organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4,5,6,7-Tetra­bromo-1,1,3-tri­methyl-3-(2,3,4,5-tetra­bromo­phen­yl)indane

aWellington Laboratories, Research Division, Guelph, Ontario, Canada N1G 3M5, bDepartment of Chemistry, University of Guelph, Ontario, Canada N1G 2W1, and cDepartment of Chemistry, University of Toronto, Ontario, Canada M5S 3H6
*Correspondence e-mail: alough@chem.utoronto.ca

(Received 3 December 2007; accepted 7 January 2008; online 16 January 2008)

The title compound (OctaInd), C18H12Br8, is a commercial brominated flame retardant (BFR). In the mol­ecule, the five-membered ring has a slight envelope conformation, with a deviation of 0.317 (9) Å for the flap C atom from four essentially planar C atoms. The dihedral angle between the two benzene rings is 74.00 (16) Å.

Related literature

For related literature, see: Andersson et al. (2006[Andersson, P. L., Öberg, K. & Örn, U. (2006). Environ. Toxicol. Chem. 25, 1275-1282.]); Muir et al. (2007[Muir, D., Howard, P. H. & Metlan, W. (2007). Organohalogen Compd. 69, 1053-1056.]); Richardson (2007[Richardson, S. D. (2007). Anal. Chem. 79, 4295-4324.]). See also Appendix 3 in a Danish EPA report published in 1999 on `Physical-chemical Properties of Brominated Flame Retardants'; http://www2.mst.dk/udgiv/Publications/1999/87-7909-416-3/html/bil03_eng.htm .

[Scheme 1]

Experimental

Crystal data
  • C18H12Br8

  • Mr = 867.56

  • Monoclinic, P 21 /c

  • a = 20.2603 (6) Å

  • b = 7.3862 (2) Å

  • c = 15.2233 (8) Å

  • β = 110.4070 (15)°

  • V = 2135.14 (14) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 15.03 mm−1

  • T = 150 (1) K

  • 0.16 × 0.14 × 0.14 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.057, Tmax = 0.122

  • 13121 measured reflections

  • 4862 independent reflections

  • 3509 reflections with I > 2σ(I)

  • Rint = 0.059

Refinement
  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.111

  • S = 0.99

  • 4862 reflections

  • 238 parameters

  • H-atom parameters constrained

  • Δρmax = 1.33 e Å−3

  • Δρmin = −1.34 e Å−3

Data collection: COLLECT (Nonius, 2002[Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO–SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXTL (Sheldrick, 2001[Sheldrick, G. M. (2001). SHELXTL/PC. Version 6.1. Windows XP Version. Bruker AXS Inc., Madison, USA.]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Tetrabromotrimethylphenylindane (OctaInd) is a commercial brominated flame retardant (BFR) used in styrenic and engineering thermoplastics (http://www2.mst.dk/udgiv/Publications/1999/87–7909-416–3/html/bil03_eng.htm). The major component in the commercial mixture is believed to be 1,1,3-trimethyl-4,5,6,7-tetrabromo-3-(2,3,4,5-tetrabromophenyl)indane. BFRs have been used in a variety of products to protect human life and property against fires. However, there is a growing concern that these BFR compounds are becoming significant environmental contaminants because of their widespread presence in the environment and in human and wildlife samples (Richardson, 2007). Very little is known about OctaInd and, to the best of our knowledge, it has not been reported in the environmental literature. However, OctaInd was one of the top ten persistent brominated or chlorinated compounds identified by QSPR screening that deserves greater attention (Muir et al., 2007). In a recent modeling study (Andersson et al., 2006) OctaInd was described as being 1,1,3-trimethyl-4,5,6,7-tetrabromo-3-(2,3,4,6-tetrabromophenyl)indane (note the different substitution pattern on the C1'-C6' ring in Fig 2) but our X-ray structure determination estabilshed that OctaInd has the structure shown in Fig. 1. This information is important to researchers wishing to model the behaviour of OctaInd.

Related literature top

For related literature, see: Andersson et al. (2006); Muir et al. (2007); Richardson (2007). See also Appendix 3 in a Danish EPA report published in 1999 on `Physical-chemical Properties of Brominated Flame Retardants'; http://www2.mst.dk/udgiv/Publications/1999/87–7909-416–3/html/bil03_eng.htm.

Experimental top

1,1,3-trimethyl-4,5,6,7-tetrabromo-3-(2,3,4,5-tetrabromophenyl)indane was obtained by bromination of 1,1,3-trimethyl-3-phenylindane using proprietary methods. The compound was isolated using chromatographic techniques. Colorless crystals were obtained from a solution of the title compound in toluene.

