2,3,4,5,6 Penta­bromo­phenyl phenyl ether

organic papers

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Structure Reports Online

ISSN 1600-5368

2,3,4,5,6-Pentabromophenyl phenyl ether

Lars Erikssona_{* and Jiwei Hu}b

a_{Division of Structural Chemistry, Arrhenius}

Laboratory, Stockholm University, S-106 91 Stockholm, Sweden, andb_{Department of} Chemistry, University of JyvaÈskylaÈ, FIN-40 351 JyvaÈskylaÈ, Finland

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.010 AÊ Rfactor = 0.036 wRfactor = 0.066

Data-to-parameter ratio = 17.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C12H5Br5O, belongs to a group of ¯ame

retardants known as polybrominated diphenyl ethers (PBDE). Salient features of the packing are stabilization due to intermolecular Br Br contacts in theabplane and aromatic intermolecular contacts along thecdirection.

Comment

An important group of ¯ame retardants are the poly-brominated diphenyl ethers (PBDE). There are a total of 209 different PBDE's. The modelling of the reactivity of different PBDE's is a task that requires accurate geometries of the molecular species. Geometric data from crystallographic measurements on brominated diphenyl ethers without hetero substituents other than bromine are rather limited (OÈrnet al., 1996; Erikssonet al., 1999; Mrseet al., 2000; Eriksson & Hu, 2001, 2002; Eriksson et al., 2002a,b). In addition, a partial structure of bis(4-bromophenyl) ether (Toussaint, 1946) has been published. In a search of the Cambridge Structural Database (Allen & Kennard, 1993), including hetero substit-uents other than bromine, a larger set of structures for use as model compounds was found, but still only in the order of 10± 15 different structures.

The bromine-substituted ring is planar with an r.m.s. deviation of 0.012 AÊ for the C atoms (C1±C6) of the ring. The O atom deviates most from this plane, by 0.163 (8) AÊ, while atoms Br1, Br2 and Br3 lie within 2of the plane; atoms Br4 and Br5 deviate by 0.037 (8) and 0.035 (8) AÊ, respectively. The second, unsubstituted, aromatic ring (C7±C12) is more strictly planar, with an r.m.s. deviation of 0.004 AÊ for the C atoms. The O atom is coplanar with this ring. The angle between the two ring planes is 89.7 (2)_.

A view of the arrangement of the molecules of the title compound, (I), is shown in Fig. 2, where the two shortest intermolecular Br Br contacts are marked. The closest intermolecular Br Br contacts are: Br3 Br4i_{= 3.567 (1) AÊ}

and Br2 Br2ii _{= 3.698 (1) AÊ [symmetry codes: (i) ÿx,}

ÿ1/2+y, 1/2ÿz; (ii) 1ÿx, 1/2+y, 1/2ÿz]. The Br2 atoms of different molecules form a connected zigzag chain of close contacts along thebaxis. Similarly, atoms Br3 and Br4 form a set of intermolecular contacts along the b axis and also

contribute to the bonding in the a-axis direction. The short intermolecular Br Br contacts stabilize the structure in the

abplane, as shown in Fig. 3. Along the c-axis direction, the structure is essentially stabilized by interaction between the unsubstituted aromatic ring system and symmetry-related equivalents, also interactions between both Br1 and Br5 with the unsubstituted aromatic ring.

A related packing pattern was found for 2,4-dibromophenyl 4-bromophenyl ether (Eriksson & Hu, 2002), where the bonding in two directions of the unit cell can be described as partly due to Br Br interactions. The packing in the third direction is governed mainly by interactions between the aromatic ring systems. The molecules form sheets, with the less substituted ring pointing outwards in every second molecule (cf. Fig. 3) of the title compound, while for the aforementioned 2,4-dibromophenyl 4-bromophenyl ether (Eriksson & Hu, 2002), there are larger cavities where two equivalents of the less substituted ring may ®t.

Experimental

The synthesis of the PBDE was carried out by coupling of di-phenyliodonium bromide with sodium pentabromophenylate (Beringeret al., 1959; Ziegler & Marr, 1962; Hu, 1996, 1999). The title compound was recrystallized from methanol.

