1,3-Dibenz­yloxy-5-(bromo­meth­yl)benzene

Zhu, P.; Zhao, Y.; Chen, H.; Cui, Q.; Wei, Q.

doi:10.1107/S1600536809009672

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o823

doi:10.1107/S1600536809009672

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1,3-Dibenzyloxy-5-(bromomethyl)benzene

Peihua Zhu,^a ^* Yanfang Zhao,^a Haiyan Chen,^a Qingtao Cui ^a and Qin Wei ^a

^aSchool of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, People's Republic of China
^*Correspondence e-mail: chm_zhuph@ujn.edu.cn

(Received 13 March 2009; accepted 16 March 2009; online 25 March 2009)

In the title compound, C₂₁H₁₉BrO₂, the dihedral angles between the central benzene ring and the two peripheral rings are 50.28 (5) and 69.75 (2)°. The O—CH₂ bonds lie in the plane of the central ring and adopt a syn–anti conformation.

Related literature

For related compounds, see: Pan et al. (2005 ); Xiao et al. (2007 ); For the synthesis, see: Hawker & Fréchet (1990 ).

Experimental

Crystal data

C₂₁H₁₉BrO₂
M_r = 383.27
Triclinic, $[P \overline 1]$
a = 4.4449 (17) Å
b = 11.982 (5) Å
c = 16.726 (6) Å
α = 86.834 (7)°
β = 87.509 (7)°
γ = 86.524 (7)°
V = 887.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.33 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.653, T_max = 0.801
4223 measured reflections
3030 independent reflections
2199 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.090
S = 1.02
3030 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009672/hg2488sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009672/hg2488Isup2.hkl

checkCIF report

Comment top

The chemistry and physics of dendritic compounds started a decade ago. Today, this science of uniquely shaped molecules, namely, dendrite-shaped molecules, is one of the most exciting topics of contemporary interdisciplinary research. As a part of our structural investigations on dendritic macromolecules, the single-crystal X-ray diffraction study on the title compound was carried out. The compound crystallizes in the triclinic system with a P-1 space group. In the title compound, the O—CH₂ bonds lie in the plane of the central phenyl ring and adopt a syn, anti conformation. Comparatively, the O—CH₂ bonds adopt a syn,syn conformation in the structure of other analogues reported. (Pan et al.2005, Xiao et al.2007) The dihedral angles between the central benzene ring and the two peripheral ones are 50.28 (5)°, 69.75 (2)° respectively. Although structure of the title compound is similiar to those reported, the dihedral angles in different compounds are sgnificantly different.(Xiao et al.2007)

Related literature top

For related compounds, see: Pan et al. (2005); Xiao et al. (2007); For the synthesis, see: Hawker & Fréchet (1990).

Experimental top

(3,5-Bis-benzyloxy-phenyl)-methanol (4.89 g, 15 mmol) was prepared by treatment with CBr₄ (6.23 g, 18.75 mmol) and triphenylphosphine(4.92 g, 18.75 mmol) in THF(85 ml) for 15 min at room temperature. Conventional workup and purification with silica-gel column chromatography (eluent: chloroform) gave 5.8 g of1,3-Bis-benzyloxy-5-bromomethyl-benzene (65%) as a colorless needles (Hawker & Fréchet, 1990). Single crystals suitable for X-ray study were grown by diffusion method[dichloromethane/n-hexane (1:6, V/V)] at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure, with atom labels and 25% probability displacement ellipsoids for non-H atoms.

