Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680102061X/ob6099sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680102061X/ob6099Isup2.hkl |
CCDC reference: 180528
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.008 Å
- R factor = 0.033
- wR factor = 0.080
- Data-to-parameter ratio = 16.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
A mixture of dibromoanthracene (1.00 g, 2.98 mmol) and bromine (1.20 g, 7.44 mmol) in chloroform (15 ml) was externally irradiated with 150 W projector lamp for 2 h at 303 K. The reaction was monitored by TLC and the solvent with the excess of bromine was removed under the reduced pressure. The residue was chromatographed by using silica gel. Compound (I) was recrystallized from chloroform, yield 1.56 g (m.p. 353 K).
Most of the H atoms were positioned from difference maps and refined isotropically; the C—H lengths are 0.80 (7)–1.02 (5) Å. The positions of the remaining H atoms (H6 and H8) were calculated geometrically at distances of 0.93 Å (CH) from the corresponding C atoms, and a riding model was used during the refinement process.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. |
C14H8Br6 | Z = 2 |
Mr = 655.60 | F(000) = 604 |
Triclinic, P1 | Dx = 2.632 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9289 (10) Å | Cell parameters from 25 reflections |
b = 8.4017 (10) Å | θ = 9–18° |
c = 13.285 (1) Å | µ = 14.55 mm−1 |
α = 79.759 (5)° | T = 293 K |
β = 82.136 (6)° | Rod-shaped, colorless |
γ = 72.503 (5)° | 0.3 × 0.1 × 0.1 mm |
V = 827.31 (14) Å3 |
Enraf-Nonius TurboCAD-4 diffractometer | 2228 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 26.3°, θmin = 2.6° |
non–profiled ω/2θ scans | h = −9→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→9 |
Tmin = 0.190, Tmax = 0.234 | l = −16→16 |
3596 measured reflections | 3 standard reflections every 120 min |
3347 independent reflections | intensity decay: 1% |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.032P)2 + 1.4128P] where P = (Fo2 + 2Fc2)/3 |
3347 reflections | (Δ/σ)max = 0.001 |
203 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.69 e Å−3 |
C14H8Br6 | γ = 72.503 (5)° |
Mr = 655.60 | V = 827.31 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9289 (10) Å | Mo Kα radiation |
b = 8.4017 (10) Å | µ = 14.55 mm−1 |
c = 13.285 (1) Å | T = 293 K |
α = 79.759 (5)° | 0.3 × 0.1 × 0.1 mm |
β = 82.136 (6)° |
Enraf-Nonius TurboCAD-4 diffractometer | 2228 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.022 |
Tmin = 0.190, Tmax = 0.234 | 3 standard reflections every 120 min |
3596 measured reflections | intensity decay: 1% |
3347 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.58 e Å−3 |
3347 reflections | Δρmin = −0.69 e Å−3 |
