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

Şahin, E.; Balaydın, H.T.; Göksu, S.; Menzek, A.

doi:10.1107/S1600536810043758

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3029

https://doi.org/10.1107/S1600536810043758

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

Ertan Şahin,^a ^* Halis T. Balaydın,^b Süleyman Göksu ^a and Abdullah Menzek ^a

^aAtatürk University, Department of Chemistry, 25240 Erzurum, Turkey, and ^bArtvin Çoruh University, Education Faculty, 08100 Artvin, Turkey
^*Correspondence e-mail: ertan@atauni.edu.tr

(Received 8 October 2010; accepted 26 October 2010; online 31 October 2010)

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 ); Glombitza et al. (1985 ); Akbaba et al. (2010 ); Balaydın et al. (2009 , 2010 ).

Experimental

Crystal data

C₂₆H₂₆Br₄O₆
M_r = 754.07
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.078
wR(F²) = 0.125
S = 1.45
2793 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.50 e Å⁻³

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810043758/gk2308Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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.

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

Computing details top

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

Figures top

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.

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

Crystal data top

C₂₆H₂₆Br₄O₆	F(000) = 740
M_r = 754.07	D_x = 1.837 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6447 reflections
a = 11.193 (5) Å	θ = 2.7–26.4°
b = 9.645 (4) Å	µ = 5.94 mm⁻¹
c = 13.212 (5) Å	T = 293 K
β = 107.125 (5)°	Prism, colourless
V = 1363.1 (10) Å³	0.3 × 0.2 × 0.1 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	2564 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ω scans	θ_max = 26.5°, θ_min = 2.7°
Absorption correction: multi-scan (Blessing, 1995)	h = −14→13
T_min = 0.250, T_max = 0.552	k = −12→12
27932 measured reflections	l = −16→16
2793 independent reflections

