Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002301/bt6108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002301/bt6108Isup2.hkl |
CCDC reference: 182613
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.039
- wR factor = 0.060
- Data-to-parameter ratio = 17.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The synthesis of the PBDE was carried out by coupling the diphenyl iodonium salt with a bromophenylate (Beringer et al., 1959; Ziegler & Marr, 1962; Hu, 1996, 1999). The title compound was recrystallized from methanol.
Two data sets were collected with the Stoe IPDS system (Stoe, 1997), merged and scaled together. The rather high internal R value is to a large extent dependent on the contribution from the large number of non-significant reflections. The internal R value using the reflections with I ≥ 2σ(I) is 0.0398.
Data collection: EXPOSE (Stoe & Cie, 1997); cell refinement: CELL (Stoe & Cie, 1997); data reduction: INTEGRATE (Stoe & Cie, 1997) and X-RED (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996).
C12H7Br3O | F(000) = 768 |
Mr = 406.91 | Dx = 2.081 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.935 (3) Å | Cell parameters from 1153 reflections |
b = 4.9785 (10) Å | θ = 1.7–26.1° |
c = 22.151 (9) Å | µ = 9.30 mm−1 |
β = 99.43 (4)° | T = 293 K |
V = 1298.5 (7) Å3 | Prism, colourless |
Z = 4 | 0.12 × 0.10 × 0.08 mm |
Stoe IPDS diffractometer | 2491 independent reflections |
Radiation source: fine-focus sealed tube | 1100 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 6.0 pixels mm-1 | θmax = 26.0°, θmin = 2.1° |
area detector scans | h = −14→14 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1998) | k = −6→5 |
Tmin = 0.323, Tmax = 0.487 | l = −27→27 |
18021 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.01P)2] where P = (Fo2 + 2Fc2)/3 |
2491 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.64 e Å−3 |
40 restraints | Δρmin = −0.54 e Å−3 |
C12H7Br3O | V = 1298.5 (7) Å3 |
Mr = 406.91 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.935 (3) Å | µ = 9.30 mm−1 |
b = 4.9785 (10) Å | T = 293 K |
c = 22.151 (9) Å | 0.12 × 0.10 × 0.08 mm |
β = 99.43 (4)° |
Stoe IPDS diffractometer | 2491 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1998) | 1100 reflections with I > 2σ(I) |
Tmin = 0.323, Tmax = 0.487 | Rint = 0.081 |
18021 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 40 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.64 e Å−3 |
2491 reflections | Δρmin = −0.54 e Å−3 |
145 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 | −0.00006 (4) | 0.05406 (14) | 0.10226 (3) | 0.1041 (3) | |
Br2 | −0.41284 (5) | −0.47510 (18) | 0.11464 (4) | 0.1224 (3) | |
Br3 | −0.29389 (5) | −0.47975 (18) | −0.18963 (3) | 0.1037 (3) | |
O | −0.2518 (2) | −0.0764 (7) | 0.06950 (18) | 0.0709 (10) | |
C1 | −0.2594 (4) | −0.1819 (12) | 0.0110 (3) | 0.0612 (15) | |
C2 | −0.3354 (4) | −0.0544 (12) | −0.0338 (3) | 0.0731 (15) | |
H2 | −0.3793 | 0.0882 | −0.0239 | 0.088* | |
C3 | −0.3448 (4) | −0.1414 (13) | −0.0927 (3) | 0.0789 (18) | |
H3 | −0.3952 | −0.0564 | −0.1233 | 0.095* | |
C4 | −0.2807 (4) | −0.3537 (13) | −0.1075 (2) | 0.0663 (16) | |
C5 | −0.2061 (4) | −0.4834 (12) | −0.0630 (2) | 0.0629 (14) | |
H5 | −0.1637 | −0.6286 | −0.0730 | 0.075* | |
