2′,10′-Dibromo­spiro­[cylohexane-1,6-di­benzo[d,f][1,3]dioxepine]

Zhang, C.-B.; Zhang, H.-Q.; Li, Q.-S.; Xing, G.-Z.

doi:10.1107/S1600536810012535

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1047

https://doi.org/10.1107/S1600536810012535

Open

access

2′,10′-Dibromospiro[cylohexane-1,6-dibenzo[d,f][1,3]dioxepine]

Cheng-Bo Zhang,^a Hai-Quan Zhang,^a ^* Qing-Shan Li ^a and Guang-Zhong Xing ^a

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

(Received 25 March 2010; accepted 3 April 2010; online 10 April 2010)

In the title compound, C₁₈H₁₆Br₂O₂, the dihedral angle between the aromatic rings is 35.55 (17)° and the cyclohexyl ring adopts a chair-like conformation. In the crystal, molecules are linked by van der Waals forces.

Related literature

For background literature concerning title compound, see Dean (1963 ); Yang et al. (2004 ). For details of the synthesis, see Zhang et al. (2003 ).

Experimental

Crystal data

C₁₈H₁₆Br₂O₂
M_r = 424.13
Orthorhombic, P b c a
a = 17.793 (4) Å
b = 10.143 (5) Å
c = 18.279 (5) Å
V = 3299 (2) Å³
Z = 8
Mo Kα radiation
μ = 4.92 mm⁻¹
T = 290 K
0.13 × 0.12 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.567, T_max = 0.614
29533 measured reflections
3735 independent reflections
2294 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.111
S = 1.00
3735 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: 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, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012535/ng2752sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012535/ng2752Isup2.hkl

checkCIF report

Comment top

Dibenzo[d,f] [1,3] dioxepine derivatives are important seven-member-ring type bridged biphenyl compounds, which proved highly significant for pharmaceutical field (Dean, 1963). Introducing functional group Br on benzene ring of dibenzo[d,f][1,3] dioxepine derivatives can expandthe field of their application, such as photoluminescence, electro-luminescence devices and nonlinear potics etc ( Yang et al., 2004). Herein we present the crysal structure of the title compound.

The molecule structure of title compound, (I), C₁₈H₁₆Br₂O₂, as shown in Fig. 1, all bond lengths and angles are in normal range. In the crystal structure, the six-membered ring formed by C13 to C18 is in the chair-like comformation. The plane of two benzene rings form a dihedral angle of 35.33 (17) °. The crystal packing is stabilized by van der Waals' force.

Related literature top

For background literature concerning title compound, see Dean (1963); Yang et al. (2004). For details of the synthesis, see Zhang et al. (2003).

Experimental top

The title compound was prepared according to the literature (Zhang et al., 2003). Single crystals suitable for X-ray diffraction were prepared by slow evaperation of an ethanol soluion.

Structure description top

For background literature concerning title compound, see Dean (1963); Yang et al. (2004). For details of the synthesis, see Zhang et al. (2003).

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, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric of title compound, with the atom numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probalility level.

2',10'-Dibromospiro[cylohexane-1,6-dibenzo[d,f][1,3]dioxepine] top

Crystal data top

C₁₈H₁₆Br₂O₂	F(000) = 1680
M_r = 424.13	D_x = 1.708 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3788 reflections
a = 17.793 (4) Å	θ = 2.2–54.8°
b = 10.143 (5) Å	µ = 4.92 mm⁻¹
c = 18.279 (5) Å	T = 290 K
V = 3299 (2) Å³	Block, white
Z = 8	0.13 × 0.12 × 0.11 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3735 independent reflections
Radiation source: fine-focus sealed tube	2294 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→23
T_min = 0.567, T_max = 0.614	k = −12→12
29533 measured reflections	l = −23→23

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.049P)² + 1.6141P] where P = (F_o² + 2F_c²)/3
3735 reflections	(Δ/σ)_max = 0.016
199 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

