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access2,10-Dibromo-6,6-dimethyldibenzo[d,f][1,3]dioxepine
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
In the of the title compound, C15H12Br2O2, which was synthesized from 2,10-dibromo-2,2′-dihydroxybiphenyl and 2,2-dimethoxypropane, the aromatic rings are twisted by 35 (1)°. The heterocyclic ring exhibits a twisted conformation.
Related literature
For background literarture on dibenzo[d,f][1,3]dioxepine derivatives, see: Dean (1963![[Dean, F. M. (1963). Naturally Occurring Oxygen Ring Compounds, p. 549. London: Butterworths.]](../../../../../../logos/arrows/e_arr.gif "Dean, F. M. (1963). Naturally Occurring Oxygen Ring Compounds, p. 549. London: Butterworths.")
). For applications, see: He et al. (2003). For the synthesis of the title compound, see: Zhang et al. (2003).
![[Scheme 1]](ng2433scheme1.gif)
Experimental
Crystal data
|
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/S1600536808007186/ng2433sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808007186/ng2433Isup2.hkl
The 2,10-dibro-dimethyl-dibenzo[d,f][1,3]dioxepine was dissolved in ethanol.The solution was allowed to stand at room temperature for several day, white block-shaped crystal was obtained with slow volative solvent.
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 other 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]](./ng2433fig1thm.gif) | Fig. 1. The structure of the title compound, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level of arbitrary radii. |
| C15H12Br2O2 | F(000) = 752 |
| Mr = 384.07 | Dx = 1.854 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 8634 reflections |
| a = 10.8411 (6) Å | θ = 2.5–54.9° |
| b = 7.6902 (3) Å | µ = 5.89 mm−1 |
| c = 16.7466 (8) Å | T = 291 K |
| β = 99.824 (2)° | Block, colorless |
| V = 1375.70 (11) Å3 | 0.07 × 0.06 × 0.06 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID diffractometer | 3145 independent reflections |
| Radiation source: fine-focus sealed tube | 2211 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.023 |
| ω scans | θmax = 27.5°, θmin = 2.1° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −14→14 |
| Tmin = 0.690, Tmax = 0.726 | k = −9→9 |
| 5409 measured reflections | l = −21→21 |
| 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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.058 | H-atom parameters constrained |
| S = 0.94 | w = 1/[σ2(Fo2) + (0.0241P)2] where P = (Fo2 + 2Fc2)/3 |
| 3145 reflections | (Δ/σ)max = 0.002 |
| 174 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| C15H12Br2O2 | V = 1375.70 (11) Å3 |
| Mr = 384.07 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 10.8411 (6) Å | µ = 5.89 mm−1 |
| b = 7.6902 (3) Å | T = 291 K |
| c = 16.7466 (8) Å | 0.07 × 0.06 × 0.06 mm |
| β = 99.824 (2)° |
| Rigaku R-AXIS RAPID diffractometer | 3145 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2211 reflections with I > 2σ(I) |
| Tmin = 0.690, Tmax = 0.726 | Rint = 0.023 |
| 5409 measured reflections |
| R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
| wR(F2) = 0.058 | H-atom parameters constrained |
| S = 0.94 | Δρmax = 0.27 e Å−3 |
| 3145 reflections | Δρmin = −0.29 e Å−3 |
| 174 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 | 0.86808 (3) | 1.13273 (4) | 0.551106 (16) | 0.03688 (10) | |
| Br2 | 1.02801 (3) | 0.90894 (4) | 0.113685 (17) | 0.03706 (10) | |
| C1 | 0.5935 (2) | 0.8979 (3) | 0.33413 (15) | 0.0231 (6) | |
| C2 | 0.5678 (3) | 0.8810 (4) | 0.41168 (15) | 0.0275 (6) | |
| H2 | 0.4948 | 0.8261 | 0.4202 | 0.033* | |