1,3-Dibenzyloxy-5-(bromomethyl)benzene top

Crystal data top

C₂₁H₁₉BrO₂	Z = 2
M_r = 383.27	F(000) = 392
Triclinic, P1	D_x = 1.435 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4449 (17) Å	Cell parameters from 1804 reflections
b = 11.982 (5) Å	θ = 2.4–25.7°
c = 16.726 (6) Å	µ = 2.33 mm⁻¹
α = 86.834 (7)°	T = 298 K
β = 87.509 (7)°	Needle, colorless
γ = 86.524 (7)°	0.20 × 0.15 × 0.10 mm
V = 887.1 (6) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3030 independent reflections
Radiation source: fine-focus sealed tube	2199 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ϕ and ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→14
T_min = 0.653, T_max = 0.801	l = −19→16
4223 measured 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0439P)²] where P = (F_o² + 2F_c²)/3
3030 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₁H₁₉BrO₂	γ = 86.524 (7)°
M_r = 383.27	V = 887.1 (6) Å³
Triclinic, P1	Z = 2
a = 4.4449 (17) Å	Mo Kα radiation
b = 11.982 (5) Å	µ = 2.33 mm⁻¹
c = 16.726 (6) Å	T = 298 K
α = 86.834 (7)°	0.20 × 0.15 × 0.10 mm
β = 87.509 (7)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3030 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2199 reflections with I > 2σ(I)
T_min = 0.653, T_max = 0.801	R_int = 0.023
4223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	Δρ_max = 0.38 e Å⁻³
3030 reflections	Δρ_min = −0.40 e Å⁻³
217 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	1.29871 (8)	0.68293 (3)	0.023543 (18)	0.07695 (18)
O1	0.8518 (4)	0.63235 (14)	0.34038 (10)	0.0550 (5)
O2	0.9591 (4)	0.27865 (14)	0.22300 (11)	0.0564 (5)
C19	0.7393 (9)	−0.1122 (3)	0.2047 (3)	0.0876 (12)
H19	0.6533	−0.1810	0.2129	0.105*
C5	0.9054 (6)	0.4506 (2)	0.28173 (14)	0.0425 (6)
H5	0.7738	0.4187	0.3200	0.051*
C12	0.4165 (10)	0.8523 (4)	0.5579 (2)	0.0898 (12)
H12	0.3621	0.9099	0.5917	0.108*
C6	1.0397 (6)	0.3871 (2)	0.22160 (15)	0.0428 (6)
C2	1.2996 (5)	0.5448 (2)	0.16780 (14)	0.0402 (6)
C4	0.9692 (6)	0.5614 (2)	0.28420 (14)	0.0422 (6)
C9	0.5721 (6)	0.6814 (2)	0.45747 (15)	0.0467 (6)
C16	0.9864 (6)	0.0932 (2)	0.18116 (17)	0.0502 (7)
C7	1.2350 (6)	0.4338 (2)	0.16442 (14)	0.0425 (6)
H7	1.3223	0.3908	0.1240	0.051*
C3	1.1667 (6)	0.6085 (2)	0.22694 (14)	0.0427 (6)
H3	1.2089	0.6834	0.2287	0.051*
C10	0.3915 (7)	0.7726 (3)	0.43176 (19)	0.0670 (9)
H10	0.3194	0.7761	0.3803	0.080*
C8	0.6577 (6)	0.5895 (2)	0.40320 (15)	0.0493 (7)
H8A	0.7606	0.5275	0.4326	0.059*
H8B	0.4789	0.5627	0.3812	0.059*
C17	0.9854 (8)	0.0362 (3)	0.2548 (2)	0.0673 (9)
H17	1.0693	0.0677	0.2976	0.081*
