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access2,2′-Bi[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
The title compound, C30H26O4, is a dimer of 6,6′-dimethyldibenzo[d,f][1,3]dioxepine linked by formation of a C—C bond in the para position with respect to one O atom. The dimer is arranged around an inversion centre. As is usually observed in related compounds, the dibenzo group is twisted, the two benzene rings making a dihedral angle of 41.56 (9)°. The seven-membered ring exhibits a twisted conformation.
Related literature
For related literature, see: Colon & Kelsey (1986![[Colon, I. & Kelsey, D. R. (1986). J. Org. Chem. 51, 2627-2637. ]](../../../../../../logos/arrows/e_arr.gif "Colon, I. & Kelsey, D. R. (1986). J. Org. Chem. 51, 2627-2637.")
); McCullough (1998); Samdal & Bastiansen (1985); Silcox Yoder & Zuckerman (1967); Suzuki (1959); Harada et al. (1994, 1997); Pajunen et al. (1996).
![[Scheme 1]](dn2334scheme1.gif)
Experimental
Crystal data
|
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku , 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536808009094/dn2334sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808009094/dn2334Isup2.hkl
Synthesis approach of dimeric 6,6'-dimethyl-dibenzo [d,f][1,3]dioxepine was described as follows: The precursor 5-bromo-2,2'-dihydroxybiphenyl was synthesized by directly brominating of dihydroxybiphenyl. The 2-bromo-6,6'-dimethyl- dibenzo [d, f][1, 3] dioxepine was obtained according to the previously reportable reaction condition (Silcox Yoder & Zuckerman, 1967). Finally, the meta-linked dimeric 6,6'-dimethyl-dibenzo [d, f][1, 3] dioxepine was prepared according to the typical Yamamoto condition (Colon et al., 1986). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a ethanol solution.
All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) and 0.96 Å (methyl) with Uiso(H) = 1.2Ueq(aromatic) or Uiso(H) = 1.5Ueq(methyl).
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku , 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2334fig1thm.gif) | Fig. 1. Molecular view of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry code: (i) 1-x, 1-y, 1-z]. |
| C30H26O4 | F(000) = 476 |
| Mr = 450.51 | Dx = 1.245 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2961 reflections |
| a = 13.2938 (16) Å | θ = 5.1–54.6° |
| b = 7.3200 (17) Å | µ = 0.08 mm−1 |
| c = 12.7067 (11) Å | T = 293 K |
| β = 103.61 (3)° | Block, colorless |
| V = 1201.8 (4) Å3 | 0.18 × 0.13 × 0.13 mm |
| Z = 2 |
| Rigaku R-AXIS RAPID diffractometer | 2712 independent reflections |
| Radiation source: fine-focus sealed tube | 1170 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.072 |
| ω scans | θmax = 27.5°, θmin = 1.6° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −17→16 |
| Tmin = 0.985, Tmax = 0.990 | k = −9→9 |
