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

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

doi:10.1107/S1600536808011665

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o925

doi:10.1107/S1600536808011665

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2,10-Dibromo-6-isobutyl-6-methyldibenzo[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 3 April 2008; accepted 23 April 2008; online 26 April 2008)

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

Related literature

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

Experimental

Crystal data

C₁₈H₁₈Br₂O₂
M_r = 426.14
Monoclinic, P 2₁ /c
a = 8.3372 (9) Å
b = 19.362 (2) Å
c = 10.8066 (16) Å
β = 100.803 (5)°
V = 1713.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.74 mm⁻¹
T = 193 (2) K
0.13 × 0.12 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.587, T_max = 0.607 (expected range = 0.547–0.567)
7425 measured reflections
3924 independent reflections
2495 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.052
S = 0.85
3924 reflections
202 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.51 e Å⁻³

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011665/nc2099sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011665/nc2099Isup2.hkl

checkCIF report

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.

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

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

C₁₈H₁₈Br₂O₂	F(000) = 848
M_r = 426.14	D_x = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	3924 independent reflections
Radiation source: fine-focus sealed tube	2495 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.587, T_max = 0.607	k = −25→25
7425 measured reflections	l = −14→14

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H-atom parameters constrained
S = 0.85	w = 1/[σ²(F_o²) + (0.0206P)²] where P = (F_o² + 2F_c²)/3
3924 reflections	(Δ/σ)_max = 0.001
202 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₈H₁₈Br₂O₂	V = 1713.5 (4) Å³
M_r = 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)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3924 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2495 reflections with I > 2σ(I)
T_min = 0.587, T_max = 0.607	R_int = 0.028
7425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.052	H-atom parameters constrained
S = 0.85	Δρ_max = 0.41 e Å⁻³
3924 reflections	Δρ_min = −0.51 e Å⁻³
202 parameters

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.587, 0.607
No. of measured, independent and observed [I > 2σ(I)] reflections	7425, 3924, 2495
R_int	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
Δρ_max, Δρ_min (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
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