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Acta Cryst. (2008). E64, o925    [ doi:10.1107/S1600536808011665 ]

2,10-Dibromo-6-isobutyl-6-methyldibenzo[d,f][1,3]dioxepine

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

Abstract top

In the crystal structure of the title compound, C18H18Br2O2, the two benzene rings of the bridged biphenyl unit are twisted by 38.0 (1)°.

Comment top

Recently we have reported on the synthesis of the title compound 2,10-Dibromo -6-isobutyl-6-methyl-Dibenzo [d,f][1,3] Dioxepine (Zhang et al. 2003). Herein we present the crysal structure of this compound. In the crystal structure of the title compound the two benzene rings of the bridged biphenyl unit are twisted by 38.0 (1)° and the 7-membered ring is in a boat conformation.

Related literature top

For the synthesis of the title compound, see: Zhang et al. (2003).

Experimental top

The title compound was synthesized as described previously (Zhang et al. 2003). Single crystals were obtained by slow evaporation of the solvent from a methanol solution at room temperature.

Refinement top

All H atoms were positioned with idealized geometry and refined isotropic with Uiso(H) = 1.5Ueq(C) for methyl and Uiso(H) = 1.2Ueq(C)for all other H atoms using a riding model with C—H = 0.97 Å for methyl and C—H = 0.93 Å for all other H atoms.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC and Rigaku, 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).