| 5035 measured reflections | l = 0→16 |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.126 | H-atom parameters constrained |
| S = 0.81 | w = 1/[σ2(Fo2) + (0.0601P)2] where P = (Fo2 + 2Fc2)/3 |
| 2712 reflections | (Δ/σ)max < 0.001 |
| 156 parameters | Δρmax = 0.13 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C30H26O4 | V = 1201.8 (4) Å3 |
| Mr = 450.51 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 13.2938 (16) Å | µ = 0.08 mm−1 |
| b = 7.3200 (17) Å | T = 293 K |
| c = 12.7067 (11) Å | 0.18 × 0.13 × 0.13 mm |
| β = 103.61 (3)° |
| Rigaku R-AXIS RAPID diffractometer | 2712 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1170 reflections with I > 2σ(I) |
| Tmin = 0.985, Tmax = 0.990 | Rint = 0.072 |
| 5035 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
| wR(F2) = 0.126 | H-atom parameters constrained |
| S = 0.81 | Δρmax = 0.13 e Å−3 |
| 2712 reflections | Δρmin = −0.17 e Å−3 |
| 156 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| C1 | 0.65924 (15) | 0.3273 (3) | 0.74573 (16) | 0.0426 (5) | |
| C2 | 0.59655 (17) | 0.4785 (3) | 0.74799 (17) | 0.0541 (6) | |
| H2 | 0.5968 | 0.5361 | 0.8133 | 0.065* | |
| C3 | 0.53331 (16) | 0.5431 (3) | 0.65184 (17) | 0.0554 (6) | |
| H3 | 0.4909 | 0.6434 | 0.6542 | 0.066* | |
| C4 | 0.53170 (14) | 0.4619 (3) | 0.55227 (16) | 0.0400 (5) | |
| C5 | 0.59453 (15) | 0.3071 (3) | 0.55358 (16) | 0.0411 (5) | |
| H5 | 0.5941 | 0.2488 | 0.4884 | 0.049* | |
| C6 | 0.65776 (15) | 0.2372 (3) | 0.64907 (16) | 0.0394 (5) | |
| C7 | 0.72262 (15) | 0.0713 (3) | 0.65022 (17) | 0.0418 (5) | |
| C8 | 0.68640 (17) | −0.0820 (3) | 0.58720 (19) | 0.0523 (6) | |
| H8 | 0.6193 | −0.0829 | 0.5441 | 0.063* | |
| C9 | 0.74995 (19) | −0.2334 (3) | 0.5884 (2) | 0.0610 (7) | |
| H9 | 0.7250 | −0.3349 | 0.5463 | 0.073* | |
| C10 | 0.85074 (19) | −0.2339 (3) | 0.6522 (2) | 0.0605 (7) | |
| H10 | 0.8932 | −0.3348 | 0.6517 | 0.073* | |
| C11 | 0.88765 (17) | −0.0849 (3) | 0.71621 (18) | 0.0524 (6) | |
| H11 | 0.9546 | −0.0854 | 0.7595 | 0.063* | |
| C12 | 0.82413 (15) | 0.0658 (3) | 0.71547 (16) | 0.0409 (5) | |
| C13 | 0.82810 (16) | 0.2702 (3) | 0.86599 (17) | 0.0477 (6) | |
| C14 | 0.86854 (19) | 0.1391 (4) | 0.95822 (19) | 0.0705 (8) | |
| H14A | 0.8475 | 0.0170 | 0.9356 | 0.106* | |
| H14B | 0.8411 | 0.1718 | 1.0191 | 0.106* | |
| H14C | 0.9427 | 0.1453 | 0.9785 | 0.106* | |
| C15 | 0.86209 (18) | 0.4649 (4) | 0.89127 (19) | 0.0651 (7) | |
| H15A | 0.9360 | 0.4726 | 0.9031 | 0.098* | |
| H15B | 0.8416 | 0.5042 | 0.9552 | 0.098* | |
| H15C | 0.8303 | 0.5420 | 0.8315 | 0.098* | |
| O1 | 0.86503 (10) | 0.2224 (2) | 0.77162 (11) | 0.0462 (4) | |
| O2 | 0.71592 (11) | 0.2534 (2) | 0.84347 (11) | 0.0493 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0361 (12) | 0.0505 (14) | 0.0436 (13) | 0.0058 (10) | 0.0139 (10) | 0.0117 (11) |
