organic compounds
2,10-Dibromo-6-isobutyl-6-methyldibenzo[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 18H18Br2O2, the two benzene rings of the bridged biphenyl unit are twisted by 38.0 (1)°.
of the title compound, CExperimental
Crystal data
|
Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; 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 .
Supporting information
10.1107/S1600536808011665/nc2099sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011665/nc2099Isup2.hkl
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.
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.
Data collection: RAPID-AUTO (Rigaku, 1998); cell
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).C18H18Br2O2 | F(000) = 848 |
Mr = 426.14 | Dx = 1.652 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 12167 reflections |
a = 8.3372 (9) Å | θ = 2.1–54.9° |
b = 19.362 (2) Å | µ = 4.74 mm−1 |
c = 10.8066 (16) Å | T = 193 K |
β = 100.803 (5)° | Block, colorless |
V = 1713.5 (4) Å3 | 0.13 × 0.12 × 0.12 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 3924 independent reflections |
Radiation source: fine-focus sealed tube | 2495 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→10 |
Tmin = 0.587, Tmax = 0.607 | k = −25→25 |
7425 measured reflections | l = −14→14 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0206P)2] where P = (Fo2 + 2Fc2)/3 |
3924 reflections | (Δ/σ)max = 0.001 |
202 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C18H18Br2O2 | V = 1713.5 (4) Å3 |
Mr = 426.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3372 (9) Å | µ = 4.74 mm−1 |
b = 19.362 (2) Å | T = 193 K |
c = 10.8066 (16) Å | 0.13 × 0.12 × 0.12 mm |
β = 100.803 (5)° |
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 = 0.607 | Rint = 0.028 |
7425 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.41 e Å−3 |
3924 reflections | Δρmin = −0.51 e Å−3 |
202 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 | 1.32353 (3) | 0.596022 (13) | 0.68875 (3) | 0.03946 (9) | |
Br2 | 1.32322 (4) | 0.994048 (14) | 0.80855 (4) | 0.06258 (12) | |
C1 | 1.0296 (3) | 0.70180 (11) | 0.9608 (2) | 0.0219 (5) | |
C2 | 1.0540 (3) | 0.63147 (11) | 0.9678 (2) | 0.0273 (6) | |
H2 | 1.0100 | 0.6051 | 1.0276 | 0.033* | |
C3 | 1.1424 (3) | 0.59896 (11) | 0.8880 (2) | 0.0294 (6) | |
H3 | 1.1596 | 0.5504 | 0.8921 | 0.035* | |
C4 | 1.2052 (3) | 0.63899 (12) | 0.8022 (2) | 0.0264 (6) | |
C5 | 1.1833 (3) | 0.70927 (11) | 0.7948 (2) | 0.0238 (5) | |
H5 | 1.2283 | 0.7354 | 0.7353 | 0.029* | |
C6 | 1.0946 (3) | 0.74206 (11) | 0.8752 (2) | 0.0220 (5) | |
C7 | 0.9182 (3) | 0.84461 (11) | 0.8840 (2) | 0.0240 (5) | |
C8 | 1.0681 (3) | 0.81720 (11) | 0.8698 (2) | 0.0226 (5) | |