Crystal data

C12H5Br5O Mr= 564.71

Monoclinic,P21=c a= 11.579 (4) AÊ

b= 5.3284 (11) AÊ

c= 24.133 (6) AÊ

= 102.66 (3)

V= 1452.7 (6) AÊ3 Z= 4

Dx= 2.582 Mg mÿ3

MoKradiation Cell parameters from 1573

re¯ections

= 1.7±26.0

= 13.82 mmÿ1 T= 293 (2) K Slab, colourless 0.300.090.08 mm

Data collection

Stoe IPDS area-detector diffractometer

'scans

Absorption correction: numerical (X-RED; Stoe & Cie, 1997)

Tmin= 0.081,Tmax= 0.328

18710 measured re¯ections

2843 independent re¯ections 1503 re¯ections withI> 2(I)

Rint= 0.114

max= 26.0 h=ÿ14!14

k=ÿ6!6

l=ÿ29!29

Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.036} wR(F2_{) = 0.066} S= 1.03 2843 re¯ections 163 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.005P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.55 e AÊÿ3

min=ÿ0.68 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

Br1ÐC2 1.866 (6) Br2ÐC3 1.900 (6) Br3ÐC4 1.880 (6) Br4ÐC5 1.882 (6)

Br5ÐC6 1.876 (6) OÐC1 1.371 (7) OÐC7 1.403 (8) C1ÐOÐC7 118.9 (4)

OÐC1ÐC2 119.1 (5) OÐC1ÐC6 119.0 (6) C2ÐC1ÐC6 121.6 (6)

C12ÐC7ÐC8 120.8 (6) C12ÐC7ÐO 123.8 (6) C8ÐC7ÐO 115.5 (6) C7ÐOÐC1ÐC2 100.4 (7)

C7ÐOÐC1ÐC6 ÿ86.2 (7) C1ÐOÐC7ÐC12C1ÐOÐC7ÐC8 ÿ166.8 (5)12.9 (9)

Two data sets were recorded with the Stoe IPDS system, using different settings of the crystal. The data sets were brought to a

Acta Cryst.(2002). E58, o794±o796 Eriksson and Hu C₁₂H₅Br₅O

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organic papers

Figure 1

The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms

are shown as small circles of arbitrary radii. Figure 2_{Stereoview of the packing, viewed along thebdirection, with the two} shortest Br Br contacts indicated by thick dashed bonds.

Figure 3

organic papers

o796

common scale by use of batch scale factors (BASF) determined with

SHELXL97, and were merged. The rather high internalRvalue of 0.114 decreases to 0.073 when only re¯ections withI2(I) are used. Data collection: EXPOSE in IPDS (Stoe & Cie, 1997); cell re®nement:CELLinIPDS; data reduction:INTEGRATEinIPDS

andX-RED(Stoe & Cie, 1997); program(s) used to solve structure:

SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND

(Bergerhoff, 1996).

This work was supported by a grant from the Swedish Natural Science Research Council.

References

Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Bergerhoff, G. (1996).DIAMOND. Gerhard-Domagk-Straûe 1, 53121 Bonn,

Germany.

Beringer, F. M., Falk, R. A., Karniol, M., Lillien, G., Masullo, M., Mausner, M. & Sommer, E. (1959).J. Am. Chem. Soc.81, 342±351.

Eriksson, J., Eriksson, L. & Hu, J. (2002a).Acta Cryst.E58, o263±o265. Eriksson, J., Eriksson, L. & Hu, J. (2002b).Acta Cryst.E58, o347±o349. Eriksson, J., Eriksson, L. & Jakobsson, E. (1999).Acta Cryst. C55, 2169±

2171.

Eriksson, L. & Hu, J. (2001).Acta Cryst.E57, o930±o932. Eriksson, L. & Hu, J. (2002).Acta Cryst.E58, o696±o698.

Hu, J. (1996). Licenciate Thesis, Department of Environmental Chemistry, Stockholm University, Sweden.

Hu, J. (1999). Doctorate Thesis, Department of Chemistry, Research Report No. 73, University of JyvaÈskylaÈ, JyvaÈskylaÈ, Finland.

Mrse, A. A., Watkins, S. F. & Fronczek, F. R. (2000).Acta Cryst.C56, e576± e577.

OÈrn, U., Eriksson, L., Jakobsson, E. & Bergman, AÊ. (1996).Acta Chem. Scand.

