organic compounds
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
The title compound (OctaInd), C18H12Br8, is a commercial brominated flame retardant (BFR). In the molecule, the five-membered ring has a slight 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); 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
Crystal data
|
Data collection: COLLECT (Nonius, 2002); cell DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808000494/bv2087sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808000494/bv2087Isup2.hkl
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.
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
in a riding-model approximation with Uiso = 1.2Ueq(C) or 1.5Ueq(C) for methyl C atoms.Data collection: COLLECT (Nonius, 2002); cell
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).C18H12Br8 | F(000) = 1600 |
Mr = 867.56 | Dx = 2.699 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 13121 reflections |
a = 20.2603 (6) Å | θ = 2.7–27.5° |
b = 7.3862 (2) Å | µ = 15.03 mm−1 |
c = 15.2233 (8) Å | T = 150 K |
β = 110.4070 (15)° | Block, colourless |
V = 2135.14 (14) Å3 | 0.16 × 0.14 × 0.14 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 4862 independent reflections |
Radiation source: fine-focus sealed tube | 3509 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ϕ scans and ω scans with κ offsets | h = −25→26 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −9→8 |
Tmin = 0.057, Tmax = 0.122 | l = −19→19 |
13121 measured reflections |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-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 parameters | Δρmax = 1.33 e Å−3 |
0 restraints | Δρmin = −1.34 e Å−3 |
C18H12Br8 | V = 2135.14 (14) Å3 |
Mr = 867.56 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.2603 (6) Å | µ = 15.03 mm−1 |
b = 7.3862 (2) Å | T = 150 K |
c = 15.2233 (8) Å | 0.16 × 0.14 × 0.14 mm |
β = 110.4070 (15)° |
Nonius KappaCCD diffractometer | 4862 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3509 reflections with I > 2σ(I) |
Tmin = 0.057, Tmax = 0.122 | Rint = 0.059 |
13121 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 0.99 | Δρmax = 1.33 e Å−3 |
4862 reflections | Δρmin = −1.34 e Å−3 |
238 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.27614 (3) | 0.65858 (8) | 0.41094 (4) | 0.02811 (17) | |
Br2 | 0.42084 (3) | 0.88707 (8) | 0.48485 (5) | 0.03059 (17) | |
Br3 | 0.56522 (3) | 0.70567 (8) | 0.63052 (4) | 0.02834 (17) | |
Br4 | 0.55454 (3) | 0.31103 (9) | 0.72840 (4) | 0.03124 (17) | |
Br5 | 0.28644 (3) | 0.57820 (9) | 0.70187 (4) | 0.03205 (17) | |
Br6 | 0.14076 (4) | 0.81344 (9) | 0.65538 (5) | 0.03543 (19) | |
Br7 | 0.01011 (3) | 0.75190 (9) | 0.45738 (5) | 0.03139 (17) | |
Br8 | 0.01921 (3) | 0.43423 (9) | 0.31278 (4) | 0.03253 (18) | |
C1 | 0.1758 (3) | 0.2215 (7) | 0.3861 (4) | 0.0219 (13) | |
C1A | 0.1588 (4) | 0.2594 (8) | 0.2807 (4) | 0.0288 (15) | |
H1AA | 0.1810 | 0.3735 | 0.2731 | 0.043* | |
H1AB | 0.1077 | 0.2685 | 0.2493 | 0.043* | |
H1AC | 0.1770 | 0.1604 | 0.2529 | 0.043* | |
C1' | 0.3483 (3) | 0.3945 (7) | 0.5524 (4) | 0.0206 (13) | |