Refinement top

All hydrogen atoms were placed in calculated positions with C—H distances of 0.98 and 0.99 Å and they were included in the refinement in a riding-model approximation with Uiso = 1.2Ueq(C) or 1.5Ueq(C) for methyl C atoms.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are at the 30% probability level. H atoms are not shown.
[Figure 2] Fig. 2. Schematic representation of 1,1,3-trimethyl-4,5,6,7-tetrabromo-3-(2,3,4,6-tetrabromophenyl)indane which is an isomer of the title compound.
4,5,6,7-Tetrabromo-1,1,3-trimethyl-3-(2,3,4,5-tetrabromophenyl)indane top
Crystal data top
C18H12Br8F(000) = 1600
Mr = 867.56Dx = 2.699 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 13121 reflections
a = 20.2603 (6) Åθ = 2.7–27.5°
b = 7.3862 (2) ŵ = 15.03 mm1
c = 15.2233 (8) ÅT = 150 K
β = 110.4070 (15)°Block, colourless
V = 2135.14 (14) Å30.16 × 0.14 × 0.14 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
4862 independent reflections
Radiation source: fine-focus sealed tube3509 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 2.7°
ϕ scans and ω scans with κ offsetsh = 2526
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 98
Tmin = 0.057, Tmax = 0.122l = 1919
13121 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0587P)2]
where P = (Fo2 + 2Fc2)/3
4862 reflections(Δ/σ)max = 0.001
238 parametersΔρmax = 1.33 e Å3
0 restraintsΔρmin = 1.34 e Å3
Crystal data top
C18H12Br8V = 2135.14 (14) Å3
Mr = 867.56Z = 4
Monoclinic, P21/cMo Kα radiation
a = 20.2603 (6) ŵ = 15.03 mm1
b = 7.3862 (2) ÅT = 150 K
c = 15.2233 (8) Å0.16 × 0.14 × 0.14 mm
β = 110.4070 (15)°
Data collection top
Nonius KappaCCD
diffractometer
4862 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
3509 reflections with I > 2σ(I)
Tmin = 0.057, Tmax = 0.122Rint = 0.059
13121 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 0.99Δρmax = 1.33 e Å3
4862 reflectionsΔρmin = 1.34 e Å3
238 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
xyzUiso*/Ueq
Br10.27614 (3)0.65858 (8)0.41094 (4)0.02811 (17)
Br20.42084 (3)0.88707 (8)0.48485 (5)0.03059 (17)
Br30.56522 (3)0.70567 (8)0.63052 (4)0.02834 (17)
Br40.55454 (3)0.31103 (9)0.72840 (4)0.03124 (17)
Br50.28644 (3)0.57820 (9)0.70187 (4)0.03205 (17)
Br60.14076 (4)0.81344 (9)0.65538 (5)0.03543 (19)
Br70.01011 (3)0.75190 (9)0.45738 (5)0.03139 (17)
Br80.01921 (3)0.43423 (9)0.31278 (4)0.03253 (18)
C10.1758 (3)0.2215 (7)0.3861 (4)0.0219 (13)
C1A0.1588 (4)0.2594 (8)0.2807 (4)0.0288 (15)
H1AA0.18100.37350.27310.043*
H1AB0.10770.26850.24930.043*
H1AC0.17700.16040.25290.043*
C1'0.3483 (3)0.3945 (7)0.5524 (4)0.0206 (13)
C20.2562 (3)0.2027 (8)0.4324 (4)0.0226 (13)
H2A0.28000.26520.39400.027*
H2B0.26980.07330.43720.027*
C2A0.1361 (3)0.0495 (7)0.3963 (5)0.0294 (15)
H2AA0.08530.07300.37230.044*
H2AB0.15080.01550.46260.044*
H2AC0.14690.04950.36060.044*
C2'0.3537 (3)0.5593 (7)0.5085 (4)0.0205 (12)
C30.2792 (3)0.2890 (7)0.5320 (4)0.0212 (13)
C3A0.2846 (3)0.1397 (8)0.6056 (4)0.0294 (15)
H3AA0.30160.19290.66850.044*
H3AB0.31750.04590.60120.044*
H3AC0.23810.08580.59350.044*
C3'0.4168 (3)0.6534 (8)0.5333 (4)0.0240 (13)
C40.2098 (3)0.5358 (8)0.5891 (4)0.0249 (14)
C4'0.4786 (3)0.5817 (7)0.5981 (4)0.0201 (13)
C50.1486 (3)0.6364 (8)0.5695 (4)0.0253 (14)
C5'0.4740 (3)0.4165 (8)0.6388 (4)0.0232 (13)
C60.0929 (3)0.6090 (8)0.4852 (4)0.0229 (13)
C6'0.4110 (3)0.3272 (7)0.6172 (4)0.0208 (13)
H6'A0.40990.21530.64740.025*
C70.0975 (3)0.4758 (8)0.4235 (4)0.0232 (13)
C80.1586 (3)0.3757 (8)0.4420 (4)0.0244 (13)