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.45	w = 1/[σ²(F_o²) + (0.0035P)² + 2.976P] where P = (F_o² + 2F_c²)/3
2793 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₂₆H₂₆Br₄O₆	V = 1363.1 (10) Å³
M_r = 754.07	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.193 (5) Å	µ = 5.94 mm⁻¹
b = 9.645 (4) Å	T = 293 K
c = 13.212 (5) Å	0.3 × 0.2 × 0.1 mm
β = 107.125 (5)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	2793 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	2564 reflections with I > 2σ(I)
T_min = 0.250, T_max = 0.552	R_int = 0.080
27932 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.45	Δρ_max = 0.29 e Å⁻³
2793 reflections	Δρ_min = −0.50 e Å⁻³
166 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.34470 (6)	0.34698 (9)	0.98736 (6)	0.0672 (3)
Br2	0.53324 (6)	0.33264 (8)	0.83484 (5)	0.0593 (2)
O1	0.6334 (4)	0.0000 (5)	1.2376 (3)	0.0564 (12)
O2	0.4301 (4)	0.1588 (5)	1.1761 (3)	0.0560 (12)
O3	1.0448 (4)	−0.2703 (5)	0.9540 (4)	0.0617 (13)
C1	0.6977 (5)	0.0659 (6)	1.0834 (4)	0.0404 (13)
H1	0.7682	0.0096	1.1038	0.049*
C2	0.6735 (5)	0.1422 (6)	0.9902 (4)	0.0387 (13)
C3	0.5684 (5)	0.2278 (6)	0.9617 (4)	0.0396 (13)
C4	0.4892 (5)	0.2351 (6)	1.0257 (5)	0.0429 (14)
C5	0.5125 (5)	0.1579 (6)	1.1164 (5)	0.0411 (14)
C6	0.6183 (5)	0.0727 (6)	1.1462 (5)	0.0431 (14)
C7	0.7351 (7)	−0.0943 (7)	1.2701 (6)	0.0602 (18)
H7A	0.7309	−0.1595	1.2142	0.09*
H7B	0.7307	−0.1431	1.3322	0.09*
H7C	0.8124	−0.044	1.2858	0.09*
C8	0.4678 (8)	0.2424 (9)	1.2687 (6)	0.076 (2)
H8A	0.5509	0.2169	1.3096	0.114*
H8B	0.4114	0.2284	1.3101	0.114*
H8C	0.4667	0.3382	1.2487	0.114*
C9	0.7554 (5)	0.1280 (7)	0.9173 (5)	0.0458 (15)
H9A	0.7093	0.0755	0.8556	0.055*
H9B	0.7691	0.22	0.8931	0.055*
C10	0.8809 (5)	0.0600 (7)	0.9629 (4)	0.0430 (14)
C11	0.9001 (6)	−0.0763 (6)	0.9392 (5)	0.0450 (14)
H11	0.8332	−0.1287	0.8988	0.054*
C12	1.0184 (5)	−0.1362 (6)	0.9752 (5)	0.0422 (14)
C13	0.9451 (7)	−0.3596 (7)	0.9009 (6)	0.0652 (19)
H13A	0.8909	−0.3738	0.9444	0.098*
H13B	0.9784	−0.4471	0.8874	0.098*
H13C	0.8986	−0.3182	0.835	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0497 (4)	0.0838 (6)	0.0731 (5)	0.0230 (4)	0.0257 (4)	−0.0002 (4)
Br2	0.0595 (4)	0.0687 (5)	0.0533 (4)	0.0172 (3)	0.0221 (3)	0.0135 (3)
O1	0.063 (3)	0.062 (3)	0.055 (3)	0.009 (2)	0.035 (2)	0.015 (2)
O2	0.048 (3)	0.071 (3)	0.060 (3)	−0.007 (2)	0.034 (2)	−0.012 (2)
O3	0.056 (3)	0.055 (3)	0.078 (3)	0.005 (2)	0.025 (3)	−0.012 (2)
C1	0.040 (3)	0.043 (3)	0.044 (3)	0.005 (2)	0.020 (3)	0.000 (3)
C2	0.032 (3)	0.044 (3)	0.044 (3)	−0.006 (2)	0.017 (2)	−0.007 (3)
C3	0.039 (3)	0.044 (3)	0.036 (3)	0.000 (3)	0.010 (3)	−0.002 (3)
C4	0.032 (3)	0.050 (4)	0.048 (4)	0.004 (3)	0.012 (3)	−0.006 (3)
C5	0.033 (3)	0.049 (4)	0.047 (3)	−0.008 (3)	0.021 (3)	−0.012 (3)
C6	0.044 (3)	0.045 (3)	0.046 (3)	−0.006 (3)	0.022 (3)	−0.004 (3)
C7	0.070 (5)	0.055 (4)	0.060 (4)	0.004 (4)	0.025 (4)	0.004 (3)
C8	0.093 (6)	0.088 (6)	0.065 (5)	−0.004 (5)	0.053 (4)	−0.021 (4)
C9	0.036 (3)	0.065 (4)	0.042 (3)	0.007 (3)	0.020 (3)	0.007 (3)
C10	0.039 (3)	0.060 (4)	0.038 (3)	0.003 (3)	0.024 (3)	0.006 (3)
C11	0.042 (3)	0.055 (4)	0.043 (3)	0.000 (3)	0.020 (3)	−0.003 (3)
C12	0.045 (3)	0.045 (4)	0.043 (3)	0.007 (3)	0.023 (3)	0.002 (3)
C13	0.075 (5)	0.053 (4)	0.073 (5)	−0.001 (4)	0.031 (4)	−0.002 (4)

Geometric parameters (Å, º) top

Br2—C3	1.897 (6)	C9—H9B	0.97
Br1—C4	1.886 (6)	C11—H11	0.93
O1—C6	1.363 (6)	C8—H8A	0.96
O1—C7	1.422 (5)	C8—H8B	0.96
O2—C5	1.379 (6)	C8—H8C	0.96
O2—C8	1.421 (5)	C1—C6	1.385 (5)
O3—C12	1.374 (5)	C1—C2	1.390 (6)
O3—C13	1.420 (6)	C1—H1	0.93
C12—C10ⁱ	1.392 (6)	C6—C5	1.400 (6)
C12—C11	1.393 (6)	C4—C5	1.370 (6)
C3—C4	1.394 (6)	C13—H13A	0.96
C3—C2	1.395 (6)	C13—H13B	0.96
C10—C11	1.383 (6)	C13—H13C	0.96
C10—C12ⁱ	1.392 (6)	C7—H7A	0.96
C10—C9	1.507 (6)	C7—H7B	0.96
C9—C2	1.518 (5)	C7—H7C	0.96
C9—H9A	0.97