| C3 | 0.6512 (3) | 0.9460 (4) | 0.47671 (16) | 0.0282 (7) | |
| H3 | 0.6350 | 0.9342 | 0.5292 | 0.034* | |
| C4 | 0.7584 (3) | 1.0285 (4) | 0.46290 (15) | 0.0255 (6) | |
| C5 | 0.7875 (3) | 1.0420 (4) | 0.38539 (14) | 0.0256 (6) | |
| H5 | 0.8616 | 1.0949 | 0.3773 | 0.031* | |
| C6 | 0.7041 (3) | 0.9752 (4) | 0.31986 (14) | 0.0224 (6) | |
| C7 | 0.6336 (3) | 1.0283 (4) | 0.17277 (15) | 0.0237 (6) | |
| C8 | 0.7306 (3) | 0.9841 (4) | 0.23570 (15) | 0.0216 (6) | |
| C9 | 0.8488 (3) | 0.9485 (3) | 0.21775 (15) | 0.0242 (6) | |
| H9 | 0.9145 | 0.9188 | 0.2588 | 0.029* | |
| C10 | 0.8673 (3) | 0.9578 (4) | 0.13799 (15) | 0.0247 (6) | |
| C11 | 0.7722 (3) | 1.0031 (4) | 0.07585 (15) | 0.0282 (7) | |
| H11 | 0.7869 | 1.0095 | 0.0228 | 0.034* | |
| C12 | 0.6549 (3) | 1.0388 (4) | 0.09347 (15) | 0.0286 (7) | |
| H12 | 0.5901 | 1.0699 | 0.0521 | 0.034* | |
| C13 | 0.4400 (3) | 0.9391 (4) | 0.21344 (16) | 0.0263 (7) | |
| C14 | 0.3410 (3) | 1.0282 (4) | 0.25113 (17) | 0.0345 (7) | |
| H14A | 0.2855 | 0.9428 | 0.2672 | 0.052* | |
| H14B | 0.2944 | 1.1061 | 0.2125 | 0.052* | |
| H14C | 0.3797 | 1.0927 | 0.2978 | 0.052* | |
| C15 | 0.3877 (3) | 0.8282 (4) | 0.14128 (16) | 0.0339 (7) | |
| H15A | 0.4553 | 0.7807 | 0.1179 | 0.051* | |
| H15B | 0.3354 | 0.8981 | 0.1017 | 0.051* | |
| H15C | 0.3392 | 0.7352 | 0.1583 | 0.051* | |
| O1 | 0.51386 (17) | 0.8227 (2) | 0.26952 (10) | 0.0258 (4) | |
| O2 | 0.51830 (17) | 1.0765 (2) | 0.19107 (10) | 0.0261 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0428 (2) | 0.0392 (2) | 0.02494 (13) | −0.00242 (16) | −0.00487 (12) | −0.00039 (14) |
| Br2 | 0.03242 (18) | 0.0427 (2) | 0.03910 (17) | 0.00823 (16) | 0.01491 (13) | 0.00811 (15) |
| C1 | 0.0206 (14) | 0.0192 (16) | 0.0281 (13) | 0.0013 (13) | 0.0004 (11) | −0.0015 (12) |
| C2 | 0.0244 (15) | 0.0257 (17) | 0.0341 (14) | 0.0030 (13) | 0.0099 (12) | 0.0030 (13) |
| C3 | 0.0309 (17) | 0.0292 (18) | 0.0255 (13) | 0.0066 (14) | 0.0072 (12) | 0.0028 (12) |
| C4 | 0.0297 (17) | 0.0210 (16) | 0.0236 (13) | 0.0043 (13) | −0.0017 (12) | −0.0003 (12) |
| C5 | 0.0206 (15) | 0.0269 (17) | 0.0289 (14) | −0.0012 (13) | 0.0027 (12) | 0.0015 (12) |
| C6 | 0.0222 (16) | 0.0193 (16) | 0.0247 (13) | 0.0027 (12) | 0.0014 (11) | 0.0019 (11) |
| C7 | 0.0223 (16) | 0.0178 (16) | 0.0296 (14) | −0.0020 (12) | 0.0004 (12) | −0.0009 (12) |
| C8 | 0.0218 (15) | 0.0167 (15) | 0.0254 (13) | −0.0026 (12) | 0.0016 (11) | 0.0016 (11) |
| C9 | 0.0212 (16) | 0.0236 (17) | 0.0261 (13) | −0.0033 (12) | −0.0002 (11) | 0.0032 (11) |
| C10 | 0.0225 (16) | 0.0225 (17) | 0.0296 (14) | −0.0011 (13) | 0.0058 (12) | −0.0002 (12) |
| C11 | 0.0302 (18) | 0.0300 (18) | 0.0242 (13) | −0.0056 (14) | 0.0043 (13) | −0.0008 (13) |
| C12 | 0.0265 (17) | 0.0311 (18) | 0.0251 (14) | −0.0027 (14) | −0.0045 (12) | 0.0028 (12) |
| C13 | 0.0190 (16) | 0.0256 (18) | 0.0325 (14) | −0.0018 (13) | −0.0009 (12) | −0.0018 (12) |
| C14 | 0.0241 (17) | 0.035 (2) | 0.0433 (17) | 0.0016 (14) | 0.0042 (14) | −0.0088 (15) |
| C15 | 0.0248 (17) | 0.037 (2) | 0.0376 (15) | −0.0035 (14) | −0.0011 (13) | −0.0103 (15) |
| O1 | 0.0213 (11) | 0.0220 (11) | 0.0323 (9) | −0.0027 (9) | −0.0002 (8) | −0.0019 (9) |
| O2 | 0.0209 (11) | 0.0225 (12) | 0.0337 (10) | 0.0032 (9) | 0.0007 (8) | 0.0023 (9) |
| Br1—C4 | 1.908 (3) | C9—C10 | 1.386 (3) |
| Br2—C10 | 1.893 (3) | C9—H9 | 0.9300 |
| C1—C2 | 1.380 (3) | C10—C11 | 1.379 (4) |
| C1—O1 | 1.390 (3) | C11—C12 | 1.381 (4) |
| C1—C6 | 1.395 (4) | C11—H11 | 0.9300 |
| C2—C3 | 1.385 (4) | C12—H12 | 0.9300 |