C2 | 0.2562 (3) | 0.2027 (8) | 0.4324 (4) | 0.0226 (13) | |
H2A | 0.2800 | 0.2652 | 0.3940 | 0.027* | |
H2B | 0.2698 | 0.0733 | 0.4372 | 0.027* | |
C2A | 0.1361 (3) | 0.0495 (7) | 0.3963 (5) | 0.0294 (15) | |
H2AA | 0.0853 | 0.0730 | 0.3723 | 0.044* | |
H2AB | 0.1508 | 0.0155 | 0.4626 | 0.044* | |
H2AC | 0.1469 | −0.0495 | 0.3606 | 0.044* | |
C2' | 0.3537 (3) | 0.5593 (7) | 0.5085 (4) | 0.0205 (12) | |
C3 | 0.2792 (3) | 0.2890 (7) | 0.5320 (4) | 0.0212 (13) | |
C3A | 0.2846 (3) | 0.1397 (8) | 0.6056 (4) | 0.0294 (15) | |
H3AA | 0.3016 | 0.1929 | 0.6685 | 0.044* | |
H3AB | 0.3175 | 0.0459 | 0.6012 | 0.044* | |
H3AC | 0.2381 | 0.0858 | 0.5935 | 0.044* | |
C3' | 0.4168 (3) | 0.6534 (8) | 0.5333 (4) | 0.0240 (13) | |
C4 | 0.2098 (3) | 0.5358 (8) | 0.5891 (4) | 0.0249 (14) | |
C4' | 0.4786 (3) | 0.5817 (7) | 0.5981 (4) | 0.0201 (13) | |
C5 | 0.1486 (3) | 0.6364 (8) | 0.5695 (4) | 0.0253 (14) | |
C5' | 0.4740 (3) | 0.4165 (8) | 0.6388 (4) | 0.0232 (13) | |
C6 | 0.0929 (3) | 0.6090 (8) | 0.4852 (4) | 0.0229 (13) | |
C6' | 0.4110 (3) | 0.3272 (7) | 0.6172 (4) | 0.0208 (13) | |
H6'A | 0.4099 | 0.2153 | 0.6474 | 0.025* | |
C7 | 0.0975 (3) | 0.4758 (8) | 0.4235 (4) | 0.0232 (13) | |
C8 | 0.1586 (3) | 0.3757 (8) | 0.4420 (4) | 0.0244 (13) | |
C9 | 0.2156 (3) | 0.4084 (7) | 0.5251 (4) | 0.0222 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0233 (3) | 0.0283 (3) | 0.0269 (3) | −0.0021 (3) | 0.0014 (3) | 0.0100 (2) |
Br2 | 0.0284 (4) | 0.0269 (3) | 0.0339 (4) | −0.0043 (3) | 0.0076 (3) | 0.0071 (3) |
Br3 | 0.0214 (3) | 0.0361 (4) | 0.0255 (4) | −0.0062 (3) | 0.0058 (3) | 0.0005 (3) |
Br4 | 0.0226 (3) | 0.0402 (4) | 0.0257 (4) | 0.0027 (3) | 0.0019 (3) | 0.0090 (3) |
Br5 | 0.0270 (4) | 0.0470 (4) | 0.0193 (3) | −0.0080 (3) | 0.0046 (3) | −0.0090 (3) |
Br6 | 0.0361 (4) | 0.0397 (4) | 0.0333 (4) | −0.0052 (3) | 0.0155 (3) | −0.0145 (3) |
Br7 | 0.0281 (4) | 0.0332 (4) | 0.0333 (4) | 0.0045 (3) | 0.0112 (3) | 0.0007 (3) |
Br8 | 0.0250 (4) | 0.0405 (4) | 0.0239 (4) | 0.0027 (3) | −0.0018 (3) | −0.0040 (3) |
C1 | 0.021 (3) | 0.026 (3) | 0.018 (3) | 0.000 (2) | 0.005 (3) | 0.000 (2) |
C1A | 0.035 (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) |
C2 | 0.022 (3) | 0.023 (3) | 0.020 (3) | 0.001 (2) | 0.003 (3) | −0.002 (2) |
C2A | 0.029 (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) |
C3 | 0.019 (3) | 0.024 (3) | 0.017 (3) | −0.008 (2) | 0.002 (2) | 0.002 (2) |
C3A | 0.025 (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) |
C4 | 0.023 (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) |
C5 | 0.031 (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) |
C6 | 0.017 (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) |
C7 | 0.023 (3) | 0.025 (3) | 0.020 (3) | −0.008 (3) | 0.005 (3) | 0.003 (2) |
C8 | 0.027 (3) | 0.026 (3) | 0.019 (3) | −0.004 (3) | 0.005 (3) | 0.003 (2) |
C9 | 0.023 (3) | 0.024 (3) | 0.021 (3) | −0.008 (3) | 0.009 (3) | 0.002 (2) |
Br1—C2' | 1.894 (6) | C2—H2B | 0.9900 |
Br2—C3' | 1.890 (6) | C2A—H2AA | 0.9800 |
Br3—C4' | 1.886 (6) | C2A—H2AB | 0.9800 |
Br4—C5' | 1.892 (6) | C2A—H2AC | 0.9800 |
Br5—C4 | 1.897 (6) | C2'—C3' | 1.387 (8) |
