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The title compound, C14H8Br6, consists of a tetra­hydro­anthracene skeleton composed of a six-membered ring A with four bromine atoms in trans,cis,trans configuration held in a boat conformation and two six-membered nearly coplanar rings B and C, where the ring B carries two Br atoms. The repulsive interactions between the Br atoms affect the topology of the tetra­hydro­anthracene moieties.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680102061X/ob6099sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680102061X/ob6099Isup2.hkl
Contains datablock I

CCDC reference: 180528

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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








Comment top

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.

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] 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.
(I) top
Crystal data top
C14H8Br6Z = 2
Mr = 655.60F(000) = 604
Triclinic, P1Dx = 2.632 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9289 (10) ÅCell parameters from 25 reflections
b = 8.4017 (10) Åθ = 9–18°
c = 13.285 (1) ŵ = 14.55 mm1
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
Data collection top
Enraf-Nonius TurboCAD-4
diffractometer
2228 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
Graphite monochromatorθmax = 26.3°, θmin = 2.6°
non–profiled ω/2θ scansh = 90
Absorption correction: ψ scan
(North et al., 1968)
k = 109
Tmin = 0.190, Tmax = 0.234l = 1616
3596 measured reflections3 standard reflections every 120 min
3347 independent reflections intensity decay: 1%
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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H 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 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.69 e Å3
Crystal data top
C14H8Br6γ = 72.503 (5)°
Mr = 655.60V = 827.31 (14) Å3
Triclinic, P1Z = 2
a = 7.9289 (10) ÅMo Kα radiation
b = 8.4017 (10) ŵ = 14.55 mm1
c = 13.285 (1) ÅT = 293 K
α = 79.759 (5)°0.3 × 0.1 × 0.1 mm
β = 82.136 (6)°
Data collection top
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 = 0.2343 standard reflections every 120 min
3596 measured reflections intensity decay: 1%
3347 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.58 e Å3
3347 reflectionsΔρmin = 0.69 e Å3
203 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
Br10.11808 (10)1.51524 (7)0.75478 (6)0.0521 (2)
Br20.17882 (9)1.40347 (8)0.59044 (5)0.04705 (18)
Br30.00175 (9)0.96729 (8)0.65348 (5)0.04360 (18)
Br40.48367 (9)1.17985 (9)0.58084 (5)0.04476 (17)
Br90.00626 (10)1.29374 (8)0.98628 (5)0.05004 (19)
Br100.59474 (10)0.73338 (9)0.74579 (6)0.0630 (2)
C10.0592 (8)1.3026 (6)0.7499 (4)0.0290 (12)
C20.0587 (8)1.2968 (7)0.6360 (4)0.0302 (13)
C30.1402 (8)1.1258 (7)0.6027 (4)0.0320 (13)
C40.3176 (8)1.0458 (7)0.6449 (4)0.0309 (13)
C50.5044 (10)0.7234 (8)0.9838 (6)0.0484 (18)
C60.4822 (10)0.7019 (9)1.0874 (6)0.056 (2)
C70.3597 (11)0.8235 (10)1.1378 (5)0.054 (2)
C80.2547 (9)0.9653 (8)1.0841 (4)0.0418 (16)
C90.1631 (7)1.1315 (6)0.9153 (4)0.0289 (12)
C100.4167 (7)0.8930 (7)0.8159 (4)0.0317 (13)