| C2 | 0.0607 (14) | 0.0664 (17) | 0.0377 (12) | 0.0200 (13) | 0.0166 (11) | 0.0001 (11) |
| C3 | 0.0576 (15) | 0.0582 (16) | 0.0529 (14) | 0.0273 (12) | 0.0183 (12) | 0.0067 (12) |
| C4 | 0.0332 (11) | 0.0441 (13) | 0.0430 (12) | 0.0054 (9) | 0.0098 (9) | 0.0036 (10) |
| C5 | 0.0393 (12) | 0.0404 (13) | 0.0430 (12) | 0.0015 (10) | 0.0089 (10) | −0.0004 (10) |
| C6 | 0.0349 (11) | 0.0384 (13) | 0.0457 (12) | 0.0019 (9) | 0.0110 (10) | 0.0073 (11) |
| C7 | 0.0384 (12) | 0.0401 (13) | 0.0483 (12) | 0.0036 (10) | 0.0129 (10) | 0.0064 (10) |
| C8 | 0.0451 (13) | 0.0463 (15) | 0.0636 (15) | 0.0007 (12) | 0.0090 (11) | 0.0006 (12) |
| C9 | 0.0665 (18) | 0.0381 (15) | 0.0815 (19) | 0.0002 (12) | 0.0234 (15) | −0.0035 (13) |
| C10 | 0.0590 (16) | 0.0491 (17) | 0.0763 (17) | 0.0181 (12) | 0.0218 (14) | 0.0135 (14) |
| C11 | 0.0453 (13) | 0.0566 (16) | 0.0551 (14) | 0.0131 (12) | 0.0114 (11) | 0.0078 (12) |
| C12 | 0.0403 (12) | 0.0411 (13) | 0.0428 (12) | 0.0027 (10) | 0.0127 (10) | 0.0069 (10) |
| C13 | 0.0401 (13) | 0.0612 (17) | 0.0413 (12) | 0.0084 (11) | 0.0085 (10) | 0.0063 (12) |
| C14 | 0.0671 (16) | 0.090 (2) | 0.0531 (15) | 0.0251 (15) | 0.0109 (13) | 0.0220 (14) |
| C15 | 0.0653 (16) | 0.074 (2) | 0.0551 (15) | 0.0012 (14) | 0.0116 (13) | −0.0098 (13) |
| O1 | 0.0390 (8) | 0.0568 (10) | 0.0443 (8) | 0.0003 (7) | 0.0127 (7) | 0.0004 (8) |
| O2 | 0.0426 (9) | 0.0647 (11) | 0.0422 (8) | 0.0092 (7) | 0.0131 (7) | 0.0162 (8) |
| C1—C2 | 1.389 (3) | C9—H9 | 0.9300 |
| C1—C6 | 1.390 (3) | C10—C11 | 1.380 (3) |
| C1—O2 | 1.401 (2) | C10—H10 | 0.9300 |
| C2—C3 | 1.393 (3) | C11—C12 | 1.388 (3) |
| C2—H2 | 0.9300 | C11—H11 | 0.9300 |
| C3—C4 | 1.394 (3) | C12—O1 | 1.391 (2) |
| C3—H3 | 0.9300 | C13—O1 | 1.442 (3) |
| C4—C5 | 1.405 (3) | C13—O2 | 1.456 (3) |
| C4—C4i | 1.503 (4) | C13—C15 | 1.507 (3) |
| C5—C6 | 1.400 (3) | C13—C14 | 1.512 (3) |
| C5—H5 | 0.9300 | C14—H14A | 0.9600 |
| C6—C7 | 1.488 (3) | C14—H14B | 0.9600 |
| C7—C8 | 1.397 (3) | C14—H14C | 0.9600 |
| C7—C12 | 1.408 (3) | C15—H15A | 0.9600 |
| C8—C9 | 1.391 (3) | C15—H15B | 0.9600 |
| C8—H8 | 0.9300 | C15—H15C | 0.9600 |
| C9—C10 | 1.393 (3) | ||
| C2—C1—C6 | 120.82 (19) | C11—C10—H10 | 120.0 |
| C2—C1—O2 | 119.3 (2) | C9—C10—H10 | 120.0 |
| C6—C1—O2 | 119.53 (19) | C10—C11—C12 | 119.5 (2) |
| C1—C2—C3 | 119.6 (2) | C10—C11—H11 | 120.2 |
| C1—C2—H2 | 120.2 | C12—C11—H11 | 120.2 |
| C3—C2—H2 | 120.2 | C11—C12—O1 | 119.18 (18) |
| C2—C3—C4 | 121.9 (2) | C11—C12—C7 | 121.6 (2) |
| C2—C3—H3 | 119.0 | O1—C12—C7 | 118.90 (19) |
| C4—C3—H3 | 119.0 | O1—C13—O2 | 110.46 (15) |
| C3—C4—C5 | 116.81 (19) | O1—C13—C15 | 105.26 (18) |
| C3—C4—C4i | 122.0 (2) | O2—C13—C15 | 111.31 (18) |
| C5—C4—C4i | 121.2 (2) | O1—C13—C14 | 111.23 (19) |
| C6—C5—C4 | 122.6 (2) | O2—C13—C14 | 105.06 (19) |
