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

Konstantinov, A.; McCrindle, R.; Arsenault, G.; Lough, A.J.

doi:10.1107/S1600536808000494

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o439

doi:10.1107/S1600536808000494

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

Alex Konstantinov,^a Robert McCrindle,^b Gilles Arsenault ^a and Alan J. Lough ^c ^*

^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 ); 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

C₁₈H₁₂Br₈
M_r = 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 ) T_min = 0.057, T_max = 0.122
13121 measured reflections
4862 independent reflections
3509 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.111
S = 0.99
4862 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000494/bv2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000494/bv2087Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are at the 30% probability level. H atoms are not shown.
	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

C₁₈H₁₂Br₈	F(000) = 1600
M_r = 867.56	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	4862 independent reflections
Radiation source: fine-focus sealed tube	3509 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ϕ scans and ω scans with κ offsets	h = −25→26
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −9→8
T_min = 0.057, T_max = 0.122	l = −19→19
13121 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0587P)²] where P = (F_o² + 2F_c²)/3
4862 reflections	(Δ/σ)_max = 0.001
238 parameters	Δρ_max = 1.33 e Å⁻³
0 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

C₁₈H₁₂Br₈	V = 2135.14 (14) Å³
M_r = 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)°

Data collection top

Nonius KappaCCD diffractometer	4862 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	3509 reflections with I > 2σ(I)
T_min = 0.057, T_max = 0.122	R_int = 0.059
13121 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 0.99	Δρ_max = 1.33 e Å⁻³
4862 reflections	Δρ_min = −1.34 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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)
T_min, T_max	0.057, 0.122
No. of measured, independent and observed [I > 2σ(I)] reflections	13121, 4862, 3509
R_int	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
Δρ_max, Δρ_min (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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