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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o3029.
Published online 2010 October 31. doi:  10.1107/S1600536810043758
PMCID: PMC3009213

2,3-Dibromo-1-[4-(2,3-dibromo-4,5-di­meth­oxy­benz­yl)-2,5-dimeth­oxy­benz­yl]-4,5-dimeth­oxy­benzene

Abstract

The mol­ecule of the title compound, C26H26Br4O6, is located around a crystallographic inversion center. The dihedral angle between the central benzene ring and the outer benzene ring is 89.26 (1)°.

Related literature

For information related to the synthesis of the title compound, see: Ford & Davidson (1993 [triangle]); Glombitza et al. (1985 [triangle]); Akbaba et al. (2010 [triangle]); Balaydın et al. (2009 [triangle], 2010 [triangle]).

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Object name is e-66-o3029-scheme1.jpg

Experimental

Crystal data

  • C26H26Br4O6
  • M r = 754.07
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3029-efi1.jpg
  • a = 11.193 (5) Å
  • b = 9.645 (4) Å
  • c = 13.212 (5) Å
  • β = 107.125 (5)°
  • V = 1363.1 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.94 mm−1
  • T = 293 K
  • 0.3 × 0.2 × 0.1 mm

Data collection

  • Rigaku R-AXIS RAPID-S diffractometer
  • Absorption correction: multi-scan (Blessing, 1995 [triangle]) T min = 0.250, T max = 0.552
  • 27932 measured reflections
  • 2793 independent reflections
  • 2564 reflections with I > 2σ(I)
  • R int = 0.080

Refinement

  • R[F 2 > 2σ(F 2)] = 0.078
  • wR(F 2) = 0.125
  • S = 1.45
  • 2793 reflections
  • 166 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043758/gk2308sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043758/gk2308Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are indebted to Atatürk University and TÜBİTAK (grant No. 107 T348) for financial support.

supplementary crystallographic information

Comment

2,3-Dibromo-1-[4 -(2,3-dibromo-4,5-dimethoxybenzyl)-2,5-dimethoxybenzyl]-4, 5-dimethoxybenzene (1) was synthesized from reaction of bromoalcohol 2 (Ford & Davidson, 1993; Glombitza et al., 1985) with 1,4-dimethoxybenzene in polyphosphoric acid (PPA) (Akbaba, et al. 2010; Balaydın et al., 2010). From demethylation of this compound with BBr3, a bromophenol derivative can be easily obtained which may show important biological activities in further studies. The primary reason for the X-ray analysis of the title compound was to designate the position of Br atoms and methoxy groups and to obtain detailed information on the molecular structure. This information will be useful in structure-activity relationship (SAR) studies.

The title compound packs with half molecule in the asymmetric unit. Its molecular structure is shown in Fig. 1. Compound 1 includes three aromatic rings containing methoxy and bromide groups.

Experimental

Polyphosphoric acid (PPA), prepared from conc. H3PO4 (85%, 0.57 g, 0.006 mmol) and P2O5 (1.03 g, 0.007 mmol), was heated to 80 °C in a beaker (100 ml) (Akbaba et al., 2010; Balaydın et al., 2010, 2009). To this mixture were added 1,4-dimethoxybenzene (0.138 g, 1 mmol) and synthesized bromoalcohol 2 (see Sscheme 2) (Ford & Davidson, 1993; Glombitza et al., 1985) respectively and quickly. The mixture was stirred with a glass stick at 80 °C for 60 minutes and was cooled to room temperature. Mixture (50 ml) of water-ice and ethyl acetate (EtOA, 50 ml) was carefully added to the cooled mixture, respectively. The organic phase was separated and then the water phase was extracted with EtOAc (2x40 ml). The combined organic layers were dried over Na2SO4 and the solvent was evaporated. The product 1 (0.73 g, 97%) was obtained and crystallized from ethyl acetate/hexane as colorless crystals. M.p. 442–444 K. 1H-NMR (400 MHz, CDCl3) δ 6.71 (s, 2H), 6.67 (s, 2H), 4.09 (s, CH2, 4H), 3.83 (s, methoxide, 6H), 3.73 (s, methoxide,6H), 3.72 (s, methoxide, 6H); 13 C-NMR (100 MHz, CDCl3) δ 152.58 (C), 151.64 (C), 146.30 (C), 137.89 (C), 126.90 (C), 121.90(C), 118.01 (C), 114.01 (CH), 113.74 (CH), 60.71 (OCH3), 56.37 (OCH3), 56.32 (OCH3), 37.92 (CH2); IR (CH2Cl2, cm -1): 2997,2935, 2829, 1546, 1507, 1463, 1421, 1402, 1371, 1310, 1282, 1212,1160, 1057, 1038,1006.

Refinement

All H atoms were placed in calculated positions and allowed to ride on their carrier atoms with C—H = 0.93 - 0.97 Å and with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl).

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Atoms denoted as 'a' are generated by inversion operation 2-x,y,2-z.