C₁₈H₁₆Br₂O₂	V = 3299 (2) Å³
M_r = 424.13	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 17.793 (4) Å	µ = 4.92 mm⁻¹
b = 10.143 (5) Å	T = 290 K
c = 18.279 (5) Å	0.13 × 0.12 × 0.11 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3735 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2294 reflections with I > 2σ(I)
T_min = 0.567, T_max = 0.614	R_int = 0.088
29533 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
3735 reflections	Δρ_min = −0.64 e Å⁻³
199 parameters

Special details top

Experimental. (See detailed section in the paper)

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
Br1	1.04490 (3)	0.06701 (5)	0.35791 (2)	0.07070 (18)
Br2	0.85968 (3)	0.22102 (6)	0.73751 (2)	0.0790 (2)
C1	1.0023 (2)	0.2318 (4)	0.38479 (19)	0.0504 (10)
C2	1.0211 (2)	0.3410 (4)	0.3440 (2)	0.0509 (10)
H2	1.0543	0.3341	0.3049	0.061*
C3	0.9896 (2)	0.4612 (4)	0.36234 (18)	0.0468 (9)
H3	1.0008	0.5357	0.3348	0.056*
C4	0.94151 (19)	0.4708 (4)	0.42156 (18)	0.0384 (8)
C5	0.92258 (19)	0.3603 (4)	0.46297 (17)	0.0393 (8)
C6	0.9533 (2)	0.2386 (4)	0.44328 (18)	0.0447 (9)
H6	0.9409	0.1629	0.4693	0.054*
C7	0.8410 (2)	0.3224 (4)	0.65214 (18)	0.0487 (9)
C8	0.8863 (2)	0.3024 (4)	0.59131 (18)	0.0436 (9)
H8	0.9245	0.2400	0.5928	0.052*
C9	0.87442 (18)	0.3757 (4)	0.52831 (17)	0.0375 (8)
C10	0.81592 (19)	0.4670 (4)	0.52830 (17)	0.0399 (8)
C11	0.7721 (2)	0.4878 (4)	0.5897 (2)	0.0485 (9)
H11	0.7339	0.5504	0.5887	0.058*
C12	0.7850 (2)	0.4158 (4)	0.65240 (19)	0.0532 (10)
H12	0.7564	0.4302	0.6942	0.064*
C13	0.84221 (18)	0.6288 (4)	0.43511 (18)	0.0402 (8)
C14	0.8204 (2)	0.6406 (4)	0.35503 (17)	0.0488 (9)
H14A	0.7663	0.6509	0.3512	0.059*
H14B	0.8343	0.5603	0.3295	0.059*
C15	0.8591 (2)	0.7583 (5)	0.3188 (2)	0.0610 (12)
H15A	0.9128	0.7420	0.3163	0.073*
H15B	0.8406	0.7681	0.2692	0.073*
C16	0.8450 (3)	0.8833 (5)	0.3606 (2)	0.0709 (13)
H16A	0.7919	0.9043	0.3588	0.085*
H16B	0.8723	0.9551	0.3377	0.085*
C17	0.8696 (3)	0.8706 (4)	0.4399 (2)	0.0634 (11)
H17A	0.9236	0.8582	0.4420	0.076*
H17B	0.8575	0.9511	0.4660	0.076*
C18	0.8310 (2)	0.7552 (4)	0.4764 (2)	0.0507 (10)
H18A	0.8506	0.7451	0.5256	0.061*
H18B	0.7776	0.7735	0.4802	0.061*
O1	0.91933 (12)	0.5946 (2)	0.44369 (12)	0.0406 (6)
O2	0.79528 (13)	0.5265 (3)	0.46336 (12)	0.0439 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0773 (3)	0.0523 (3)	0.0825 (3)	0.0132 (2)	0.0174 (2)	−0.0179 (2)
Br2	0.1021 (4)	0.0865 (4)	0.0482 (3)	0.0256 (3)	0.0059 (2)	0.0173 (2)
C1	0.050 (2)	0.049 (3)	0.052 (2)	0.0083 (19)	−0.0017 (17)	−0.0152 (18)
C2	0.050 (2)	0.053 (3)	0.049 (2)	0.0007 (19)	0.0078 (17)	−0.0141 (19)
C3	0.042 (2)	0.049 (3)	0.049 (2)	−0.0094 (18)	0.0049 (16)	−0.0013 (17)
C4	0.0355 (19)	0.036 (2)	0.0436 (18)	−0.0013 (15)	−0.0019 (14)	−0.0083 (15)
C5	0.0358 (19)	0.041 (2)	0.0407 (17)	−0.0019 (16)	−0.0029 (14)	−0.0054 (15)
C6	0.047 (2)	0.037 (2)	0.051 (2)	0.0000 (18)	0.0004 (16)	−0.0026 (16)
C7	0.055 (2)	0.050 (3)	0.0416 (19)	−0.0012 (19)	0.0015 (16)	0.0006 (17)
C8	0.045 (2)	0.040 (2)	0.0448 (19)	0.0040 (17)	−0.0025 (15)	−0.0028 (16)
C9	0.0367 (19)	0.035 (2)	0.0406 (18)	−0.0023 (16)	0.0005 (14)	−0.0033 (15)
C10	0.039 (2)	0.040 (2)	0.0413 (18)	−0.0010 (16)	−0.0017 (14)	0.0008 (15)
C11	0.039 (2)	0.050 (3)	0.057 (2)	0.0081 (18)	0.0087 (16)	0.0004 (18)
C12	0.055 (2)	0.059 (3)	0.046 (2)	0.007 (2)	0.0129 (17)	−0.0014 (18)
C13	0.033 (2)	0.037 (2)	0.0505 (19)	0.0008 (16)	0.0029 (14)	0.0023 (16)
C14	0.047 (2)	0.054 (3)	0.046 (2)	0.0001 (19)	0.0004 (16)	0.0043 (17)
C15	0.052 (2)	0.072 (4)	0.058 (2)	0.004 (2)	0.0043 (18)	0.018 (2)
C16	0.062 (3)	0.057 (3)	0.094 (3)	0.003 (2)	0.009 (2)	0.025 (3)
C17	0.065 (3)	0.039 (3)	0.086 (3)	0.001 (2)	0.007 (2)	−0.003 (2)
C18	0.050 (2)	0.044 (3)	0.058 (2)	0.0050 (19)	0.0041 (17)	−0.0028 (18)
O1	0.0348 (13)	0.0354 (16)	0.0516 (13)	−0.0005 (11)	−0.0001 (10)	−0.0037 (11)
O2	0.0379 (14)	0.0448 (17)	0.0489 (13)	−0.0042 (11)	−0.0044 (11)	0.0071 (11)