203 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 | 0.11808 (10) | 1.51524 (7) | 0.75478 (6) | 0.0521 (2) | |
Br2 | −0.17882 (9) | 1.40347 (8) | 0.59044 (5) | 0.04705 (18) | |
Br3 | −0.00175 (9) | 0.96729 (8) | 0.65348 (5) | 0.04360 (18) | |
Br4 | 0.48367 (9) | 1.17985 (9) | 0.58084 (5) | 0.04476 (17) | |
Br9 | −0.00626 (10) | 1.29374 (8) | 0.98628 (5) | 0.05004 (19) | |
Br10 | 0.59474 (10) | 0.73338 (9) | 0.74579 (6) | 0.0630 (2) | |
C1 | 0.0592 (8) | 1.3026 (6) | 0.7499 (4) | 0.0290 (12) | |
C2 | 0.0587 (8) | 1.2968 (7) | 0.6360 (4) | 0.0302 (13) | |
C3 | 0.1402 (8) | 1.1258 (7) | 0.6027 (4) | 0.0320 (13) | |
C4 | 0.3176 (8) | 1.0458 (7) | 0.6449 (4) | 0.0309 (13) | |
C5 | 0.5044 (10) | 0.7234 (8) | 0.9838 (6) | 0.0484 (18) | |
C6 | 0.4822 (10) | 0.7019 (9) | 1.0874 (6) | 0.056 (2) | |
C7 | 0.3597 (11) | 0.8235 (10) | 1.1378 (5) | 0.054 (2) | |
C8 | 0.2547 (9) | 0.9653 (8) | 1.0841 (4) | 0.0418 (16) | |
C9 | 0.1631 (7) | 1.1315 (6) | 0.9153 (4) | 0.0289 (12) | |
C10 | 0.4167 (7) | 0.8930 (7) | 0.8159 (4) | 0.0317 (13) | |
C11 | 0.4022 (8) | 0.8667 (7) | 0.9241 (4) | 0.0333 (13) | |
C12 | 0.2714 (8) | 0.9902 (7) | 0.9760 (4) | 0.0304 (13) | |
C13 | 0.1796 (7) | 1.1553 (6) | 0.8101 (4) | 0.0228 (11) | |
C14 | 0.3101 (7) | 1.0300 (6) | 0.7577 (4) | 0.0247 (11) | |
H1 | −0.052 (7) | 1.323 (6) | 0.776 (4) | 0.012 (12)* | |
H2 | 0.123 (7) | 1.365 (7) | 0.599 (4) | 0.035 (16)* | |
H3 | 0.154 (6) | 1.135 (6) | 0.525 (4) | 0.020 (13)* | |
H4 | 0.366 (8) | 0.948 (7) | 0.621 (4) | 0.038 (16)* | |
H5 | 0.571 (10) | 0.656 (9) | 0.950 (6) | 0.067* | |
H6 | 0.5497 | 0.6050 | 1.1250 | 0.067* | |
H7 | 0.353 (9) | 0.821 (8) | 1.208 (6) | 0.067* | |
H8 | 0.1720 | 1.0454 | 1.1193 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0724 (5) | 0.0258 (3) | 0.0610 (5) | −0.0130 (3) | −0.0208 (4) | −0.0038 (3) |
Br2 | 0.0407 (4) | 0.0501 (4) | 0.0425 (4) | −0.0051 (3) | −0.0142 (3) | 0.0081 (3) |
Br3 | 0.0585 (4) | 0.0431 (3) | 0.0368 (4) | −0.0254 (3) | −0.0083 (3) | −0.0033 (3) |
Br4 | 0.0411 (4) | 0.0613 (4) | 0.0317 (3) | −0.0194 (3) | 0.0059 (3) | −0.0047 (3) |
Br9 | 0.0615 (5) | 0.0510 (4) | 0.0410 (4) | −0.0183 (3) | 0.0125 (3) | −0.0243 (3) |
Br10 | 0.0592 (5) | 0.0482 (4) | 0.0574 (5) | 0.0185 (3) | 0.0000 (4) | −0.0077 (3) |
C1 | 0.028 (3) | 0.025 (3) | 0.033 (3) | −0.005 (2) | −0.005 (3) | −0.005 (2) |
C2 | 0.031 (3) | 0.027 (3) | 0.032 (3) | −0.010 (2) | −0.009 (3) | 0.004 (2) |
C3 | 0.040 (3) | 0.032 (3) | 0.025 (3) | −0.011 (3) | −0.002 (3) | −0.005 (2) |
C4 | 0.041 (3) | 0.025 (3) | 0.022 (3) | −0.001 (2) | −0.001 (3) | −0.008 (2) |
C5 | 0.050 (5) | 0.043 (4) | 0.052 (5) | −0.019 (3) | −0.017 (4) | 0.012 (3) |
C6 | 0.066 (5) | 0.060 (5) | 0.048 (4) | −0.035 (4) | −0.033 (4) | 0.026 (4) |
C7 | 0.082 (6) | 0.075 (5) | 0.024 (3) | −0.058 (5) | −0.016 (4) | 0.016 (4) |