C15	1.1188 (7)	0.2048 (2)	0.16995 (17)	0.0560 (7)
H15A	1.3311	0.1981	0.1818	0.067*
H15B	1.1004	0.2336	0.1149	0.067*
C18	0.8630 (9)	−0.0662 (3)	0.2663 (2)	0.0809 (10)
H18	0.8654	−0.1037	0.3165	0.097*
C14	0.6715 (8)	0.6790 (3)	0.53462 (17)	0.0669 (8)
H14	0.7948	0.6184	0.5531	0.080*
C13	0.5932 (10)	0.7634 (3)	0.5845 (2)	0.0875 (12)
H13	0.6611	0.7597	0.6364	0.105*
C11	0.3172 (9)	0.8579 (3)	0.4810 (2)	0.0894 (11)
H11	0.1990	0.9199	0.4626	0.107*
C1	1.5149 (6)	0.5949 (2)	0.10714 (15)	0.0523 (7)
H1A	1.6408	0.5358	0.0831	0.063*
H1B	1.6449	0.6426	0.1333	0.063*
C20	0.7390 (10)	−0.0585 (3)	0.1296 (3)	0.0965 (13)
H20	0.6564	−0.0909	0.0870	0.116*
C21	0.8642 (9)	0.0451 (3)	0.1187 (2)	0.0784 (10)
H21	0.8649	0.0821	0.0683	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0785 (3)	0.0946 (3)	0.0517 (2)	0.01328 (19)	0.01038 (15)	0.02101 (17)
O1	0.0725 (13)	0.0473 (11)	0.0460 (11)	−0.0111 (10)	0.0159 (9)	−0.0164 (9)
O2	0.0716 (13)	0.0400 (11)	0.0572 (12)	−0.0051 (9)	0.0170 (10)	−0.0124 (9)
C19	0.083 (3)	0.052 (2)	0.129 (4)	−0.0135 (19)	0.010 (2)	−0.024 (2)
C5	0.0473 (16)	0.0435 (15)	0.0366 (14)	−0.0023 (12)	0.0006 (11)	−0.0030 (11)
C12	0.108 (3)	0.085 (3)	0.080 (3)	−0.019 (2)	0.034 (2)	−0.050 (2)
C6	0.0455 (15)	0.0430 (16)	0.0404 (14)	0.0007 (12)	−0.0035 (12)	−0.0077 (12)
C2	0.0348 (14)	0.0499 (16)	0.0364 (13)	−0.0010 (12)	−0.0070 (11)	−0.0034 (12)
C4	0.0452 (15)	0.0466 (16)	0.0353 (13)	0.0001 (12)	−0.0032 (11)	−0.0088 (12)
C9	0.0504 (17)	0.0514 (16)	0.0380 (14)	−0.0055 (13)	0.0068 (12)	−0.0046 (12)
C16	0.0511 (17)	0.0415 (16)	0.0582 (18)	0.0036 (13)	0.0017 (13)	−0.0140 (14)
C7	0.0461 (16)	0.0450 (16)	0.0363 (14)	0.0047 (12)	−0.0003 (11)	−0.0096 (11)
C3	0.0459 (15)	0.0436 (15)	0.0392 (14)	−0.0052 (12)	−0.0025 (12)	−0.0053 (12)
C10	0.071 (2)	0.071 (2)	0.0597 (19)	0.0100 (18)	−0.0068 (16)	−0.0173 (17)
C8	0.0568 (18)	0.0486 (16)	0.0419 (15)	−0.0026 (14)	0.0053 (13)	−0.0030 (12)
C17	0.081 (2)	0.058 (2)	0.065 (2)	−0.0096 (17)	−0.0008 (17)	−0.0114 (16)
C15	0.0654 (19)	0.0506 (17)	0.0520 (17)	−0.0011 (15)	0.0092 (14)	−0.0154 (14)
C18	0.095 (3)	0.060 (2)	0.086 (3)	−0.003 (2)	0.010 (2)	−0.004 (2)
C14	0.090 (2)	0.065 (2)	0.0463 (17)	−0.0059 (17)	−0.0089 (15)	−0.0032 (15)
C13	0.130 (3)	0.091 (3)	0.0449 (19)	−0.025 (3)	0.004 (2)	−0.019 (2)
C11	0.096 (3)	0.069 (2)	0.102 (3)	0.019 (2)	0.007 (2)	−0.029 (2)
C1	0.0479 (17)	0.0649 (18)	0.0443 (15)	−0.0028 (14)	−0.0011 (12)	−0.0059 (14)
C20	0.108 (3)	0.074 (3)	0.115 (4)	−0.012 (2)	−0.026 (3)	−0.045 (3)
C21	0.100 (3)	0.063 (2)	0.075 (2)	0.004 (2)	−0.0199 (19)	−0.0196 (18)