C6 | −0.1951 (4) | −0.3946 (11) | −0.0032 (2) | 0.0611 (15) | |
H6 | −0.1443 | −0.4784 | 0.0274 | 0.073* | |
C7 | −0.1991 (4) | −0.2294 (11) | 0.1182 (3) | 0.0592 (14) | |
C8 | −0.2577 (4) | −0.4181 (14) | 0.1474 (3) | 0.0732 (16) | |
C9 | −0.2064 (7) | −0.5607 (14) | 0.1969 (3) | 0.096 (2) | |
H9 | −0.2470 | −0.6892 | 0.2148 | 0.116* | |
C10 | −0.0960 (7) | −0.5139 (17) | 0.2197 (3) | 0.107 (2) | |
H10 | −0.0614 | −0.6082 | 0.2540 | 0.128* | |
C11 | −0.0350 (5) | −0.3314 (15) | 0.1933 (3) | 0.089 (2) | |
H11 | 0.0409 | −0.3022 | 0.2095 | 0.107* | |
C12 | −0.0846 (4) | −0.1888 (11) | 0.1425 (3) | 0.0677 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0714 (4) | 0.0723 (5) | 0.1754 (7) | −0.0135 (4) | 0.0408 (4) | −0.0173 (6) |
Br2 | 0.0693 (4) | 0.1216 (7) | 0.1842 (8) | −0.0243 (5) | 0.0446 (4) | −0.0231 (7) |
Br3 | 0.0909 (4) | 0.1532 (8) | 0.0648 (3) | −0.0071 (6) | 0.0064 (3) | 0.0088 (5) |
O | 0.069 (2) | 0.057 (3) | 0.085 (3) | 0.013 (2) | 0.0079 (19) | −0.005 (2) |
C1 | 0.046 (3) | 0.062 (4) | 0.076 (4) | 0.001 (3) | 0.011 (3) | −0.003 (3) |
C2 | 0.057 (3) | 0.062 (4) | 0.100 (4) | 0.010 (3) | 0.012 (3) | 0.018 (4) |
C3 | 0.053 (3) | 0.081 (5) | 0.101 (5) | 0.001 (3) | 0.006 (3) | 0.032 (4) |
C4 | 0.054 (3) | 0.086 (5) | 0.057 (3) | −0.018 (3) | 0.002 (3) | 0.014 (3) |
C5 | 0.058 (3) | 0.065 (4) | 0.066 (3) | 0.009 (3) | 0.010 (2) | 0.002 (4) |
C6 | 0.060 (3) | 0.064 (5) | 0.056 (3) | 0.009 (3) | −0.001 (3) | 0.010 (3) |
C7 | 0.061 (3) | 0.049 (4) | 0.069 (4) | 0.005 (3) | 0.015 (3) | −0.012 (3) |
C8 | 0.065 (3) | 0.072 (5) | 0.087 (4) | −0.005 (3) | 0.027 (3) | −0.018 (4) |
C9 | 0.133 (5) | 0.089 (6) | 0.079 (4) | 0.008 (5) | 0.049 (4) | 0.010 (5) |
C10 | 0.140 (6) | 0.113 (7) | 0.067 (4) | 0.035 (6) | 0.019 (4) | 0.004 (5) |
C11 | 0.078 (4) | 0.096 (6) | 0.086 (5) | 0.021 (4) | −0.011 (4) | −0.027 (4) |
C12 | 0.054 (3) | 0.055 (4) | 0.094 (4) | −0.005 (3) | 0.012 (3) | −0.017 (3) |
Br1—C12 | 1.890 (5) | C4—C5 | 1.376 (6) |
Br2—C8 | 1.897 (5) | C5—C6 | 1.383 (6) |
Br3—C4 | 1.907 (5) | C7—C8 | 1.393 (7) |
O—C7 | 1.384 (6) | C7—C12 | 1.400 (7) |
O—C1 | 1.388 (6) | C8—C9 | 1.364 (8) |
C1—C6 | 1.374 (6) | C9—C10 | 1.352 (8) |
C1—C2 | 1.384 (7) | C10—C11 | 1.355 (8) |
C2—C3 | 1.361 (7) | C11—C12 | 1.378 (8) |
C3—C4 | 1.376 (7) | ||
C7—O—C1 | 118.1 (4) | O—C7—C12 | 120.8 (5) |
C6—C1—C2 | 121.0 (6) | C8—C7—C12 | 116.8 (5) |
C6—C1—O | 123.4 (5) | C9—C8—C7 | 122.1 (5) |
C2—C1—O | 115.6 (5) | C9—C8—Br2 | 120.8 (5) |
C3—C2—C1 | 118.9 (6) | C7—C8—Br2 | 117.1 (5) |
C2—C3—C4 | 120.7 (6) | C10—C9—C8 | 119.5 (7) |
C3—C4—C5 | 120.6 (5) | C9—C10—C11 | 120.9 (7) |
C3—C4—Br3 | 121.2 (5) | C10—C11—C12 | 120.6 (6) |
C5—C4—Br3 | 118.2 (5) | C11—C12—C7 | 120.1 (6) |
C4—C5—C6 | 119.0 (5) | C11—C12—Br1 | 121.6 (5) |
C1—C6—C5 | 119.7 (5) | C7—C12—Br1 | 118.2 (5) |
O—C7—C8 | 122.4 (5) | ||
C12—C7—O—C1 | 96.4 (6) | C6—C1—O—C7 | −16.5 (7) |
C8—C7—O—C1 | −87.4 (6) | C2—C1—O—C7 | 164.9 (4) |
Experimental details
Crystal data | |
Chemical formula | C12H7Br3O |
Mr | 406.91 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.935 (3), 4.9785 (10), 22.151 (9) |
β (°) | 99.43 (4) |
V (Å3) | 1298.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.30 |
