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access3,9-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
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.]](../../../../../../logos/arrows/e_arr.gif "Mislow, K. & Glass, M. (1961). J. Am. Chem. Soc. 83, 2780-2781.")
).
![[Scheme 1]](bv2098scheme1.gif)
Experimental
Crystal data
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; 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.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536808018175/bv2098sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808018175/bv2098Isup2.hkl
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.
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.
Data collection: RAPID-AUTO (Rigaku, 1998); cell 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).
![[Figure 1]](./bv2098fig1thm.gif) | 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]](./bv2098fig2thm.gif) | Fig. 2. The synthesis route for the preparation of 3,9-dibromo-5,7-dihydro-dibenzo[c,e]oxepine. |
| C14H10Br2O | F(000) = 688 |
| Mr = 354.04 | Dx = 1.904 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 10356 reflections |
| a = 16.5965 (3) Å | θ = 2.5–54.9° |
| b = 10.2476 (6) Å | µ = 6.54 mm−1 |
| c = 7.2626 (14) Å | T = 291 K |
| V = 1235.2 (2) Å3 | Block, colorless |
| Z = 4 | 0.14 × 0.14 × 0.12 mm |
| Rigaku R-AXIS RAPID diffractometer | 1371 independent reflections |
| Radiation source: fine-focus sealed tube | 896 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.014 |
| ω scans | θmax = 27.5°, θmin = 2.3° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −21→21 |
| Tmin = 0.457, Tmax = 0.498 | k = −13→12 |
| 2468 measured reflections | l = −9→9 |
| 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.042 | H-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 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.46 e Å−3 |
| C14H10Br2O | V = 1235.2 (2) Å3 |
| Mr = 354.04 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 16.5965 (3) Å | µ = 6.54 mm−1 |
| b = 10.2476 (6) Å | T = 291 K |
| c = 7.2626 (14) Å | 0.14 × 0.14 × 0.12 mm |
| 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 = 0.498 | Rint = 0.014 |
| 2468 measured reflections |
| R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
| wR(F2) = 0.042 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.28 e Å−3 |
| 1371 reflections | Δρmin = −0.46 e Å−3 |
| 78 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.677363 (15) | 0.36711 (3) | 0.14224 (4) | 0.04966 (11) | |
| O1 | 1.0000 | 0.0746 (2) | 0.2500 | 0.0401 (7) | |
| C1 | 0.79077 (14) | 0.3698 (3) | 0.1813 (3) | 0.0333 (6) | |
| C6 | 0.82561 (17) | 0.4814 (3) | 0.2538 (3) | 0.0392 (7) | |
| H6A | 0.7943 | 0.5534 | 0.2846 | 0.047* | |
| C3 | 0.91882 (13) | 0.2642 (2) | 0.1600 (3) | 0.0251 (5) | |
| C7 | 0.96934 (14) | 0.1504 (2) | 0.1017 (3) | 0.0342 (6) | |
| H7A | 0.9373 | 0.0944 | 0.0228 | 0.041* | |
| H7B | 1.0143 | 0.1825 | 0.0293 | 0.041* | |
| C4 | 0.95561 (13) | 0.3761 (2) | 0.2353 (3) | 0.0273 (5) | |
| C2 | 0.83600 (13) | 0.2626 (2) | 0.1339 (3) | 0.0295 (6) | |
| H2A | 0.8112 | 0.1891 | 0.0845 | 0.035* | |
| C5 | 0.90852 (16) | 0.4830 (3) | 0.2793 (3) | 0.0361 (7) | |
| H5A | 0.9329 | 0.5574 | 0.3270 | 0.043* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.03162 (14) | 0.0648 (2) | 0.05259 (17) | 0.01473 (19) | −0.00240 (17) | 0.0052 (2) |
| O1 | 0.0350 (15) | 0.0224 (14) | 0.0629 (18) | 0.000 | −0.0084 (15) | 0.000 |
| C1 | 0.0301 (13) | 0.0443 (16) | 0.0257 (13) | 0.0091 (16) | 0.0001 (11) | 0.0004 (15) |
| C6 | 0.0487 (17) | 0.0390 (16) | 0.0299 (13) | 0.0231 (19) | −0.0067 (15) | −0.0083 (12) |
| C3 | 0.0245 (13) | 0.0250 (13) | 0.0260 (12) | 0.0011 (12) | 0.0036 (13) | 0.0030 (12) |
| C7 | 0.0270 (13) | 0.0304 (15) | 0.0452 (16) | −0.0031 (13) | 0.0024 (12) | −0.0083 (12) |
| C4 | 0.0331 (13) | 0.0259 (13) | 0.0230 (11) | 0.0045 (14) | −0.0011 (12) | 0.0022 (12) |
| C2 | 0.0321 (15) | 0.0282 (13) | 0.0283 (12) | 0.0001 (12) | 0.0023 (15) | −0.0005 (12) |
| C5 | 0.0489 (18) | 0.0275 (15) | 0.0321 (13) | 0.0069 (16) | −0.0108 (14) | −0.0061 (12) |
| Br1—C1 | 1.904 (2) | C3—C4 | 1.410 (3) |
| O1—C7i | 1.422 (3) | C3—C7 | 1.497 (3) |
| O1—C7 | 1.422 (3) | C7—H7A | 0.9700 |
| C1—C2 | 1.375 (3) | C7—H7B | 0.9700 |
| C1—C6 | 1.386 (3) | C4—C5 | 1.383 (3) |
| C6—C5 | 1.389 (3) | C4—C4i | 1.489 (4) |
| C6—H6A | 0.9300 | C2—H2A | 0.9300 |
| C3—C2 | 1.388 (3) | C5—H5A | 0.9300 |
| C7i—O1—C7 | 113.8 (2) | O1—C7—H7B | 108.7 |
| C2—C1—C6 | 121.8 (2) | C3—C7—H7B | 108.7 |
| C2—C1—Br1 | 119.40 (19) | H7A—C7—H7B | 107.6 |
| C6—C1—Br1 | 118.8 (2) | C5—C4—C3 | 119.3 (2) |
| C1—C6—C5 | 118.3 (2) | C5—C4—C4i | 121.75 (17) |
| C1—C6—H6A | 120.9 | C3—C4—C4i | 118.96 (16) |
| C5—C6—H6A | 120.9 | C1—C2—C3 | 119.8 (2) |
| C2—C3—C4 | 119.5 (2) | C1—C2—H2A | 120.1 |
| C2—C3—C7 | 120.5 (2) | C3—C2—H2A | 120.1 |
| C4—C3—C7 | 120.0 (2) | C4—C5—C6 | 121.4 (3) |
| O1—C7—C3 | 114.29 (19) | C4—C5—H5A | 119.3 |
| O1—C7—H7A | 108.7 | C6—C5—H5A | 119.3 |
| C3—C7—H7A | 108.7 |
| Symmetry code: (i) −x+2, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C14H10Br2O |
| Mr | 354.04 |
| Crystal system, space group | Orthorhombic, Pbcn |
| Temperature (K) | 291 |
| a, b, c (Å) | 16.5965 (3), 10.2476 (6), 7.2626 (14) |
| V (Å3) | 1235.2 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 6.54 |
| Crystal size (mm) | 0.14 × 0.14 × 0.12 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID diffractometer |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.457, 0.498 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 2468, 1371, 896 |
| Rint | 0.014 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.042, 1.05 |
| No. of reflections | 1371 |
| No. of parameters | 78 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 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
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Mislow, K. & Glass, M. (1961). J. Am. Chem. Soc. 83, 2780–2781. CrossRef CAS Web of Science Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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.