C6—O1—C7	118.4 (5)	C6—C1—C2	120.9 (5)
C5—O2—C8	114.6 (5)	C6—C1—H1	119.6
C12—O3—C13	119.1 (5)	C2—C1—H1	119.6
O3—C12—C10ⁱ	115.5 (5)	C1—C2—C3	118.8 (5)
O3—C12—C11	124.1 (6)	C1—C2—C9	121.1 (5)
C10ⁱ—C12—C11	120.4 (5)	C3—C2—C9	120.0 (5)
C4—C3—C2	120.1 (5)	O1—C6—C1	125.0 (5)
C4—C3—Br2	120.3 (4)	O1—C6—C5	115.1 (5)
C2—C3—Br2	119.6 (4)	C1—C6—C5	119.9 (5)
C11—C10—C12ⁱ	118.8 (5)	C5—C4—C3	120.8 (5)
C11—C10—C9	120.8 (6)	C5—C4—Br1	118.2 (4)
C12ⁱ—C10—C9	120.2 (6)	C3—C4—Br1	120.9 (4)
C10—C9—C2	116.9 (5)	C4—C5—O2	120.7 (5)
C10—C9—H9A	108.1	C4—C5—C6	119.5 (5)
C2—C9—H9A	108.1	O2—C5—C6	119.7 (5)
C10—C9—H9B	108.1	O3—C13—H13A	109.5
C2—C9—H9B	108.1	O3—C13—H13B	109.5
H9A—C9—H9B	107.3	H13A—C13—H13B	109.5
C10—C11—C12	120.8 (6)	O3—C13—H13C	109.5
C10—C11—H11	119.6	H13A—C13—H13C	109.5
C12—C11—H11	119.6	H13B—C13—H13C	109.5
O2—C8—H8A	109.5	O1—C7—H7A	109.5
O2—C8—H8B	109.5	O1—C7—H7B	109.5
H8A—C8—H8B	109.5	H7A—C7—H7B	109.5
O2—C8—H8C	109.5	O1—C7—H7C	109.5
H8A—C8—H8C	109.5	H7A—C7—H7C	109.5
H8B—C8—H8C	109.5	H7B—C7—H7C	109.5

C13—O3—C12—C10ⁱ	173.5 (5)	C7—O1—C6—C5	176.8 (5)
C13—O3—C12—C11	−6.3 (9)	C2—C1—C6—O1	178.8 (5)
C11—C10—C9—C2	102.1 (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—C5	178.8 (4)
C9—C10—C11—C12	175.4 (5)	C2—C3—C4—Br1	−178.7 (4)
O3—C12—C11—C10	−179.3 (5)	Br2—C3—C4—Br1	0.8 (7)
C10ⁱ—C12—C11—C10	0.9 (9)	C3—C4—C5—O2	−176.0 (5)
C6—C1—C2—C3	1.0 (8)	Br1—C4—C5—O2	2.0 (8)
C6—C1—C2—C9	−175.9 (5)	C3—C4—C5—C6	1.2 (9)
C4—C3—C2—C1	−0.4 (8)	Br1—C4—C5—C6	179.3 (4)
Br2—C3—C2—C1	−179.9 (4)	C8—O2—C5—C4	−102.1 (7)
C4—C3—C2—C9	176.5 (5)	C8—O2—C5—C6	80.7 (7)
Br2—C3—C2—C9	−3.0 (7)	O1—C6—C5—C4	180.0 (5)
C10—C9—C2—C1	−16.1 (8)	C1—C6—C5—C4	−0.7 (9)
C10—C9—C2—C3	167.1 (5)	O1—C6—C5—O2	−2.8 (8)
C7—O1—C6—C1	−2.6 (9)	C1—C6—C5—O2	176.6 (5)

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₆Br₄O₆
M_r	754.07
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.193 (5), 9.645 (4), 13.212 (5)
β (°)	107.125 (5)
V (Å³)	1363.1 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.94
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.250, 0.552
No. of measured, independent and observed [I > 2σ(I)] reflections	27932, 2793, 2564
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.125, 1.45
No. of reflections	2793
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.50

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

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

References

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