.0361 (7)
H5A0.93290.55740.32700.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.03162 (14)0.0648 (2)0.05259 (17)0.01473 (19)−0.00240 (17)0.0052 (2)
O10.0350 (15)0.0224 (14)0.0629 (18)0.000−0.0084 (15)0.000
C10.0301 (13)0.0443 (16)0.0257 (13)0.0091 (16)0.0001 (11)0.0004 (15)
C60.0487 (17)0.0390 (16)0.0299 (13)0.0231 (19)−0.0067 (15)−0.0083 (12)
C30.0245 (13)0.0250 (13)0.0260 (12)0.0011 (12)0.0036 (13)0.0030 (12)
C70.0270 (13)0.0304 (15)0.0452 (16)−0.0031 (13)0.0024 (12)−0.0083 (12)
C40.0331 (13)0.0259 (13)0.0230 (11)0.0045 (14)−0.0011 (12)0.0022 (12)
C20.0321 (15)0.0282 (13)0.0283 (12)0.0001 (12)0.0023 (15)−0.0005 (12)
C50.0489 (18)0.0275 (15)0.0321 (13)0.0069 (16)−0.0108 (14)−0.0061 (12)

Geometric parameters (Å, °)

Br1—C11.904 (2)C3—C41.410 (3)
O1—C7i1.422 (3)C3—C71.497 (3)
O1—C71.422 (3)C7—H7A0.9700
C1—C21.375 (3)C7—H7B0.9700
C1—C61.386 (3)C4—C51.383 (3)
C6—C51.389 (3)C4—C4i1.489 (4)
C6—H6A0.9300C2—H2A0.9300
C3—C21.388 (3)C5—H5A0.9300
C7i—O1—C7113.8 (2)O1—C7—H7B108.7
C2—C1—C6121.8 (2)C3—C7—H7B108.7
C2—C1—Br1119.40 (19)H7A—C7—H7B107.6
C6—C1—Br1118.8 (2)C5—C4—C3119.3 (2)
C1—C6—C5118.3 (2)C5—C4—C4i121.75 (17)
C1—C6—H6A120.9C3—C4—C4i118.96 (16)
C5—C6—H6A120.9C1—C2—C3119.8 (2)
C2—C3—C4119.5 (2)C1—C2—H2A120.1
C2—C3—C7120.5 (2)C3—C2—H2A120.1
C4—C3—C7120.0 (2)C4—C5—C6121.4 (3)
O1—C7—C3114.29 (19)C4—C5—H5A119.3
O1—C7—H7A108.7C6—C5—H5A119.3
C3—C7—H7A108.7

Symmetry codes: (i) −x+2, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2098).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Mislow, K. & Glass, M. (1961). J. Am. Chem. Soc.83, 2780–2781.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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