C9 | 1.1879 (3) | 0.86301 (12) | 0.8475 (2) | 0.0305 (6) | |
H9 | 1.2914 | 0.8460 | 0.8370 | 0.037* | |
C10 | 1.1573 (3) | 0.93303 (12) | 0.8403 (2) | 0.0329 (7) | |
C11 | 1.0099 (3) | 0.95998 (11) | 0.8559 (2) | 0.0333 (6) | |
H11 | 0.9914 | 1.0084 | 0.8517 | 0.040* | |
C12 | 0.8886 (3) | 0.91495 (11) | 0.8779 (2) | 0.0297 (6) | |
H12 | 0.7856 | 0.9324 | 0.8887 | 0.036* | |
C13 | 0.7930 (3) | 0.76216 (11) | 1.0048 (2) | 0.0231 (5) | |
C14 | 0.7645 (3) | 0.81026 (11) | 1.1085 (2) | 0.0304 (6) | |
H14A | 0.7726 | 0.7843 | 1.1873 | 0.046* | |
H14B | 0.6554 | 0.8308 | 1.0860 | 0.046* | |
H14C | 0.8469 | 0.8470 | 1.1195 | 0.046* | |
C15 | 0.6684 (3) | 0.70529 (11) | 0.9684 (2) | 0.0239 (5) | |
H15A | 0.7027 | 0.6767 | 0.9020 | 0.029* | |
H15B | 0.5622 | 0.7267 | 0.9316 | 0.029* | |
C16 | 0.6434 (3) | 0.65766 (12) | 1.0774 (2) | 0.0271 (6) | |
H16 | 0.7452 | 0.6592 | 1.1431 | 0.032* | |
C17 | 0.6163 (3) | 0.58315 (12) | 1.0329 (2) | 0.0404 (7) | |
H17A | 0.6030 | 0.5538 | 1.1041 | 0.061* | |
H17B | 0.7106 | 0.5673 | 0.9984 | 0.061* | |
H17C | 0.5177 | 0.5804 | 0.9674 | 0.061* | |
C18 | 0.5010 (3) | 0.68121 (13) | 1.1386 (2) | 0.0414 (7) | |
H18A | 0.3989 | 0.6784 | 1.0767 | 0.062* | |
H18B | 0.5193 | 0.7290 | 1.1677 | 0.062* | |
H18C | 0.4938 | 0.6512 | 1.2104 | 0.062* | |
O1 | 0.95321 (18) | 0.73412 (7) | 1.04861 (13) | 0.0232 (4) | |
O2 | 0.78958 (17) | 0.79979 (7) | 0.88965 (14) | 0.0243 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.03994 (16) | 0.03630 (15) | 0.04601 (17) | 0.00641 (13) | 0.01797 (13) | −0.00815 (14) |
Br2 | 0.0675 (2) | 0.03245 (16) | 0.1003 (3) | −0.01841 (15) | 0.0480 (2) | −0.00512 (17) |
C1 | 0.0173 (13) | 0.0274 (13) | 0.0206 (13) | 0.0013 (10) | 0.0024 (11) | 0.0006 (10) |
C2 | 0.0242 (13) | 0.0273 (13) | 0.0309 (15) | 0.0009 (11) | 0.0066 (12) | 0.0070 (11) |
C3 | 0.0267 (13) | 0.0213 (12) | 0.0391 (16) | 0.0033 (11) | 0.0029 (12) | 0.0019 (12) |
C4 | 0.0170 (13) | 0.0304 (13) | 0.0316 (15) | 0.0042 (10) | 0.0039 (12) | −0.0069 (11) |
C5 | 0.0198 (12) | 0.0276 (13) | 0.0243 (14) | 0.0006 (10) | 0.0050 (11) | 0.0011 (11) |
C6 | 0.0178 (13) | 0.0247 (12) | 0.0225 (13) | −0.0005 (10) | 0.0016 (11) | −0.0007 (10) |
C7 | 0.0244 (14) | 0.0260 (13) | 0.0212 (14) | −0.0015 (10) | 0.0030 (11) | −0.0009 (10) |
C8 | 0.0283 (13) | 0.0207 (11) | 0.0205 (13) | −0.0008 (10) | 0.0083 (11) | −0.0004 (10) |
C9 | 0.0306 (15) | 0.0298 (14) | 0.0338 (17) | −0.0028 (11) | 0.0131 (14) | −0.0036 (11) |
C10 | 0.0423 (16) | 0.0252 (13) | 0.0362 (17) | −0.0089 (12) | 0.0203 (14) | −0.0007 (11) |
C11 | 0.0458 (18) | 0.0205 (12) | 0.0354 (16) | 0.0023 (12) | 0.0122 (14) | 0.0013 (11) |
C12 | 0.0313 (14) | 0.0279 (14) | 0.0303 (15) | 0.0064 (11) | 0.0067 (12) | 0.0034 (11) |
