2,2′-Bi[6,6′-dimethyl­dibenzo[d,f][1,3]dioxepine]

Zhang, H.-Q.; Bao-Li; Yang, G.-D.; Ma, Y.-G.

doi:10.1107/S1600536808009094

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o817

doi:10.1107/S1600536808009094

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2,2′-Bi[6,6′-dimethyldibenzo[d,f][1,3]dioxepine]

Hai-Quan Zhang,^a ^* Bao-Li,^b Guang-Di Yang ^b and Yu-Guang Ma ^b

^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 31 March 2008; accepted 3 April 2008; online 10 April 2008)

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 ); McCullough (1998 ); Samdal & Bastiansen (1985 ); Silcox Yoder & Zuckerman (1967 ); Suzuki (1959 ); Harada et al. (1994 , 1997 ); Pajunen et al. (1996 ).

Experimental

Crystal data

C₃₀H₂₆O₄
M_r = 450.51
Monoclinic, P 2₁ /c
a = 13.2938 (16) Å
b = 7.3200 (17) Å
c = 12.7067 (11) Å
β = 103.61 (3)°
V = 1201.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.18 × 0.13 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.985, T_max = 0.990
5035 measured reflections
2712 independent reflections
1170 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.126
S = 0.81
2712 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009094/dn2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808009094/dn2334Isup2.hkl

checkCIF report

Comment top

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)°.

Related literature top

For related literature, see: Colon & Kelsey (1986); McCullough (1998); Samdal & Bastiansen (1985); Silcox Yoder & Zuckerman (1967); Suzuki (1959); Harada et al. (1994, 1997); Pajunen et al. (1996).

Experimental top

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.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: 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).

Figures top

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].

2,2'-Bi[6,6'-dimethyldibenzo[d,f][1,3]dioxepine] top

Crystal data top

C₃₀H₂₆O₄	F(000) = 476
M_r = 450.51	D_x = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	2712 independent reflections
Radiation source: fine-focus sealed tube	1170 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.072
ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −17→16
T_min = 0.985, T_max = 0.990	k = −9→9
5035 measured reflections	l = 0→16

Refinement top

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(F_o²) + (0.0601P)²] where P = (F_o² + 2F_c²)/3
2712 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₃₀H₂₆O₄	V = 1201.8 (4) Å³
M_r = 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)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2712 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1170 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.990	R_int = 0.072
5035 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 0.81	Δρ_max = 0.13 e Å⁻³
2712 reflections	Δρ_min = −0.17 e Å⁻³
156 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.985, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	5035, 2712, 1170
R_int	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
Δρ_max, Δρ_min (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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