| C2—H2 | 0.9300 | C13—O1 | 1.438 (3) |
| C3—C4 | 1.378 (4) | C13—O2 | 1.444 (3) |
| C3—H3 | 0.9300 | C13—C14 | 1.501 (4) |
| C4—C5 | 1.391 (3) | C13—C15 | 1.508 (4) |
| C5—C6 | 1.396 (3) | C14—H14A | 0.9600 |
| C5—H5 | 0.9300 | C14—H14B | 0.9600 |
| C6—C8 | 1.487 (3) | C14—H14C | 0.9600 |
| C7—O2 | 1.387 (3) | C15—H15A | 0.9600 |
| C7—C12 | 1.389 (3) | C15—H15B | 0.9600 |
| C7—C8 | 1.398 (3) | C15—H15C | 0.9600 |
| C8—C9 | 1.393 (4) | ||
| C2—C1—O1 | 119.7 (2) | C11—C10—Br2 | 119.0 (2) |
| C2—C1—C6 | 121.2 (3) | C9—C10—Br2 | 119.1 (2) |
| O1—C1—C6 | 118.8 (2) | C10—C11—C12 | 119.1 (2) |
| C1—C2—C3 | 119.8 (3) | C10—C11—H11 | 120.5 |
| C1—C2—H2 | 120.1 | C12—C11—H11 | 120.5 |
| C3—C2—H2 | 120.1 | C11—C12—C7 | 120.2 (3) |
| C4—C3—C2 | 119.4 (2) | C11—C12—H12 | 119.9 |
| C4—C3—H3 | 120.3 | C7—C12—H12 | 119.9 |
| C2—C3—H3 | 120.3 | O1—C13—O2 | 109.8 (2) |
| C3—C4—C5 | 121.6 (3) | O1—C13—C14 | 111.6 (2) |
| C3—C4—Br1 | 119.7 (2) | O2—C13—C14 | 105.6 (2) |
| C5—C4—Br1 | 118.7 (2) | O1—C13—C15 | 105.2 (2) |
| C4—C5—C6 | 119.1 (3) | O2—C13—C15 | 111.3 (2) |
| C4—C5—H5 | 120.5 | C14—C13—C15 | 113.4 (2) |
| C6—C5—H5 | 120.5 | C13—C14—H14A | 109.5 |
| C1—C6—C5 | 118.9 (2) | C13—C14—H14B | 109.5 |
| C1—C6—C8 | 119.5 (2) | H14A—C14—H14B | 109.5 |
| C5—C6—C8 | 121.6 (2) | C13—C14—H14C | 109.5 |
| O2—C7—C12 | 119.9 (2) | H14A—C14—H14C | 109.5 |
| O2—C7—C8 | 119.3 (2) | H14B—C14—H14C | 109.5 |
| C12—C7—C8 | 120.5 (3) | C13—C15—H15A | 109.5 |
| C9—C8—C7 | 119.1 (2) | C13—C15—H15B | 109.5 |
| C9—C8—C6 | 122.0 (2) | H15A—C15—H15B | 109.5 |
| C7—C8—C6 | 118.9 (2) | C13—C15—H15C | 109.5 |
| C10—C9—C8 | 119.2 (3) | H15A—C15—H15C | 109.5 |
| C10—C9—H9 | 120.4 | H15B—C15—H15C | 109.5 |
| C8—C9—H9 | 120.4 | C1—O1—C13 | 116.9 (2) |
| C11—C10—C9 | 121.9 (3) | C7—O2—C13 | 116.9 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C15H12Br2O2 |
| Mr | 384.07 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 291 |
| a, b, c (Å) | 10.8411 (6), 7.6902 (3), 16.7466 (8) |
| β (°) | 99.824 (2) |
| V (Å3) | 1375.70 (11) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 5.89 |
| Crystal size (mm) | 0.07 × 0.06 × 0.06 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID diffractometer |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.690, 0.726 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5409, 3145, 2211 |
| Rint | 0.023 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.058, 0.94 |
| No. of reflections | 3145 |
| No. of parameters | 174 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.27, −0.29 |
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 by the National Science Foundation of China (20125421, 90101026, 50303007 and 60207003) and the Ministry of Science and Technology of China (2002CB6134003 and 2003 cb3147032).
References
Dean, F. M. (1963). Naturally Occurring Oxygen Ring Compounds, p. 549. London: Butterworths. Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Dibenzo[d,f][1,3]dioxepine derivatives is very important in pharmaceutical applications (Dean, 1963). In fact it has been found that such a structure, which is probably related to their pharmacological activiry, is present in many biologically active natural products. Introducing functional group Br on benzene ring of dibenzo[d,f][1,3] dioxepine can expand the field of their application, such as photoluminescence, electro-luminescence devices and nonlinear optics (. We have reported the synthesis of the 2,10-dibro-dimethyl- dibenzo[d,f][1,3]dioxepine (Zhang et al., 2003).Herein we present the crysal structure of the title compound.