C8 | 0.058 (4) | 0.059 (4) | 0.021 (3) | −0.039 (3) | −0.004 (3) | −0.001 (3) |
C9 | 0.034 (3) | 0.028 (3) | 0.027 (3) | −0.013 (2) | 0.007 (2) | −0.009 (2) |
C10 | 0.030 (3) | 0.030 (3) | 0.034 (3) | −0.006 (2) | 0.000 (3) | −0.006 (2) |
C11 | 0.038 (3) | 0.035 (3) | 0.031 (3) | −0.018 (3) | −0.007 (3) | 0.004 (2) |
C12 | 0.037 (3) | 0.039 (3) | 0.022 (3) | −0.024 (3) | −0.008 (2) | 0.003 (2) |
C13 | 0.025 (3) | 0.022 (2) | 0.023 (3) | −0.009 (2) | 0.003 (2) | −0.003 (2) |
C14 | 0.030 (3) | 0.025 (3) | 0.020 (3) | −0.010 (2) | 0.000 (2) | −0.004 (2) |
C4—C14 | 1.475 (7) | C7—H7 | 0.92 (7) |
C4—C3 | 1.502 (8) | C5—C6 | 1.351 (10) |
C4—Br4 | 1.993 (6) | C5—C11 | 1.408 (8) |
C4—H4 | 0.89 (6) | C5—H5 | 0.80 (7) |
C1—C13 | 1.493 (7) | C8—C12 | 1.407 (8) |
C1—C2 | 1.523 (8) | C8—H8 | 0.9300 |
C1—Br1 | 1.991 (5) | C6—H6 | 0.9300 |
C1—H1 | 0.88 (5) | Br9—C9 | 1.887 (5) |
C3—C2 | 1.506 (7) | Br10—C10 | 1.899 (5) |
C3—Br3 | 1.967 (6) | C9—C13 | 1.370 (7) |
C3—H3 | 1.02 (5) | C9—C12 | 1.426 (8) |
C2—Br2 | 1.955 (5) | C13—C14 | 1.439 (7) |
C2—H2 | 0.92 (6) | C14—C10 | 1.383 (7) |
C7—C8 | 1.373 (10) | C10—C11 | 1.409 (8) |
C7—C6 | 1.379 (11) | C12—C11 | 1.429 (8) |
C14—C4—C3 | 113.7 (5) | C6—C5—C11 | 121.7 (7) |
C14—C4—Br4 | 109.4 (4) | C6—C5—H5 | 125 (6) |
C3—C4—Br4 | 109.1 (4) | C11—C5—H5 | 113 (6) |
C14—C4—H4 | 113 (4) | C7—C8—C12 | 120.4 (7) |
C3—C4—H4 | 108 (4) | C7—C8—H8 | 119.8 |
Br4—C4—H4 | 103 (4) | C12—C8—H8 | 119.8 |
C13—C1—C2 | 117.1 (4) | C5—C6—C7 | 120.1 (6) |
C13—C1—Br1 | 111.2 (4) | C5—C6—H6 | 119.9 |
C2—C1—Br1 | 104.8 (4) | C7—C6—H6 | 119.9 |
C13—C1—H1 | 113 (3) | C13—C9—C12 | 123.3 (5) |
C2—C1—H1 | 106 (3) | C13—C9—Br9 | 119.7 (4) |
Br1—C1—H1 | 104 (3) | C12—C9—Br9 | 117.0 (4) |
C4—C3—C2 | 109.7 (5) | C9—C13—C14 | 118.6 (5) |
C4—C3—Br3 | 106.0 (4) | C9—C13—C1 | 121.3 (5) |
C2—C3—Br3 | 113.4 (4) | C14—C13—C1 | 120.0 (5) |
C4—C3—H3 | 110 (3) | C10—C14—C13 | 118.5 (5) |
C2—C3—H3 | 111 (3) | C10—C14—C4 | 122.2 (5) |
Br3—C3—H3 | 106 (3) | C13—C14—C4 | 119.1 (5) |
C3—C2—C1 | 115.5 (5) | C14—C10—C11 | 123.7 (5) |
C3—C2—Br2 | 112.0 (4) | C14—C10—Br10 | 118.1 (4) |
C1—C2—Br2 | 110.9 (4) | C11—C10—Br10 | 118.2 (4) |
C3—C2—H2 | 106 (4) | C8—C12—C9 | 123.5 (6) |
C1—C2—H2 | 109 (4) | C8—C12—C11 | 118.4 (5) |
Br2—C2—H2 | 103 (4) | C9—C12—C11 | 118.1 (5) |
C8—C7—C6 | 121.0 (6) | C5—C11—C10 | 124.0 (6) |
C8—C7—H7 | 116 (5) | C5—C11—C12 | 118.2 (6) |
C6—C7—H7 | 123 (5) | C10—C11—C12 | 117.7 (5) |
C14—C4—C3—C2 | 56.8 (6) | C1—C13—C14—C4 | −2.6 (8) |
Br4—C4—C3—C2 | −65.7 (5) | C3—C4—C14—C10 | 143.8 (5) |
C14—C4—C3—Br3 | −66.0 (5) | Br4—C4—C14—C10 | −93.9 (5) |
Br4—C4—C3—Br3 | 171.5 (2) | C3—C4—C14—C13 | −32.0 (7) |
C4—C3—C2—C1 | −48.5 (7) | Br4—C4—C14—C13 | 90.3 (5) |
Br3—C3—C2—C1 | 69.8 (6) | C13—C14—C10—C11 | 1.6 (8) |