Br6—C5 | 1.895 (6) | C3—C9 | 1.533 (8) |
Br7—C6 | 1.900 (6) | C3—C3A | 1.548 (8) |
Br8—C7 | 1.895 (6) | C3A—H3AA | 0.9800 |
C1—C8 | 1.533 (8) | C3A—H3AB | 0.9800 |
C1—C2 | 1.540 (8) | C3A—H3AC | 0.9800 |
C1—C2A | 1.541 (8) | C3'—C4' | 1.401 (8) |
C1—C1A | 1.544 (8) | C4—C5 | 1.386 (9) |
C1A—H1AA | 0.9800 | C4—C9 | 1.390 (8) |
C1A—H1AB | 0.9800 | C4'—C5' | 1.386 (8) |
C1A—H1AC | 0.9800 | C5—C6 | 1.396 (8) |
C1'—C6' | 1.400 (8) | C5'—C6' | 1.371 (8) |
C1'—C2' | 1.411 (8) | C6—C7 | 1.386 (8) |
C1'—C3 | 1.537 (8) | C6'—H6'A | 0.9500 |
C2—C3 | 1.560 (8) | C7—C8 | 1.384 (8) |
C2—H2A | 0.9900 | C8—C9 | 1.405 (8) |
C8—C1—C2 | 102.8 (5) | C3—C3A—H3AA | 109.5 |
C8—C1—C2A | 109.2 (5) | C3—C3A—H3AB | 109.5 |
C2—C1—C2A | 112.7 (5) | H3AA—C3A—H3AB | 109.5 |
C8—C1—C1A | 115.5 (5) | C3—C3A—H3AC | 109.5 |
C2—C1—C1A | 107.9 (5) | H3AA—C3A—H3AC | 109.5 |
C2A—C1—C1A | 108.7 (5) | H3AB—C3A—H3AC | 109.5 |
C1—C1A—H1AA | 109.5 | C2'—C3'—C4' | 121.0 (5) |
C1—C1A—H1AB | 109.5 | C2'—C3'—Br2 | 120.8 (4) |
H1AA—C1A—H1AB | 109.5 | C4'—C3'—Br2 | 118.1 (4) |
C1—C1A—H1AC | 109.5 | C5—C4—C9 | 120.0 (5) |
H1AA—C1A—H1AC | 109.5 | C5—C4—Br5 | 119.7 (4) |
H1AB—C1A—H1AC | 109.5 | C9—C4—Br5 | 120.2 (5) |
C6'—C1'—C2' | 116.1 (5) | C5'—C4'—C3' | 117.7 (5) |
C6'—C1'—C3 | 120.1 (5) | C5'—C4'—Br3 | 120.8 (4) |
C2'—C1'—C3 | 123.9 (5) | C3'—C4'—Br3 | 121.5 (4) |
C1—C2—C3 | 108.5 (5) | C4—C5—C6 | 119.8 (5) |
C1—C2—H2A | 110.0 | C4—C5—Br6 | 120.3 (5) |
C3—C2—H2A | 110.0 | C6—C5—Br6 | 119.9 (5) |
C1—C2—H2B | 110.0 | C6'—C5'—C4' | 121.3 (5) |
C3—C2—H2B | 110.0 | C6'—C5'—Br4 | 118.1 (4) |
H2A—C2—H2B | 108.4 | C4'—C5'—Br4 | 120.6 (4) |
C1—C2A—H2AA | 109.5 | C7—C6—C5 | 120.1 (5) |
C1—C2A—H2AB | 109.5 | C7—C6—Br7 | 120.4 (4) |
H2AA—C2A—H2AB | 109.5 | C5—C6—Br7 | 119.5 (4) |
C1—C2A—H2AC | 109.5 | C5'—C6'—C1' | 122.5 (5) |
H2AA—C2A—H2AC | 109.5 | C5'—C6'—H6'A | 118.7 |
H2AB—C2A—H2AC | 109.5 | C1'—C6'—H6'A | 118.7 |
C3'—C2'—C1' | 121.3 (5) | C8—C7—C6 | 120.6 (5) |
C3'—C2'—Br1 | 117.0 (4) | C8—C7—Br8 | 120.4 (4) |
C1'—C2'—Br1 | 121.7 (4) | C6—C7—Br8 | 119.0 (5) |
C9—C3—C1' | 114.0 (4) | C7—C8—C9 | 119.2 (6) |
C9—C3—C3A | 107.8 (5) | C7—C8—C1 | 130.1 (5) |
C1'—C3—C3A | 112.7 (5) | C9—C8—C1 | 110.7 (5) |
C9—C3—C2 | 102.1 (4) | C4—C9—C8 | 120.2 (6) |
C1'—C3—C2 | 110.2 (5) | C4—C9—C3 | 128.0 (5) |
C3A—C3—C2 | 109.5 (5) | C8—C9—C3 | 111.8 (5) |
Experimental details
Crystal data | |
Chemical formula | C18H12Br8 |
Mr | 867.56 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 20.2603 (6), 7.3862 (2), 15.2233 (8) |
β (°) | 110.4070 (15) |
V (Å3) | 2135.14 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 15.03 |
Crystal size (mm) | 0.16 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.057, 0.122 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13121, 4862, 3509 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.111, 0.99 |
No. of reflections | 4862 |
No. of parameters | 238 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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
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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.