Crystal data

C26H26Br4O6F(000) = 740
Mr = 754.07Dx = 1.837 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6447 reflections
a = 11.193 (5) Åθ = 2.7–26.4°
b = 9.645 (4) ŵ = 5.94 mm1
c = 13.212 (5) ÅT = 293 K
β = 107.125 (5)°Prism, colourless
V = 1363.1 (10) Å30.3 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID-S diffractometer2564 reflections with I > 2σ(I)
graphiteRint = 0.080
ω scansθmax = 26.5°, θmin = 2.7°
Absorption correction: multi-scan (Blessing, 1995)h = −14→13
Tmin = 0.250, Tmax = 0.552k = −12→12
27932 measured reflectionsl = −16→16
2793 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.078Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125H-atom parameters constrained
S = 1.45w = 1/[σ2(Fo2) + (0.0035P)2 + 2.976P] where P = (Fo2 + 2Fc2)/3
2793 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = −0.50 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
Br10.34470 (6)0.34698 (9)0.98736 (6)0.0672 (3)
Br20.53324 (6)0.33264 (8)0.83484 (5)0.0593 (2)
O10.6334 (4)0.0000 (5)1.2376 (3)0.0564 (12)
O20.4301 (4)0.1588 (5)1.1761 (3)0.0560 (12)
O31.0448 (4)−0.2703 (5)0.9540 (4)0.0617 (13)
C10.6977 (5)0.0659 (6)1.0834 (4)0.0404 (13)
H10.76820.00961.10380.049*
C20.6735 (5)0.1422 (6)0.9902 (4)0.0387 (13)
C30.5684 (5)0.2278 (6)0.9617 (4)0.0396 (13)
C40.4892 (5)0.2351 (6)1.0257 (5)0.0429 (14)
C50.5125 (5)0.1579 (6)1.1164 (5)0.0411 (14)
C60.6183 (5)0.0727 (6)1.1462 (5)0.0431 (14)
C70.7351 (7)−0.0943 (7)1.2701 (6)0.0602 (18)
H7A0.7309−0.15951.21420.09*
H7B0.7307−0.14311.33220.09*
H7C0.8124−0.0441.28580.09*
C80.4678 (8)0.2424 (9)1.2687 (6)0.076 (2)
H8A0.55090.21691.30960.114*
H8B0.41140.22841.31010.114*
H8C0.46670.33821.24870.114*
C90.7554 (5)0.1280 (7)0.9173 (5)0.0458 (15)
H9A0.70930.07550.85560.055*
H9B0.76910.220.89310.055*
C100.8809 (5)0.0600 (7)0.9629 (4)0.0430 (14)
C110.9001 (6)−0.0763 (6)0.9392 (5)0.0450 (14)
H110.8332−0.12870.89880.054*
C121.0184 (5)−0.1362 (6)0.9752 (5)0.0422 (14)
C130.9451 (7)−0.3596 (7)0.9009 (6)0.0652 (19)
H13A0.8909−0.37380.94440.098*
H13B0.9784−0.44710.88740.098*
H13C0.8986−0.31820.8350.098*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0497 (4)0.0838 (6)0.0731 (5)0.0230 (4)0.0257 (4)−0.0002 (4)
Br20.0595 (4)0.0687 (5)0.0533 (4)0.0172 (3)0.0221 (3)0.0135 (3)
O10.063 (3)0.062 (3)0.055 (3)0.009 (2)0.035 (2)0.015 (2)
O20.048 (3)0.071 (3)0.060 (3)−0.007 (2)0.034 (2)−0.012 (2)
O30.056 (3)0.055 (3)0.078 (3)0.005 (2)0.025 (3)−0.012 (2)
C10.040 (3)0.043 (3)0.044 (3)0.005 (2)0.020 (3)0.000 (3)
C20.032 (3)0.044 (3)0.044 (3)−0.006 (2)0.017 (2)−0.007 (3)
C30.039 (3)0.044 (3)0.036 (3)0.000 (3)0.010 (3)−0.002 (3)
C40.032 (3)0.050 (4)0.048 (4)0.004 (3)0.012 (3)−0.006 (3)
C50.033 (3)0.049 (4)0.047 (3)−0.008 (3)0.021 (3)−0.012 (3)
C60.044 (3)0.045 (3)0.046 (3)−0.006 (3)0.022 (3)−0.004 (3)
C70.070 (5)0.055 (4)0.060 (4)0.004 (4)0.025 (4)0.004 (3)
C80.093 (6)0.088 (6)0.065 (5)−0.004 (5)0.053 (4)−0.021 (4)
C90.036 (3)0.065 (4)0.042 (3)0.007 (3)0.020 (3)0.007 (3)
C100.039 (3)0.060 (4)0.038 (3)0.003 (3)0.024 (3)0.006 (3)
C110.042 (3)0.055 (4)0.043 (3)0.000 (3)0.020 (3)−0.003 (3)
C120.045 (3)0.045 (4)0.043 (3)0.007 (3)0.023 (3)0.002 (3)
C130.075 (5)0.053 (4)0.073 (5)−0.001 (4)0.031 (4)−0.002 (4)

Geometric parameters (Å, °)