C13 | 0.0245 (13) | 0.0279 (12) | 0.0167 (13) | 0.0044 (11) | 0.0032 (11) | 0.0033 (10) |
C14 | 0.0294 (14) | 0.0320 (14) | 0.0304 (16) | 0.0018 (12) | 0.0073 (12) | −0.0052 (12) |
C15 | 0.0207 (13) | 0.0280 (12) | 0.0222 (13) | 0.0017 (10) | 0.0020 (11) | −0.0004 (11) |
C16 | 0.0215 (13) | 0.0352 (14) | 0.0237 (14) | −0.0039 (11) | 0.0025 (11) | 0.0023 (11) |
C17 | 0.0423 (17) | 0.0333 (15) | 0.0468 (18) | −0.0035 (13) | 0.0116 (14) | 0.0074 (13) |
C18 | 0.0331 (16) | 0.0539 (17) | 0.0408 (18) | −0.0094 (13) | 0.0163 (14) | −0.0011 (14) |
O1 | 0.0193 (9) | 0.0305 (9) | 0.0197 (9) | 0.0023 (7) | 0.0033 (7) | 0.0001 (7) |
O2 | 0.0226 (9) | 0.0266 (9) | 0.0230 (9) | −0.0009 (7) | 0.0028 (8) | 0.0043 (7) |
Br1—C4 | 1.903 (2) | C11—H11 | 0.9500 |
Br2—C10 | 1.898 (2) | C12—H12 | 0.9500 |
C1—C2 | 1.377 (3) | C13—O1 | 1.437 (3) |
C1—O1 | 1.387 (2) | C13—O2 | 1.438 (2) |
C1—C6 | 1.395 (3) | C13—C14 | 1.510 (3) |
C2—C3 | 1.386 (3) | C13—C15 | 1.515 (3) |
C2—H2 | 0.9500 | C14—H14A | 0.9800 |
C3—C4 | 1.384 (3) | C14—H14B | 0.9800 |
C3—H3 | 0.9500 | C14—H14C | 0.9800 |
C4—C5 | 1.373 (3) | C15—C16 | 1.541 (3) |
C5—C6 | 1.394 (3) | C15—H15A | 0.9900 |
C5—H5 | 0.9500 | C15—H15B | 0.9900 |
C6—C8 | 1.471 (3) | C16—C17 | 1.524 (3) |
C7—C12 | 1.384 (3) | C16—C18 | 1.532 (3) |
C7—O2 | 1.390 (2) | C16—H16 | 1.0000 |
C7—C8 | 1.393 (3) | C17—H17A | 0.9800 |
C8—C9 | 1.390 (3) | C17—H17B | 0.9800 |
C9—C10 | 1.379 (3) | C17—H17C | 0.9800 |
C9—H9 | 0.9500 | C18—H18A | 0.9800 |
C10—C11 | 1.375 (3) | C18—H18B | 0.9800 |
C11—C12 | 1.390 (3) | C18—H18C | 0.9800 |
C2—C1—O1 | 119.39 (18) | O1—C13—C14 | 104.76 (18) |
C2—C1—C6 | 121.15 (19) | O2—C13—C14 | 110.46 (17) |
O1—C1—C6 | 119.15 (19) | O1—C13—C15 | 111.15 (17) |
C1—C2—C3 | 120.3 (2) | O2—C13—C15 | 103.98 (18) |
C1—C2—H2 | 119.8 | C14—C13—C15 | 116.49 (17) |
C3—C2—H2 | 119.8 | C13—C14—H14A | 109.5 |
C4—C3—C2 | 118.3 (2) | C13—C14—H14B | 109.5 |
C4—C3—H3 | 120.8 | H14A—C14—H14B | 109.5 |
C2—C3—H3 | 120.8 | C13—C14—H14C | 109.5 |
C5—C4—C3 | 122.06 (19) | H14A—C14—H14C | 109.5 |
C5—C4—Br1 | 118.37 (16) | H14B—C14—H14C | 109.5 |
C3—C4—Br1 | 119.57 (16) | C13—C15—C16 | 114.87 (19) |
C4—C5—C6 | 119.70 (19) | C13—C15—H15A | 108.6 |
C4—C5—H5 | 120.2 | C16—C15—H15A | 108.6 |
C6—C5—H5 | 120.2 | C13—C15—H15B | 108.6 |
C5—C6—C1 | 118.4 (2) | C16—C15—H15B | 108.6 |
C5—C6—C8 | 121.27 (18) | H15A—C15—H15B | 107.5 |
C1—C6—C8 | 120.31 (18) | C17—C16—C18 | 109.68 (19) |
C12—C7—O2 | 119.0 (2) | C17—C16—C15 | 111.01 (19) |
C12—C7—C8 | 121.7 (2) | C18—C16—C15 | 112.25 (19) |
O2—C7—C8 | 118.87 (18) | C17—C16—H16 | 107.9 |
C9—C8—C7 | 117.69 (19) | C18—C16—H16 | 107.9 |
C9—C8—C6 | 122.05 (19) | C15—C16—H16 | 107.9 |
C7—C8—C6 | 120.24 (18) | C16—C17—H17A | 109.5 |
C10—C9—C8 | 120.4 (2) | C16—C17—H17B | 109.5 |