C4—C3—C2—Br2 | −176.7 (4) | C4—C14—C10—C11 | −174.2 (5) |
Br3—C3—C2—Br2 | −58.4 (5) | C13—C14—C10—Br10 | −177.5 (4) |
C13—C1—C2—C3 | 16.0 (7) | C4—C14—C10—Br10 | 6.7 (7) |
Br1—C1—C2—C3 | 139.8 (4) | C7—C8—C12—C9 | 177.9 (5) |
C13—C1—C2—Br2 | 144.8 (4) | C7—C8—C12—C11 | −1.3 (9) |
Br1—C1—C2—Br2 | −91.4 (4) | C13—C9—C12—C8 | −179.9 (5) |
C6—C7—C8—C12 | −0.6 (10) | Br9—C9—C12—C8 | 1.6 (7) |
C11—C5—C6—C7 | −1.4 (11) | C13—C9—C12—C11 | −0.7 (8) |
C8—C7—C6—C5 | 2.0 (11) | Br9—C9—C12—C11 | −179.2 (4) |
C12—C9—C13—C14 | 1.3 (8) | C6—C5—C11—C10 | −178.2 (6) |
Br9—C9—C13—C14 | 179.8 (4) | C6—C5—C11—C12 | −0.6 (10) |
C12—C9—C13—C1 | 178.1 (5) | C14—C10—C11—C5 | 176.8 (6) |
Br9—C9—C13—C1 | −3.4 (7) | Br10—C10—C11—C5 | −4.2 (8) |
C2—C1—C13—C9 | −166.1 (5) | C14—C10—C11—C12 | −0.9 (8) |
Br1—C1—C13—C9 | 73.5 (6) | Br10—C10—C11—C12 | 178.2 (4) |
C2—C1—C13—C14 | 10.6 (7) | C8—C12—C11—C5 | 1.9 (8) |
Br1—C1—C13—C14 | −109.8 (5) | C9—C12—C11—C5 | −177.4 (5) |
C9—C13—C14—C10 | −1.7 (8) | C8—C12—C11—C10 | 179.7 (5) |
C1—C13—C14—C10 | −178.5 (5) | C9—C12—C11—C10 | 0.4 (8) |
C9—C13—C14—C4 | 174.2 (5) |
Experimental details
Crystal data | |
Chemical formula | C14H8Br6 |
Mr | 655.60 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.9289 (10), 8.4017 (10), 13.285 (1) |
α, β, γ (°) | 79.759 (5), 82.136 (6), 72.503 (5) |
V (Å3) | 827.31 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 14.55 |
Crystal size (mm) | 0.3 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Enraf-Nonius TurboCAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.190, 0.234 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3596, 3347, 2228 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.623 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.080, 1.02 |
No. of reflections | 3347 |
No. of parameters | 203 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.69 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C4—Br4 | 1.993 (6) | C2—Br2 | 1.955 (5) |
C1—Br1 | 1.991 (5) | Br9—C9 | 1.887 (5) |
C3—Br3 | 1.967 (6) | Br10—C10 | 1.899 (5) |
C14—C4—Br4 | 109.4 (4) | C3—C2—Br2 | 112.0 (4) |
C3—C4—Br4 | 109.1 (4) | C1—C2—Br2 | 110.9 (4) |
C13—C1—Br1 | 111.2 (4) | C13—C9—Br9 | 119.7 (4) |
C2—C1—Br1 | 104.8 (4) | C12—C9—Br9 | 117.0 (4) |
C4—C3—Br3 | 106.0 (4) | C14—C10—Br10 | 118.1 (4) |
C2—C3—Br3 | 113.4 (4) | C11—C10—Br10 | 118.2 (4) |
Br4—C4—C3—Br3 | 171.5 (2) | C13—C14—C10—Br10 | −177.5 (4) |
Br3—C3—C2—Br2 | −58.4 (5) | Br9—C9—C12—C11 | −179.2 (4) |
Br1—C1—C2—Br2 | −91.4 (4) | Br10—C10—C11—C12 | 178.2 (4) |
Br9—C9—C13—C14 | 179.8 (4) |
