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ISSN: 2056-9890

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

aState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, People's Republic of China, and bState Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, People's Republic of China
*Correspondence e-mail: hqzhang@ysu.edu.cn

(Received 10 April 2008; accepted 16 June 2008; online 19 June 2008)

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[Mislow, K. & Glass, M. (1961). J. Am. Chem. Soc. 83, 2780-2781.]).

[Scheme 1]

Experimental

Crystal data
  • C14H10Br2O

  • Mr = 354.04

  • Orthorhombic, P b c n

  • 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.457, Tmax = 0.498 (expected range = 0.419–0.456)

  • 2468 measured reflections

  • 1371 independent reflections

  • 896 reflections with I > 2σ(I)

  • Rint = 0.014

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 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[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The structure of the title compound, with the atom-labelling Displacement ellipsoids are drawn at the 30% probability level of arbitrary radii.
[Figure 2] Fig. 2. The synthesis route for the preparation of 3,9-dibromo-5,7-dihydro-dibenzo[c,e]oxepine.
3,9-Dibromo-5,7-dihydrodibenzo[c,e]oxepine top
Crystal data top
C14H10Br2OF(000) = 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 = 2.5–54.9°
b = 10.2476 (6) ŵ = 6.54 mm1
c = 7.2626 (14) ÅT = 291 K
V = 1235.2 (2) Å3Block, colorless
Z = 40.14 × 0.14 × 0.12 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1371 independent reflections
Radiation source: fine-focus sealed tube896 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 2121
Tmin = 0.457, Tmax = 0.498k = 1312
2468 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.042H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0103P)2]
where P = (Fo2 + 2Fc2)/3
1371 reflections(Δ/σ)max < 0.001
78 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C14H10Br2OV = 1235.2 (2) Å3
Mr = 354.04Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 16.5965 (3) ŵ = 6.54 mm1
b = 10.2476 (6) ÅT = 291 K
c = 7.2626 (14) Å0.14 × 0.14 × 0.12 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1371 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
896 reflections with I > 2σ(I)
Tmin = 0.457, Tmax = 0.498Rint = 0.014
2468 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.042H-atom parameters constrained
S = 1.05Δρmax = 0.28 e Å3
1371 reflectionsΔρmin = 0.46 e Å3
78 parameters
Special details top

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) top
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) top
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)0.0000.0084 (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, º) top
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 code: (i) x+2, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H10Br2O
Mr354.04
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)291
a, b, c (Å)16.5965 (3), 10.2476 (6), 7.2626 (14)
V3)1235.2 (2)
Z4
Radiation typeMo Kα
µ (mm1)6.54
Crystal size (mm)0.14 × 0.14 × 0.12
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.457, 0.498
No. of measured, independent and
observed [I > 2σ(I)] reflections
2468, 1371, 896
Rint0.014
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.042, 1.05
No. of reflections1371
No. of parameters78
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.46

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

 

Acknowledgements

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).

References

First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationMislow, K. & Glass, M. (1961). J. Am. Chem. Soc. 83, 2780–2781.  CrossRef CAS Web of Science Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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COMMUNICATIONS
ISSN: 2056-9890
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