Geometric parameters (Å, º) top

Br1—C1	1.955 (3)	C16—C17	1.374 (4)
O1—C4	1.368 (3)	C16—C15	1.493 (4)
O1—C8	1.424 (3)	C7—H7	0.9300
O2—C6	1.368 (3)	C3—H3	0.9300
O2—C15	1.425 (3)	C10—C11	1.364 (4)
C19—C18	1.348 (5)	C10—H10	0.9300
C19—C20	1.379 (6)	C8—H8A	0.9700
C19—H19	0.9300	C8—H8B	0.9700
C5—C4	1.377 (4)	C17—C18	1.372 (5)
C5—C6	1.387 (3)	C17—H17	0.9300
C5—H5	0.9300	C15—H15A	0.9700
C12—C13	1.352 (5)	C15—H15B	0.9700
C12—C11	1.375 (5)	C18—H18	0.9300
C12—H12	0.9300	C14—C13	1.365 (4)
C6—C7	1.381 (4)	C14—H14	0.9300
C2—C3	1.374 (3)	C13—H13	0.9300
C2—C7	1.383 (4)	C11—H11	0.9300
C2—C1	1.491 (4)	C1—H1A	0.9700
C4—C3	1.391 (4)	C1—H1B	0.9700
C9—C10	1.376 (4)	C20—C21	1.390 (5)
C9—C14	1.380 (4)	C20—H20	0.9300
C9—C8	1.487 (3)	C21—H21	0.9300
C16—C21	1.368 (4)

C4—O1—C8	118.8 (2)	C9—C8—H8A	110.1
C6—O2—C15	118.0 (2)	O1—C8—H8B	110.1
C18—C19—C20	120.7 (4)	C9—C8—H8B	110.1
C18—C19—H19	119.7	H8A—C8—H8B	108.4
C20—C19—H19	119.7	C18—C17—C16	121.3 (3)
C4—C5—C6	119.3 (3)	C18—C17—H17	119.3
C4—C5—H5	120.4	C16—C17—H17	119.3
C6—C5—H5	120.4	O2—C15—C16	108.0 (2)
C13—C12—C11	120.1 (3)	O2—C15—H15A	110.1
C13—C12—H12	119.9	C16—C15—H15A	110.1
C11—C12—H12	119.9	O2—C15—H15B	110.1
O2—C6—C7	123.9 (2)	C16—C15—H15B	110.1
O2—C6—C5	115.2 (2)	H15A—C15—H15B	108.4
C7—C6—C5	120.8 (2)	C19—C18—C17	119.8 (4)
C3—C2—C7	120.1 (2)	C19—C18—H18	120.1
C3—C2—C1	120.2 (2)	C17—C18—H18	120.1
C7—C2—C1	119.7 (2)	C13—C14—C9	121.6 (3)
O1—C4—C5	124.8 (2)	C13—C14—H14	119.2
O1—C4—C3	115.2 (2)	C9—C14—H14	119.2
C5—C4—C3	120.1 (2)	C12—C13—C14	119.6 (3)
C10—C9—C14	117.8 (3)	C12—C13—H13	120.2
C10—C9—C8	120.6 (2)	C14—C13—H13	120.2
C14—C9—C8	121.6 (3)	C10—C11—C12	120.2 (4)
C21—C16—C17	118.5 (3)	C10—C11—H11	119.9
C21—C16—C15	121.0 (3)	C12—C11—H11	119.9
C17—C16—C15	120.5 (3)	C2—C1—Br1	110.84 (18)
C6—C7—C2	119.5 (2)	C2—C1—H1A	109.5
C6—C7—H7	120.3	Br1—C1—H1A	109.5
C2—C7—H7	120.3	C2—C1—H1B	109.5
C2—C3—C4	120.2 (2)	Br1—C1—H1B	109.5
C2—C3—H3	119.9	H1A—C1—H1B	108.1
C4—C3—H3	119.9	C19—C20—C21	118.9 (4)
C11—C10—C9	120.7 (3)	C19—C20—H20	120.5
C11—C10—H10	119.7	C21—C20—H20	120.5
C9—C10—H10	119.7	C16—C21—C20	120.7 (4)
O1—C8—C9	108.1 (2)	C16—C21—H21	119.6
O1—C8—H8A	110.1	C20—C21—H21	119.6

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉BrO₂
M_r	383.27
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	4.4449 (17), 11.982 (5), 16.726 (6)
α, β, γ (°)	86.834 (7), 87.509 (7), 86.524 (7)
V (Å³)	887.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.33
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.653, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	4223, 3030, 2199
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.090, 1.02
No. of reflections	3030
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.40

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by Shandong Province (2007BS02016) and the Key Subject Research Foundation of Shandong Province (XTD 0705).

References

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