Geometric parameters (Å, º) top

Br1—C1	1.900 (4)	C11—H11	0.9300
Br2—C7	1.898 (4)	C12—H12	0.9300
C1—C2	1.377 (6)	C13—O1	1.424 (4)
C1—C6	1.381 (5)	C13—O2	1.428 (4)
C2—C3	1.382 (6)	C13—C18	1.501 (5)
C2—H2	0.9300	C13—C14	1.519 (5)
C3—C4	1.384 (5)	C14—C15	1.530 (5)
C3—H3	0.9300	C14—H14A	0.9700
C4—O1	1.376 (4)	C14—H14B	0.9700
C4—C5	1.394 (5)	C15—C16	1.502 (6)
C5—C6	1.398 (5)	C15—H15A	0.9700
C5—C9	1.478 (5)	C15—H15B	0.9700
C6—H6	0.9300	C16—C17	1.521 (6)
C7—C12	1.374 (5)	C16—H16A	0.9700
C7—C8	1.388 (5)	C16—H16B	0.9700
C8—C9	1.387 (5)	C17—C18	1.512 (6)
C8—H8	0.9300	C17—H17A	0.9700
C9—C10	1.394 (5)	C17—H17B	0.9700
C10—O2	1.381 (4)	C18—H18A	0.9700
C10—C11	1.383 (5)	C18—H18B	0.9700
C11—C12	1.379 (5)