C90.2156 (3)0.4084 (7)0.5251 (4)0.0222 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0233 (3)0.0283 (3)0.0269 (3)0.0021 (3)0.0014 (3)0.0100 (2)
Br20.0284 (4)0.0269 (3)0.0339 (4)0.0043 (3)0.0076 (3)0.0071 (3)
Br30.0214 (3)0.0361 (4)0.0255 (4)0.0062 (3)0.0058 (3)0.0005 (3)
Br40.0226 (3)0.0402 (4)0.0257 (4)0.0027 (3)0.0019 (3)0.0090 (3)
Br50.0270 (4)0.0470 (4)0.0193 (3)0.0080 (3)0.0046 (3)0.0090 (3)
Br60.0361 (4)0.0397 (4)0.0333 (4)0.0052 (3)0.0155 (3)0.0145 (3)
Br70.0281 (4)0.0332 (4)0.0333 (4)0.0045 (3)0.0112 (3)0.0007 (3)
Br80.0250 (4)0.0405 (4)0.0239 (4)0.0027 (3)0.0018 (3)0.0040 (3)
C10.021 (3)0.026 (3)0.018 (3)0.000 (2)0.005 (3)0.000 (2)
C1A0.035 (4)0.033 (3)0.016 (3)0.003 (3)0.005 (3)0.000 (2)
C1'0.019 (3)0.022 (3)0.020 (3)0.003 (2)0.006 (3)0.001 (2)
C20.022 (3)0.023 (3)0.020 (3)0.001 (2)0.003 (3)0.002 (2)
C2A0.029 (4)0.027 (3)0.029 (4)0.005 (3)0.005 (3)0.005 (3)
C2'0.022 (3)0.024 (3)0.015 (3)0.002 (2)0.007 (2)0.001 (2)
C30.019 (3)0.024 (3)0.017 (3)0.008 (2)0.002 (2)0.002 (2)
C3A0.025 (3)0.031 (3)0.026 (4)0.004 (3)0.002 (3)0.007 (3)
C3'0.026 (3)0.029 (3)0.017 (3)0.002 (3)0.007 (3)0.002 (2)
C40.023 (3)0.033 (3)0.016 (3)0.015 (3)0.004 (3)0.005 (2)
C4'0.019 (3)0.024 (3)0.018 (3)0.003 (2)0.007 (2)0.006 (2)
C50.031 (4)0.027 (3)0.023 (3)0.003 (3)0.016 (3)0.005 (3)
C5'0.018 (3)0.030 (3)0.020 (3)0.006 (2)0.005 (3)0.001 (2)
C60.017 (3)0.026 (3)0.026 (3)0.002 (2)0.008 (3)0.001 (2)
C6'0.023 (3)0.020 (3)0.018 (3)0.001 (2)0.004 (2)0.004 (2)
C70.023 (3)0.025 (3)0.020 (3)0.008 (3)0.005 (3)0.003 (2)
C80.027 (3)0.026 (3)0.019 (3)0.004 (3)0.005 (3)0.003 (2)
C90.023 (3)0.024 (3)0.021 (3)0.008 (3)0.009 (3)0.002 (2)
Geometric parameters (Å, º) top
Br1—C2'1.894 (6)C2—H2B0.9900
Br2—C3'1.890 (6)C2A—H2AA0.9800
Br3—C4'1.886 (6)C2A—H2AB0.9800
Br4—C5'1.892 (6)C2A—H2AC0.9800
Br5—C41.897 (6)C2'—C3'1.387 (8)
Br6—C51.895 (6)C3—C91.533 (8)
Br7—C61.900 (6)C3—C3A1.548 (8)
Br8—C71.895 (6)C3A—H3AA0.9800
C1—C81.533 (8)C3A—H3AB0.9800
C1—C21.540 (8)C3A—H3AC0.9800
C1—C2A1.541 (8)C3'—C4'1.401 (8)
C1—C1A1.544 (8)C4—C51.386 (9)
C1A—H1AA0.9800C4—C91.390 (8)
C1A—H1AB0.9800C4'—C5'1.386 (8)
C1A—H1AC0.9800C5—C61.396 (8)
C1'—C6'1.400 (8)C5'—C6'1.371 (8)
C1'—C2'1.411 (8)C6—C71.386 (8)
C1'—C31.537 (8)C6'—H6'A0.9500
C2—C31.560 (8)C7—C81.384 (8)
C2—H2A0.9900C8—C91.405 (8)
C8—C1—C2102.8 (5)C3—C3A—H3AA109.5
C8—C1—C2A109.2 (5)C3—C3A—H3AB109.5
C2—C1—C2A112.7 (5)H3AA—C3A—H3AB109.5
C8—C1—C1A115.5 (5)C3—C3A—H3AC109.5
C2—C1—C1A107.9 (5)H3AA—C3A—H3AC109.5
C2A—C1—C1A108.7 (5)H3AB—C3A—H3AC109.5
C1—C1A—H1AA109.5C2'—C3'—C4'121.0 (5)
C1—C1A—H1AB109.5C2'—C3'—Br2120.8 (4)
H1AA—C1A—H1AB109.5C4'—C3'—Br2118.1 (4)
C1—C1A—H1AC109.5C5—C4—C9120.0 (5)
H1AA—C1A—H1AC109.5C5—C4—Br5119.7 (4)
H1AB—C1A—H1AC109.5C9—C4—Br5120.2 (5)
C6'—C1'—C2'116.1 (5)C5'—C4'—C3'117.7 (5)
C6'—C1'—C3120.1 (5)C5'—C4'—Br3120.8 (4)
C2'—C1'—C3123.9 (5)C3'—C4'—Br3121.5 (4)
C1—C2—C3108.5 (5)C4—C5—C6119.8 (5)
C1—C2—H2A110.0C4—C5—Br6120.3 (5)
C3—C2—H2A110.0C6—C5—Br6119.9 (5)
C1—C2—H2B110.0C6'—C5'—C4'121.3 (5)
C3—C2—H2B110.0C6'—C5'—Br4118.1 (4)
H2A—C2—H2B108.4C4'—C5'—Br4120.6 (4)
C1—C2A—H2AA109.5C7—C6—C5120.1 (5)
C1—C2A—H2AB109.5C7—C6—Br7120.4 (4)
H2AA—C2A—H2AB109.5C5—C6—Br7119.5 (4)
C1—C2A—H2AC109.5C5'—C6'—C1'122.5 (5)
H2AA—C2A—H2AC109.5C5'—C6'—H6'A118.7
H2AB—C2A—H2AC109.5C1'—C6'—H6'A118.7
C3'—C2'—C1'121.3 (5)C8—C7—C6120.6 (5)
C3'—C2'—Br1117.0 (4)C8—C7—Br8120.4 (4)
C1'—C2'—Br1121.7 (4)C6—C7—Br8119.0 (5)
C9—C3—C1'114.0 (4)C7—C8—C9119.2 (6)
C9—C3—C3A107.8 (5)C7—C8—C1130.1 (5)
C1'—C3—C3A112.7 (5)C9—C8—C1110.7 (5)
C9—C3—C2102.1 (4)C4—C9—C8120.2 (6)
C1'—C3—C2110.2 (5)C4—C9—C3128.0 (5)
C3A—C3—C2109.5 (5)C8—C9—C3111.8 (5)