| C6—C5—H5 | 118.7 | C15—C13—C14 | 113.6 (2) |
| C4—C5—H5 | 118.7 | C13—C14—H14A | 109.5 |
| C1—C6—C5 | 118.23 (19) | C13—C14—H14B | 109.5 |
| C1—C6—C7 | 119.41 (18) | H14A—C14—H14B | 109.5 |
| C5—C6—C7 | 122.36 (19) | C13—C14—H14C | 109.5 |
| C8—C7—C12 | 117.9 (2) | H14A—C14—H14C | 109.5 |
| C8—C7—C6 | 121.97 (18) | H14B—C14—H14C | 109.5 |
| C12—C7—C6 | 120.12 (19) | C13—C15—H15A | 109.5 |
| C9—C8—C7 | 120.5 (2) | C13—C15—H15B | 109.5 |
| C9—C8—H8 | 119.8 | H15A—C15—H15B | 109.5 |
| C7—C8—H8 | 119.8 | C13—C15—H15C | 109.5 |
| C8—C9—C10 | 120.5 (2) | H15A—C15—H15C | 109.5 |
| C8—C9—H9 | 119.8 | H15B—C15—H15C | 109.5 |
| C10—C9—H9 | 119.8 | C12—O1—C13 | 117.27 (16) |
| C11—C10—C9 | 120.0 (2) | C1—O2—C13 | 117.00 (16) |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C30H26O4 |
| Mr | 450.51 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 13.2938 (16), 7.3200 (17), 12.7067 (11) |
| β (°) | 103.61 (3) |
| V (Å3) | 1201.8 (4) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.18 × 0.13 × 0.13 |
| Data collection | |
| Diffractometer | Rigaku R-AXIS RAPID diffractometer |
| Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
| Tmin, Tmax | 0.985, 0.990 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5035, 2712, 1170 |
| Rint | 0.072 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.126, 0.81 |
| No. of reflections | 2712 |
| No. of parameters | 156 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.17 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Molecular Structure Corporation & Rigaku , 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).
Acknowledgements
The authors acknowledge financial support from the National Science Foundation of China (20125421, 90101026, 50303007 and 60207003) and by the Ministry of Science and Technology of China (2002CB6134003 and 2003CB3147032).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The inter-ring twisted angles in biphenyl compounds are widely studied because changing of conformations of the conjugated molecules affect the optical and electronic properties significantly (McCullough, 1998). Most of biphenyl derivatives showed the twisting conformation in their gas phase or solution, while in crytal a few of them have planar or nearly planar conformation at room temperature (Samdal et al., 1985; Suzuki, 1959). Strong face-to-face interactions induced planar conformation of solid biphenyl.
The title compound, C30H26O4, is a dimer of the 6,6'-dimethyl-dibenzo [d,f][1,3]dioxepin linked by formation of a C-C bond in para position with respect to one O atom (Fig. 1). This dimer is arranged around inversion centre. As usually observed in related compounds ( Pajunen et al., 1996; Harada et al., 1994,1997), the dibenzo group is twisted with the two benzene rings making a dihedral angle of 41.56?(9)°.