Bromination of aromatic compounds with elemental bromine is well known. Aromatic bromination generally requires using catalyst and often gives mixture of products (Hamanoue et al., 1984). Monohalogenation of benzenoid aromatics generally does not need any catalyst unlike benzene although, further halogenation generally needs a catalyst. Therefore, synthesis of bromosubstituted anthracenes is restricted by starting anthracene because reactivity is reduced against bromine after some certain steps (Gieman, 1967).
Bromination of 9,10-dibromoanthracene is important in view of synthesis of further brominated anthracene derivatives (Pac & Sakurai, 1969). For example, polyfunctionalization of anthracene may supply synthesis of anthraquinone dyes which provide the best example of the versatility of bromine in dye stuffs. Anthraquinone dyes comprise a large group, members of which are capable of wide variations indexing characteristics depending on their substituent group. Bromoanthraquinones are frequently used as intermediates. Brominated diaminodihydroxyanthraquinones are useful disperse dyes with good light fastness (Sumitomo Chem. Co. Ltd, 1984; Mitsubishi Chem. Ind. Co. Ltd, 1981).
9,10-Dibromoanthracene was photobrominated by using projector lamp in CCl4 at room temperature. The reaction gives mixture of products. The title compound, (I), was obtained as a major component. Because of the very close structural similarity, we were not able to make a clear-cut differentation between stereochemistries in any of these compounds containing four bromo substituents at sp3 hybridized carbons. Therefore, we carried out the structure determination of the isomer (I) shown in the Scheme.
The molecule (Fig. 1) contains the tetrahydroanthracene skeleton, composed of a six-membered ring A(C1—C4/C13/C14) with four Br atoms in a trans,cis,trans configuration, held in a boat conformation and two six-membered nearly coplanar rings B(C9—C14) and C(C5—C8/C11/C12), where ring B has two bromine atoms. The Br3—C3—C2 [113.4 (4)°], Br1—C1—C13 [111.2 (4)°] and Br2—C2—C3 [112.0 (4)°] angles are larger than the ones around the C3, C1, and C2 atoms, respectively. This behaviour appears to be the result of the repulsive interactions between the related bromine atoms. The Br—C—C angles around C4 [Br4—C4—C3 109.1 (4) and Br4—C4—C14 109.4 (4)°] and C10 [Br10—C10—C14 118.1 (4) and Br10—C10—C11 118.2 (4)°] are not different.
An examination of the deviations from the least-squares planes through the individual rings shows that ring A is not planar, with a maximum deviation for the C3 [-0.346 (6) Å] atom, while rings B and C are planar. These rings are also twisted with respect to each other. The dihedral angle between the best least-squares planes are A/B = 14.9 (2)°, A/C = 16.3 (2)° and B/C = 1.8 (2)°. In ring A, the puckering parameters, i.e. the angles between the best plane C1/C2/C4/C14 with C1/C13/C14 and C2/C3/C4 are 6.2 (5)° and 46.3 (4)°, respectively. Ring A has a boat conformation.