C2—C1—C6	122.2 (4)	O1—C13—C18	106.3 (3)
C2—C1—Br1	118.1 (3)	O2—C13—C18	111.1 (3)
C6—C1—Br1	119.7 (3)	O1—C13—C14	111.8 (3)
C1—C2—C3	118.7 (3)	O2—C13—C14	104.8 (3)
C1—C2—H2	120.7	C18—C13—C14	112.6 (3)
C3—C2—H2	120.7	C13—C14—C15	111.3 (3)
C4—C3—C2	120.2 (4)	C13—C14—H14A	109.4
C4—C3—H3	119.9	C15—C14—H14A	109.4
C2—C3—H3	119.9	C13—C14—H14B	109.4
O1—C4—C3	118.2 (3)	C15—C14—H14B	109.4
O1—C4—C5	120.3 (3)	H14A—C14—H14B	108.0
C3—C4—C5	121.2 (3)	C16—C15—C14	111.3 (3)
C4—C5—C6	118.4 (3)	C16—C15—H15A	109.4
C4—C5—C9	119.6 (3)	C14—C15—H15A	109.4
C6—C5—C9	121.9 (3)	C16—C15—H15B	109.4
C1—C6—C5	119.4 (4)	C14—C15—H15B	109.4
C1—C6—H6	120.3	H15A—C15—H15B	108.0
C5—C6—H6	120.3	C15—C16—C17	111.4 (4)
C12—C7—C8	121.6 (3)	C15—C16—H16A	109.3
C12—C7—Br2	119.8 (3)	C17—C16—H16A	109.3
C8—C7—Br2	118.5 (3)	C15—C16—H16B	109.3
C9—C8—C7	119.9 (3)	C17—C16—H16B	109.3
C9—C8—H8	120.0	H16A—C16—H16B	108.0
C7—C8—H8	120.0	C18—C17—C16	110.8 (4)
C8—C9—C10	118.0 (3)	C18—C17—H17A	109.5
C8—C9—C5	121.8 (3)	C16—C17—H17A	109.5
C10—C9—C5	120.2 (3)	C18—C17—H17B	109.5
O2—C10—C11	118.7 (3)	C16—C17—H17B	109.5
O2—C10—C9	119.3 (3)	H17A—C17—H17B	108.1
C11—C10—C9	121.5 (3)	C13—C18—C17	112.2 (3)
C12—C11—C10	120.0 (3)	C13—C18—H18A	109.2
C12—C11—H11	120.0	C17—C18—H18A	109.2
C10—C11—H11	120.0	C13—C18—H18B	109.2
C7—C12—C11	118.9 (3)	C17—C18—H18B	109.2
C7—C12—H12	120.5	H18A—C18—H18B	107.9
C11—C12—H12	120.5	C4—O1—C13	117.8 (3)
O1—C13—O2	110.3 (3)	C10—O2—C13	118.2 (3)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆Br₂O₂
M_r	424.13
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	290
a, b, c (Å)	17.793 (4), 10.143 (5), 18.279 (5)
V (Å³)	3299 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.92
Crystal size (mm)	0.13 × 0.12 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.567, 0.614
No. of measured, independent and observed [I > 2σ(I)] reflections	29533, 3735, 2294
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.111, 1.00
No. of reflections	3735
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.64

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge financial support from the National Science Foundation of China (grant No. 50973010).

References

Dean, F. M. (1963). Naturally Occurring Oxygen Ring Compounds, p. 549. London: Butterworths. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. 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. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, B., Zhang, H.-Q., Xu, H., Zheng, Y., Yu, J.-S., Ma, Y.-G. & Sheng, J.-C. (2004). Chim. Sin. Acta Phys. pp. 1476–1480. CAS Google Scholar
Zhang, H.-O., Mo, Z.-C., Zheng, Y., Yang, G.-D., Ye, L., Ma, Y.-G., Chen, X.-F. & Sheng, J.-C. (2003). Chin. J. Org. Chem. pp. 578–583. Google Scholar