Figures top
[Figure 1] Fig. 1. Crystal structure 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.
2,10-Dibromo-6-isobutyl-6-methyldibenzo[d,f][1,3]dioxepine top
Crystal data top
C18H18Br2O2F000 = 848
Mr = 426.14Dx = 1.652 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12167 reflections
a = 8.3372 (9) Åθ = 2.1–54.9º
b = 19.362 (2) ŵ = 4.74 mm−1
c = 10.8066 (16) ÅT = 193 (2) K
β = 100.803 (5)ºBlock, colorless
V = 1713.5 (4) Å30.13 × 0.12 × 0.12 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3924 independent reflections
Radiation source: fine-focus sealed tube2495 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 193(2) Kθmax = 27.5º
ω scansθmin = 2.1º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→10
Tmin = 0.587, Tmax = 0.607k = −25→25
7425 measured reflectionsl = −14→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.052  w = 1/[σ2(Fo2) + (0.0206P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.85(Δ/σ)max = 0.001
3924 reflectionsΔρmax = 0.41 e Å−3
202 parametersΔρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C18H18Br2O2V = 1713.5 (4) Å3
Mr = 426.14Z = 4
Monoclinic, P21/cMo Kα
a = 8.3372 (9) ŵ = 4.74 mm−1
b = 19.362 (2) ÅT = 193 (2) K
c = 10.8066 (16) Å0.13 × 0.12 × 0.12 mm
β = 100.803 (5)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3924 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2495 reflections with I > 2σ(I)
Tmin = 0.587, Tmax = 0.607Rint = 0.028
7425 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028202 parameters
wR(F2) = 0.052H-atom parameters constrained
S = 0.85Δρmax = 0.41 e Å−3
3924 reflectionsΔρmin = −0.51 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.32353 (3)0.596022 (13)0.68875 (3)0.03946 (9)
Br21.32322 (4)0.994048 (14)0.80855 (4)0.06258 (12)
C11.0296 (3)0.70180 (11)0.9608 (2)0.0219 (5)
C21.0540 (3)0.63147 (11)0.9678 (2)0.0273 (6)
H21.01000.60511.02760.033*
C31.1424 (3)0.59896 (11)0.8880 (2)0.0294 (6)
H31.15960.55040.89210.035*
C41.2052 (3)0.63899 (12)0.8022 (2)0.0264 (6)
C51.1833 (3)0.70927 (11)0.7948 (2)0.0238 (5)
H51.22830.73540.73530.029*
C61.0946 (3)0.74206 (11)0.8752 (2)0.0220 (5)
C70.9182 (3)0.84461 (11)0.8840 (2)0.0240 (5)
C81.0681 (3)0.81720 (11)0.8698 (2)0.0226 (5)
C91.1879 (3)0.86301 (12)0.8475 (2)0.0305 (6)
H91.29140.84600.83700.037*
C101.1573 (3)0.93303 (12)0.8403 (2)0.0329 (7)
C111.0099 (3)0.95998 (11)0.8559 (2)0.0333 (6)
H110.99141.00840.85170.040*
C120.8886 (3)0.91495 (11)0.8779 (2)0.0297 (6)
H120.78560.93240.88870.036*
C130.7930 (3)0.76216 (11)1.0048 (2)0.0231 (5)
C140.7645 (3)0.81026 (11)1.1085 (2)0.0304 (6)
H14A0.77260.78431.18730.046*
H14B0.65540.83081.08600.046*
H14C0.84690.84701.11950.046*
C150.6684 (3)0.70529 (11)0.9684 (2)0.0239 (5)
H15A0.70270.67670.90200.029*
H15B0.56220.72670.93160.029*
C160.6434 (3)0.65766 (12)1.0774 (2)0.0271 (6)
H160.74520.65921.14310.032*
C170.6163 (3)0.58315 (12)1.0329 (2)0.0404 (7)
H17A0.60300.55381.10410.061*
H17B0.71060.56730.99840.061*
H17C0.51770.58040.96740.061*
C180.5010 (3)0.68121 (13)1.1386 (2)0.0414 (7)
H18A0.39890.67841.07670.062*
H18B0.51930.72901.16770.062*
H18C0.49380.65121.21040.062*
O10.95321 (18)0.73412 (7)1.04861 (13)0.0232 (4)
O20.78958 (17)0.79979 (7)0.88965 (14)0.0243 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03994 (16)0.03630 (15)0.04601 (17)0.00641 (13)0.01797 (13)−0.00815 (14)
Br20.0675 (2)0.03245 (16)0.1003 (3)−0.01841 (15)0.0480 (2)−0.00512 (17)
C10.0173 (13)0.0274 (13)0.0206 (13)0.0013 (10)0.0024 (11)0.0006 (10)
C20.0242 (13)0.0273 (13)0.0309 (15)0.0009 (11)0.0066 (12)0.0070 (11)
C30.0267 (13)0.0213 (12)0.0391 (16)0.0033 (11)0.0029 (12)0.0019 (12)
C40.0170 (13)0.0304 (13)0.0316 (15)0.0042 (10)0.0039 (12)−0.0069 (11)
C50.0198 (12)0.0276 (13)0.0243 (14)0.0006 (10)0.0050 (11)0.0011 (11)
C60.0178 (13)0.0247 (12)0.0225 (13)−0.0005 (10)0.0016 (11)−0.0007 (10)
C70.0244 (14)0.0260 (13)0.0212 (14)−0.0015 (10)0.0030 (11)−0.0009 (10)
C80.0283 (13)0.0207 (11)0.0205 (13)−0.0008 (10)0.0083 (11)−0.0004 (10)
C90.0306 (15)0.0298 (14)0.0338 (17)−0.0028 (11)0.0131 (14)−0.0036 (11)
C100.0423 (16)0.0252 (13)0.0362 (17)−0.0089 (12)0.0203 (14)−0.0007 (11)