Br2—C31.897 (6)C9—H9B0.97
Br1—C41.886 (6)C11—H110.93
O1—C61.363 (6)C8—H8A0.96
O1—C71.422 (5)C8—H8B0.96
O2—C51.379 (6)C8—H8C0.96
O2—C81.421 (5)C1—C61.385 (5)
O3—C121.374 (5)C1—C21.390 (6)
O3—C131.420 (6)C1—H10.93
C12—C10i1.392 (6)C6—C51.400 (6)
C12—C111.393 (6)C4—C51.370 (6)
C3—C41.394 (6)C13—H13A0.96
C3—C21.395 (6)C13—H13B0.96
C10—C111.383 (6)C13—H13C0.96
C10—C12i1.392 (6)C7—H7A0.96
C10—C91.507 (6)C7—H7B0.96
C9—C21.518 (5)C7—H7C0.96
C9—H9A0.97
C6—O1—C7118.4 (5)C6—C1—C2120.9 (5)
C5—O2—C8114.6 (5)C6—C1—H1119.6
C12—O3—C13119.1 (5)C2—C1—H1119.6
O3—C12—C10i115.5 (5)C1—C2—C3118.8 (5)
O3—C12—C11124.1 (6)C1—C2—C9121.1 (5)
C10i—C12—C11120.4 (5)C3—C2—C9120.0 (5)
C4—C3—C2120.1 (5)O1—C6—C1125.0 (5)
C4—C3—Br2120.3 (4)O1—C6—C5115.1 (5)
C2—C3—Br2119.6 (4)C1—C6—C5119.9 (5)
C11—C10—C12i118.8 (5)C5—C4—C3120.8 (5)
C11—C10—C9120.8 (6)C5—C4—Br1118.2 (4)
C12i—C10—C9120.2 (6)C3—C4—Br1120.9 (4)
C10—C9—C2116.9 (5)C4—C5—O2120.7 (5)
C10—C9—H9A108.1C4—C5—C6119.5 (5)
C2—C9—H9A108.1O2—C5—C6119.7 (5)
C10—C9—H9B108.1O3—C13—H13A109.5
C2—C9—H9B108.1O3—C13—H13B109.5
H9A—C9—H9B107.3H13A—C13—H13B109.5
C10—C11—C12120.8 (6)O3—C13—H13C109.5
C10—C11—H11119.6H13A—C13—H13C109.5
C12—C11—H11119.6H13B—C13—H13C109.5
O2—C8—H8A109.5O1—C7—H7A109.5
O2—C8—H8B109.5O1—C7—H7B109.5
H8A—C8—H8B109.5H7A—C7—H7B109.5
O2—C8—H8C109.5O1—C7—H7C109.5
H8A—C8—H8C109.5H7A—C7—H7C109.5
H8B—C8—H8C109.5H7B—C7—H7C109.5
C13—O3—C12—C10i173.5 (5)C7—O1—C6—C5176.8 (5)
C13—O3—C12—C11−6.3 (9)C2—C1—C6—O1178.8 (5)
C11—C10—C9—C2102.1 (7)C2—C1—C6—C5−0.5 (9)
C12i—C10—C9—C2−81.7 (7)C2—C3—C4—C5−0.7 (9)
C12i—C10—C11—C12−0.9 (9)Br2—C3—C4—C5178.8 (4)
C9—C10—C11—C12175.4 (5)C2—C3—C4—Br1−178.7 (4)
O3—C12—C11—C10−179.3 (5)Br2—C3—C4—Br10.8 (7)
C10i—C12—C11—C100.9 (9)C3—C4—C5—O2−176.0 (5)
C6—C1—C2—C31.0 (8)Br1—C4—C5—O22.0 (8)
C6—C1—C2—C9−175.9 (5)C3—C4—C5—C61.2 (9)
C4—C3—C2—C1−0.4 (8)Br1—C4—C5—C6179.3 (4)
Br2—C3—C2—C1−179.9 (4)C8—O2—C5—C4−102.1 (7)
C4—C3—C2—C9176.5 (5)C8—O2—C5—C680.7 (7)
Br2—C3—C2—C9−3.0 (7)O1—C6—C5—C4180.0 (5)
C10—C9—C2—C1−16.1 (8)C1—C6—C5—C4−0.7 (9)
C10—C9—C2—C3167.1 (5)O1—C6—C5—O2−2.8 (8)
C7—O1—C6—C1−2.6 (9)C1—C6—C5—O2176.6 (5)

Symmetry codes: (i) −x+2, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2308).

References

  • Akbaba, Y., Balaydın, H. T., Göksu, S., Şahin, E. & Menzek, A. (2010). Helv. Chim. Acta, 93, 1127–1135.
  • Balaydın, H. T., Akbaba, Y., Menzek, A., Şahin, E. & Göksu, S. (2009). Arkivoc, 14, 75–87.
  • Balaydın, H. T., Gülçin, I., Menzek, A., Göksu, S. & Şahin, E. (2010). J. Enzyme Inhib. Med. Chem.25, 685–695. [PubMed]
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Ford, P. W. & Davidson, B. S. (1993). J. Org. Chem.58, 4522–4523.
  • Glombitza, K. W., Sukopp, I. & Wiedenfeld, H. (1985). Planta Med.51, 437–440. [PubMed]
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