C10—C9—H9 | 119.8 | H17A—C17—H17B | 109.5 |
C8—C9—H9 | 119.8 | C16—C17—H17C | 109.5 |
C11—C10—C9 | 121.8 (2) | H17A—C17—H17C | 109.5 |
C11—C10—Br2 | 118.97 (17) | H17B—C17—H17C | 109.5 |
C9—C10—Br2 | 119.27 (18) | C16—C18—H18A | 109.5 |
C10—C11—C12 | 118.6 (2) | C16—C18—H18B | 109.5 |
C10—C11—H11 | 120.7 | H18A—C18—H18B | 109.5 |
C12—C11—H11 | 120.7 | C16—C18—H18C | 109.5 |
C7—C12—C11 | 119.8 (2) | H18A—C18—H18C | 109.5 |
C7—C12—H12 | 120.1 | H18B—C18—H18C | 109.5 |
C11—C12—H12 | 120.1 | C1—O1—C13 | 117.59 (17) |
O1—C13—O2 | 110.04 (15) | C7—O2—C13 | 117.64 (17) |
O1—C1—C2—C3 | −174.4 (2) | C8—C9—C10—C11 | 0.6 (4) |
C6—C1—C2—C3 | −0.9 (4) | C8—C9—C10—Br2 | −179.60 (18) |
C1—C2—C3—C4 | 0.1 (4) | C9—C10—C11—C12 | −0.8 (4) |
C2—C3—C4—C5 | 0.5 (4) | Br2—C10—C11—C12 | 179.40 (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—C11 | 0.6 (4) |
Br1—C4—C5—C6 | 178.88 (17) | C10—C11—C12—C7 | 0.2 (4) |
C4—C5—C6—C1 | −0.4 (3) | O1—C13—C15—C16 | 63.4 (2) |
C4—C5—C6—C8 | −179.8 (2) | O2—C13—C15—C16 | −178.25 (16) |
C2—C1—C6—C5 | 1.0 (4) | C14—C13—C15—C16 | −56.5 (3) |
O1—C1—C6—C5 | 174.5 (2) | C13—C15—C16—C17 | −142.7 (2) |
C2—C1—C6—C8 | −179.6 (2) | C13—C15—C16—C18 | 94.2 (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—C13 | 74.8 (3) |
O2—C7—C8—C9 | 171.5 (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—C1 | 69.3 (2) |
C5—C6—C8—C9 | −37.5 (4) | C12—C7—O2—C13 | −112.0 (2) |
C1—C6—C8—C9 | 143.1 (2) | C8—C7—O2—C13 | 75.5 (2) |
C5—C6—C8—C7 | 140.8 (2) | O1—C13—O2—C7 | −45.3 (2) |
C1—C6—C8—C7 | −38.6 (3) | C14—C13—O2—C7 | 69.9 (2) |
C7—C8—C9—C10 | 0.2 (4) | C15—C13—O2—C7 | −164.38 (16) |
C6—C8—C9—C10 | 178.5 (2) |
Experimental details
Crystal data | |
Chemical formula | C18H18Br2O2 |
Mr | 426.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 8.3372 (9), 19.362 (2), 10.8066 (16) |
β (°) | 100.803 (5) |
V (Å3) | 1713.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.74 |
Crystal size (mm) | 0.13 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.587, 0.607 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7425, 3924, 2495 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.052, 0.85 |
No. of reflections | 3924 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.51 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC and Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).
Acknowledgements
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 2003CB3147032).
References
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC and Rigaku (2002). CrystalStructure. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Google Scholar
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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.