C110.0458 (18)0.0205 (12)0.0354 (16)0.0023 (12)0.0122 (14)0.0013 (11)
C120.0313 (14)0.0279 (14)0.0303 (15)0.0064 (11)0.0067 (12)0.0034 (11)
C130.0245 (13)0.0279 (12)0.0167 (13)0.0044 (11)0.0032 (11)0.0033 (10)
C140.0294 (14)0.0320 (14)0.0304 (16)0.0018 (12)0.0073 (12)−0.0052 (12)
C150.0207 (13)0.0280 (12)0.0222 (13)0.0017 (10)0.0020 (11)−0.0004 (11)
C160.0215 (13)0.0352 (14)0.0237 (14)−0.0039 (11)0.0025 (11)0.0023 (11)
C170.0423 (17)0.0333 (15)0.0468 (18)−0.0035 (13)0.0116 (14)0.0074 (13)
C180.0331 (16)0.0539 (17)0.0408 (18)−0.0094 (13)0.0163 (14)−0.0011 (14)
O10.0193 (9)0.0305 (9)0.0197 (9)0.0023 (7)0.0033 (7)0.0001 (7)
O20.0226 (9)0.0266 (9)0.0230 (9)−0.0009 (7)0.0028 (8)0.0043 (7)
Geometric parameters (Å, °) top
Br1—C41.903 (2)C11—H110.9500
Br2—C101.898 (2)C12—H120.9500
C1—C21.377 (3)C13—O11.437 (3)
C1—O11.387 (2)C13—O21.438 (2)
C1—C61.395 (3)C13—C141.510 (3)
C2—C31.386 (3)C13—C151.515 (3)
C2—H20.9500C14—H14A0.9800
C3—C41.384 (3)C14—H14B0.9800
C3—H30.9500C14—H14C0.9800
C4—C51.373 (3)C15—C161.541 (3)
C5—C61.394 (3)C15—H15A0.9900
C5—H50.9500C15—H15B0.9900
C6—C81.471 (3)C16—C171.524 (3)
C7—C121.384 (3)C16—C181.532 (3)
C7—O21.390 (2)C16—H161.0000
C7—C81.393 (3)C17—H17A0.9800
C8—C91.390 (3)C17—H17B0.9800
C9—C101.379 (3)C17—H17C0.9800
C9—H90.9500C18—H18A0.9800
C10—C111.375 (3)C18—H18B0.9800
C11—C121.390 (3)C18—H18C0.9800
C2—C1—O1119.39 (18)O1—C13—C14104.76 (18)
C2—C1—C6121.15 (19)O2—C13—C14110.46 (17)
O1—C1—C6119.15 (19)O1—C13—C15111.15 (17)
C1—C2—C3120.3 (2)O2—C13—C15103.98 (18)
C1—C2—H2119.8C14—C13—C15116.49 (17)
C3—C2—H2119.8C13—C14—H14A109.5
C4—C3—C2118.3 (2)C13—C14—H14B109.5
C4—C3—H3120.8H14A—C14—H14B109.5
C2—C3—H3120.8C13—C14—H14C109.5
C5—C4—C3122.06 (19)H14A—C14—H14C109.5
C5—C4—Br1118.37 (16)H14B—C14—H14C109.5
C3—C4—Br1119.57 (16)C13—C15—C16114.87 (19)
C4—C5—C6119.70 (19)C13—C15—H15A108.6
C4—C5—H5120.2C16—C15—H15A108.6
C6—C5—H5120.2C13—C15—H15B108.6
C5—C6—C1118.4 (2)C16—C15—H15B108.6
C5—C6—C8121.27 (18)H15A—C15—H15B107.5
C1—C6—C8120.31 (18)C17—C16—C18109.68 (19)
C12—C7—O2119.0 (2)C17—C16—C15111.01 (19)
C12—C7—C8121.7 (2)C18—C16—C15112.25 (19)
O2—C7—C8118.87 (18)C17—C16—H16107.9
C9—C8—C7117.69 (19)C18—C16—H16107.9
C9—C8—C6122.05 (19)C15—C16—H16107.9
C7—C8—C6120.24 (18)C16—C17—H17A109.5
C10—C9—C8120.4 (2)C16—C17—H17B109.5
C10—C9—H9119.8H17A—C17—H17B109.5
C8—C9—H9119.8C16—C17—H17C109.5
C11—C10—C9121.8 (2)H17A—C17—H17C109.5
C11—C10—Br2118.97 (17)H17B—C17—H17C109.5
C9—C10—Br2119.27 (18)C16—C18—H18A109.5
C10—C11—C12118.6 (2)C16—C18—H18B109.5
C10—C11—H11120.7H18A—C18—H18B109.5
C12—C11—H11120.7C16—C18—H18C109.5
C7—C12—C11119.8 (2)H18A—C18—H18C109.5
C7—C12—H12120.1H18B—C18—H18C109.5
C11—C12—H12120.1C1—O1—C13117.59 (17)
O1—C13—O2110.04 (15)C7—O2—C13117.64 (17)
O1—C1—C2—C3−174.4 (2)C8—C9—C10—C110.6 (4)
C6—C1—C2—C3−0.9 (4)C8—C9—C10—Br2−179.60 (18)
C1—C2—C3—C40.1 (4)C9—C10—C11—C12−0.8 (4)
C2—C3—C4—C50.5 (4)Br2—C10—C11—C12179.40 (19)
C2—C3—C4—Br1−178.75 (18)O2—C7—C12—C11−171.7 (2)
C3—C4—C5—C6−0.4 (4)C8—C7—C12—C110.6 (4)
Br1—C4—C5—C6178.88 (17)C10—C11—C12—C70.2 (4)
C4—C5—C6—C1−0.4 (3)O1—C13—C15—C1663.4 (2)
C4—C5—C6—C8−179.8 (2)O2—C13—C15—C16−178.25 (16)
C2—C1—C6—C51.0 (4)C14—C13—C15—C16−56.5 (3)
O1—C1—C6—C5174.5 (2)C13—C15—C16—C17−142.7 (2)
C2—C1—C6—C8−179.6 (2)C13—C15—C16—C1894.2 (2)
O1—C1—C6—C8−6.0 (3)C2—C1—O1—C13−111.5 (2)
C12—C7—C8—C9−0.8 (4)C6—C1—O1—C1374.8 (3)
O2—C7—C8—C9171.5 (2)O2—C13—O1—C1−45.4 (2)
C12—C7—C8—C6−179.2 (2)C14—C13—O1—C1−164.10 (17)
O2—C7—C8—C6−6.8 (3)C15—C13—O1—C169.3 (2)
C5—C6—C8—C9−37.5 (4)C12—C7—O2—C13−112.0 (2)
C1—C6—C8—C9143.1 (2)C8—C7—O2—C1375.5 (2)
C5—C6—C8—C7140.8 (2)O1—C13—O2—C7−45.3 (2)
C1—C6—C8—C7−38.6 (3)C14—C13—O2—C769.9 (2)
C7—C8—C9—C100.2 (4)C15—C13—O2—C7−164.38 (16)
C6—C8—C9—C10178.5 (2)
Acknowledgements top

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 2003 cb3147032).

references
References top

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC and Rigaku (2002). CrystalStructure. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Zhang, H.Q., Mu, S.-C., Zheng, Y., Yang, G-D., Ye, , Ma, Y.-G., Chen, X.-F. & Shen J.-C. (2003). Chin. J. Org. Chem. 23, 578–583.