50, 802±807.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Stoe & Cie (1997).IPDS(Version 2.87) andX-RED(Version 1.09). Stoe &

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Acta Cryst. (2002). E58, o794–o796

supporting information

Acta Cryst. (2002). E58, o794–o796 [https://doi.org/10.1107/S1600536802010942]

2,3,4,5,6-Pentabromophenyl phenyl ether

Lars Eriksson and Jiwei Hu

2,3,4,5,6-Pentabromophenyl phenyl ether

Crystal data

C12H5Br5O Mr = 564.71

Monoclinic, P21/c a = 11.579 (4) Å

b = 5.3284 (11) Å

c = 24.133 (6) Å

β = 102.66 (3)°

V = 1452.7 (6) Å3 Z = 4

F(000) = 1040

Dx = 2.582 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1573 reflections

θ = 1.7–26.0°

µ = 13.82 mm−1 T = 293 K Slab, colourless 0.30 × 0.09 × 0.08 mm

Data collection

STOE IPDS area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 6.0 pixels mm-1 φ scans

Absorption correction: numerical (X-RED; Stoe & Cie, 1997)

Tmin = 0.081, Tmax = 0.328

18710 measured reflections 2843 independent reflections 1503 reflections with I > 2σ(I)

Rint = 0.114

θmax = 26.0°, θmin = 2.2° h = −14→14

k = −6→6

l = −29→29

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.036} wR(F2_{) = 0.066} S = 1.03 2843 reflections 163 parameters 46 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.005P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.55 e Å−3

Δρmin = −0.68 e Å−3

Special details

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Acta Cryst. (2002). E58, o794–o796

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Br1 0.41828 (7) −0.49976 (14) 0.39688 (4) 0.0702 (3)

Br2 0.43124 (8) −0.14732 (16) 0.28503 (4) 0.0776 (3)

Br3 0.22400 (9) 0.27635 (13) 0.24144 (4) 0.0742 (3)

Br4 0.01204 (8) 0.35015 (13) 0.31134 (3) 0.0643 (2)

Br5 0.00287 (7) −0.01692 (15) 0.42045 (4) 0.0643 (2)

O 0.2005 (4) −0.3910 (7) 0.44035 (19) 0.0504 (12)

C1 0.2119 (6) −0.2252 (10) 0.3984 (3) 0.0387 (15)

C2 0.3031 (6) −0.2569 (10) 0.3708 (3) 0.0437 (16)

C3 0.3068 (6) −0.1071 (12) 0.3242 (3) 0.0474 (17)

C4 0.2189 (6) 0.0720 (10) 0.3044 (3) 0.0444 (16)

C5 0.1298 (6) 0.1052 (10) 0.3346 (3) 0.0417 (16)

C6 0.1252 (6) −0.0476 (10) 0.3811 (3) 0.0377 (15)

C7 0.2418 (6) −0.3206 (11) 0.4973 (3) 0.0424 (16)

C8 0.2054 (6) −0.4716 (12) 0.5368 (3) 0.0526 (18)

H8 0.1563 −0.6085 0.5250 0.063*

C9 0.2420 (7) −0.4186 (15) 0.5935 (4) 0.068 (2)

H9 0.2184 −0.5210 0.6202 0.082*

C10 0.3125 (7) −0.2173 (14) 0.6109 (3) 0.063 (2)

H10 0.3371 −0.1821 0.6494 0.076*

C11 0.3474 (7) −0.0657 (13) 0.5715 (3) 0.065 (2)

H11 0.3947 0.0735 0.5835 0.078*

C12 0.3126 (7) −0.1186 (12) 0.5140 (3) 0.0561 (19)

H12 0.3372 −0.0177 0.4873 0.067*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Br1 0.0518 (5) 0.0524 (4) 0.0998 (7) 0.0107 (4) 0.0024 (5) −0.0123 (4)

Br2 0.0648 (6) 0.0970 (6) 0.0841 (7) −0.0227 (5) 0.0449 (5) −0.0308 (5)

Br3 0.1041 (8) 0.0737 (5) 0.0446 (5) −0.0332 (5) 0.0159 (4) 0.0063 (4)

Br4 0.0692 (6) 0.0520 (4) 0.0611 (5) 0.0118 (4) −0.0088 (4) −0.0021 (4)

Br5 0.0529 (5) 0.0799 (5) 0.0671 (5) 0.0038 (4) 0.0282 (4) −0.0030 (5)

O 0.068 (4) 0.036 (2) 0.045 (3) −0.012 (2) 0.010 (3) 0.003 (2)

C1 0.049 (4) 0.036 (3) 0.031 (4) −0.001 (3) 0.007 (3) 0.001 (3)

C2 0.043 (4) 0.033 (3) 0.055 (4) 0.005 (3) 0.010 (4) −0.011 (3)

C3 0.051 (5) 0.050 (4) 0.045 (4) −0.013 (3) 0.019 (4) −0.021 (3)