Experimental details

Crystal data
Chemical formulaC18H12Br8
Mr867.56
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)20.2603 (6), 7.3862 (2), 15.2233 (8)
β (°) 110.4070 (15)
V3)2135.14 (14)
Z4
Radiation typeMo Kα
µ (mm1)15.03
Crystal size (mm)0.16 × 0.14 × 0.14
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.057, 0.122
No. of measured, independent and
observed [I > 2σ(I)] reflections
13121, 4862, 3509
Rint0.059
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.111, 0.99
No. of reflections4862
No. of parameters238
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.33, 1.34

Computer programs: COLLECT (Nonius, 2002), DENZO–SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2001).

 

Acknowledgements

The authors acknowledge NSERC Canada and the University of Toronto for funding.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.  CrossRef Web of Science IUCr Journals Google Scholar
First citationAndersson, P. L., Öberg, K. & Örn, U. (2006). Environ. Toxicol. Chem. 25, 1275–1282.  Web of Science CrossRef PubMed CAS Google Scholar
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationMuir, D., Howard, P. H. & Metlan, W. (2007). Organohalogen Compd. 69, 1053–1056.  Google Scholar
First citationNonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationRichardson, S. D. (2007). Anal. Chem. 79, 4295–4324.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2001). SHELXTL/PC. Version 6.1. Windows XP Version. Bruker AXS Inc., Madison, USA.  Google Scholar

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