Crystal size (mm) | 0.12 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1998) |
Tmin, Tmax | 0.323, 0.487 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18021, 2491, 1100 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.060, 1.06 |
No. of reflections | 2491 |
No. of parameters | 145 |
No. of restraints | 40 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.54 |
Computer programs: EXPOSE (Stoe & Cie, 1997), CELL (Stoe & Cie, 1997), INTEGRATE (Stoe & Cie, 1997) and X-RED (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996).
Br1—C12 | 1.890 (5) | O—C7 | 1.384 (6) |
Br2—C8 | 1.897 (5) | O—C1 | 1.388 (6) |
Br3—C4 | 1.907 (5) | ||
C7—O—C1 | 118.1 (4) | O—C7—C8 | 122.4 (5) |
C6—C1—O | 123.4 (5) | O—C7—C12 | 120.8 (5) |
C2—C1—O | 115.6 (5) | ||
C12—C7—O—C1 | 96.4 (6) | C6—C1—O—C7 | −16.5 (7) |
C8—C7—O—C1 | −87.4 (6) | C2—C1—O—C7 | 164.9 (4) |
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The title compound, (I), belongs to a class of compounds known as brominated diphenyl ethers that are used as flame retardants. Commercially available mixtures mainly consists of highly brominated congeners, such as decabromodiphenyl ether (Eriksson et al., 1999). The occurrence in the environment of less brominated congeners are dependent on both primary sources and decomposition from higher brominated DE's (Eriksson et al., 2001). The crystal structure and packing pattern of these compounds are of fundamental importance in order to model the reaction mechanisms in the solid state, e.g. flame retardants adsorbed on soot particles that decompose by various reactions. [Please define DE]
Both aromatic rings of the title compound (Fig. 1) are planar within less than 0.01 Å. The O atom deviates by 0.042 (7) Å from the ring plane of the first ring (C1 → C6), while the Br3 is within the plane. The substituents of the second ring (C7 → C12) deviates more from the ring plane, O [0.071 (7) Å], Br1 [0.093 (8) Å] and Br2 [0.010 (7) Å]. The angle between the two ring planes is 85.5 (2)°. The deviations from planarity could possibly be accounted for with the observation of the short intermolecular contact distances Br1···C5(-x, -y, -z) 3.476 (5) Å and Br2···C3(-x - 1, -y - 1, -z) 3.433 (7) Å. These intermolecular Br···C contact distances (Fig. 2) can be considered as very short comparing with previously known structures (Allen & Kennard, 1993). A histogram showing distances from known aromatic C···Br distances is shown in Fig. 3. The interactions between the molecules in the present structure, mediated by the two mentioned contacts, make up chains along [110] at z ≈ 0 and along [110] at z ≈ 0.5. Each of these chains pack with symmetry-related ones into sheets parallel with the ab plane, at z ≈ 0, 1/2, 1.0, etc. The sheets make up a tweed-like pattern seen along the c axis and bind to each other partly through interactions between symmetry equivalent Br3 atoms. The intermolecular contact distance Br3···Br3(-0.5 - x, 0.5 + y, -0.5 - z) and Br3···Br3(-0.5 - x, -0.5 + y, -0.5 - z) are both 3.929 (1) Å, a fairly long distance. Thus, one might suspect that the solid phase would easily be split between these planes. Further intermolecular interactions are the usual 3.7 Å distance between the different aromatic rings in a zigzag pattern.