C4 0.047 (4) 0.044 (4) 0.042 (4) −0.013 (3) 0.012 (3) −0.009 (3)

C5 0.047 (4) 0.029 (3) 0.044 (4) −0.002 (3) −0.002 (3) −0.007 (3)

C6 0.037 (4) 0.036 (3) 0.040 (4) −0.003 (3) 0.008 (3) −0.005 (3)

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C8 0.059 (5) 0.049 (4) 0.052 (5) 0.001 (3) 0.018 (4) 0.007 (4)

C9 0.069 (6) 0.087 (6) 0.052 (5) 0.011 (4) 0.021 (5) 0.016 (4)

C10 0.061 (6) 0.076 (5) 0.049 (5) 0.026 (4) 0.007 (4) −0.007 (4)

C11 0.068 (6) 0.063 (5) 0.056 (5) 0.000 (4) −0.007 (4) −0.010 (4)

C12 0.063 (5) 0.051 (4) 0.049 (5) −0.011 (4) 0.001 (4) 0.004 (3)

Geometric parameters (Å, º)

Br1—C2 1.866 (6) C3—C4 1.401 (9)

Br2—C3 1.900 (6) C4—C5 1.400 (9)

Br3—C4 1.880 (6) C5—C6 1.397 (8)

Br4—C5 1.882 (6) C7—C12 1.359 (8)

Br5—C6 1.876 (6) C7—C8 1.383 (8)

O—C1 1.371 (7) C8—C9 1.369 (10)

O—C7 1.403 (8) C9—C10 1.358 (10)

C1—C2 1.377 (8) C10—C11 1.375 (10)

C1—C6 1.377 (8) C11—C12 1.387 (10)

C2—C3 1.388 (9)

C1—O—C7 118.9 (4) C6—C5—Br4 119.4 (5)

O—C1—C2 119.1 (5) C4—C5—Br4 120.0 (5)

O—C1—C6 119.0 (6) C1—C6—C5 119.4 (6)

C2—C1—C6 121.6 (6) C1—C6—Br5 119.2 (4)

C1—C2—C3 119.0 (6) C5—C6—Br5 121.4 (5)

C1—C2—Br1 119.3 (5) C12—C7—C8 120.8 (6)

C3—C2—Br1 121.7 (5) C12—C7—O 123.8 (6)

C2—C3—C4 121.3 (6) C8—C7—O 115.5 (6)

C2—C3—Br2 120.0 (5) C9—C8—C7 119.6 (7)

C4—C3—Br2 118.7 (5) C10—C9—C8 120.4 (7)

C5—C4—C3 118.1 (6) C9—C10—C11 119.9 (8)

C5—C4—Br3 120.3 (5) C10—C11—C12 120.5 (7)

C3—C4—Br3 121.4 (5) C7—C12—C11 118.8 (7)

C6—C5—C4 120.5 (6)

C7—O—C1—C2 100.4 (7) O—C1—C6—C5 −173.5 (5)

C7—O—C1—C6 −86.2 (7) C2—C1—C6—C5 −0.3 (9)

O—C1—C2—C3 172.7 (5) O—C1—C6—Br5 6.3 (8)

C6—C1—C2—C3 −0.5 (9) C2—C1—C6—Br5 179.5 (5)

O—C1—C2—Br1 −7.2 (8) C4—C5—C6—C1 2.6 (9)

C6—C1—C2—Br1 179.6 (5) Br4—C5—C6—C1 −179.4 (5)

C1—C2—C3—C4 −0.9 (9) C4—C5—C6—Br5 −177.2 (5)

Br1—C2—C3—C4 179.0 (5) Br4—C5—C6—Br5 0.8 (7)

C1—C2—C3—Br2 −179.8 (5) C1—O—C7—C12 −12.9 (9)

Br1—C2—C3—Br2 0.1 (7) C1—O—C7—C8 166.8 (5)

C2—C3—C4—C5 3.1 (9) C12—C7—C8—C9 −0.7 (10)

Br2—C3—C4—C5 −178.0 (4) O—C7—C8—C9 179.6 (6)

C2—C3—C4—Br3 179.7 (5) C7—C8—C9—C10 0.8 (11)

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Acta Cryst. (2002). E58, o794–o796

C3—C4—C5—C6 −3.9 (9) C9—C10—C11—C12 −0.9 (11)

Br3—C4—C5—C6 179.5 (4) C8—C7—C12—C11 −0.2 (10)

C3—C4—C5—Br4 178.1 (4) O—C7—C12—C11 179.5 (6)