C110.4022 (8)0.8667 (7)0.9241 (4)0.0333 (13)
C120.2714 (8)0.9902 (7)0.9760 (4)0.0304 (13)
C130.1796 (7)1.1553 (6)0.8101 (4)0.0228 (11)
C140.3101 (7)1.0300 (6)0.7577 (4)0.0247 (11)
H10.052 (7)1.323 (6)0.776 (4)0.012 (12)*
H20.123 (7)1.365 (7)0.599 (4)0.035 (16)*
H30.154 (6)1.135 (6)0.525 (4)0.020 (13)*
H40.366 (8)0.948 (7)0.621 (4)0.038 (16)*
H50.571 (10)0.656 (9)0.950 (6)0.067*
H60.54970.60501.12500.067*
H70.353 (9)0.821 (8)1.208 (6)0.067*
H80.17201.04541.11930.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0724 (5)0.0258 (3)0.0610 (5)0.0130 (3)0.0208 (4)0.0038 (3)
Br20.0407 (4)0.0501 (4)0.0425 (4)0.0051 (3)0.0142 (3)0.0081 (3)
Br30.0585 (4)0.0431 (3)0.0368 (4)0.0254 (3)0.0083 (3)0.0033 (3)
Br40.0411 (4)0.0613 (4)0.0317 (3)0.0194 (3)0.0059 (3)0.0047 (3)
Br90.0615 (5)0.0510 (4)0.0410 (4)0.0183 (3)0.0125 (3)0.0243 (3)
Br100.0592 (5)0.0482 (4)0.0574 (5)0.0185 (3)0.0000 (4)0.0077 (3)
C10.028 (3)0.025 (3)0.033 (3)0.005 (2)0.005 (3)0.005 (2)
C20.031 (3)0.027 (3)0.032 (3)0.010 (2)0.009 (3)0.004 (2)
C30.040 (3)0.032 (3)0.025 (3)0.011 (3)0.002 (3)0.005 (2)
C40.041 (3)0.025 (3)0.022 (3)0.001 (2)0.001 (3)0.008 (2)
C50.050 (5)0.043 (4)0.052 (5)0.019 (3)0.017 (4)0.012 (3)
C60.066 (5)0.060 (5)0.048 (4)0.035 (4)0.033 (4)0.026 (4)
C70.082 (6)0.075 (5)0.024 (3)0.058 (5)0.016 (4)0.016 (4)
C80.058 (4)0.059 (4)0.021 (3)0.039 (3)0.004 (3)0.001 (3)
C90.034 (3)0.028 (3)0.027 (3)0.013 (2)0.007 (2)0.009 (2)
C100.030 (3)0.030 (3)0.034 (3)0.006 (2)0.000 (3)0.006 (2)
C110.038 (3)0.035 (3)0.031 (3)0.018 (3)0.007 (3)0.004 (2)
C120.037 (3)0.039 (3)0.022 (3)0.024 (3)0.008 (2)0.003 (2)
C130.025 (3)0.022 (2)0.023 (3)0.009 (2)0.003 (2)0.003 (2)
C140.030 (3)0.025 (3)0.020 (3)0.010 (2)0.000 (2)0.004 (2)
Geometric parameters (Å, º) top
C4—C141.475 (7)C7—H70.92 (7)
C4—C31.502 (8)C5—C61.351 (10)
C4—Br41.993 (6)C5—C111.408 (8)
C4—H40.89 (6)C5—H50.80 (7)
C1—C131.493 (7)C8—C121.407 (8)
C1—C21.523 (8)C8—H80.9300
C1—Br11.991 (5)C6—H60.9300
C1—H10.88 (5)Br9—C91.887 (5)
C3—C21.506 (7)Br10—C101.899 (5)
C3—Br31.967 (6)C9—C131.370 (7)
C3—H31.02 (5)C9—C121.426 (8)
C2—Br21.955 (5)C13—C141.439 (7)
C2—H20.92 (6)C14—C101.383 (7)
C7—C81.373 (10)C10—C111.409 (8)
C7—C61.379 (11)C12—C111.429 (8)
C14—C4—C3113.7 (5)C6—C5—C11121.7 (7)
C14—C4—Br4109.4 (4)C6—C5—H5125 (6)
C3—C4—Br4109.1 (4)C11—C5—H5113 (6)
C14—C4—H4113 (4)C7—C8—C12120.4 (7)
C3—C4—H4108 (4)C7—C8—H8119.8
Br4—C4—H4103 (4)C12—C8—H8119.8
C13—C1—C2117.1 (4)C5—C6—C7120.1 (6)
C13—C1—Br1111.2 (4)C5—C6—H6119.9
C2—C1—Br1104.8 (4)C7—C6—H6119.9
C13—C1—H1113 (3)C13—C9—C12123.3 (5)
C2—C1—H1106 (3)C13—C9—Br9119.7 (4)
Br1—C1—H1104 (3)C12—C9—Br9117.0 (4)
C4—C3—C2109.7 (5)C9—C13—C14118.6 (5)
C4—C3—Br3106.0 (4)C9—C13—C1121.3 (5)
C2—C3—Br3113.4 (4)C14—C13—C1120.0 (5)
C4—C3—H3110 (3)C10—C14—C13118.5 (5)
C2—C3—H3111 (3)C10—C14—C4122.2 (5)
Br3—C3—H3106 (3)C13—C14—C4119.1 (5)
C3—C2—C1115.5 (5)C14—C10—C11123.7 (5)
C3—C2—Br2112.0 (4)C14—C10—Br10118.1 (4)
C1—C2—Br2110.9 (4)C11—C10—Br10118.2 (4)
C3—C2—H2106 (4)C8—C12—C9123.5 (6)
C1—C2—H2109 (4)C8—C12—C11118.4 (5)
Br2—C2—H2103 (4)C9—C12—C11118.1 (5)
C8—C7—C6121.0 (6)C5—C11—C10124.0 (6)
C8—C7—H7116 (5)C5—C11—C12118.2 (6)
C6—C7—H7123 (5)C10—C11—C12117.7 (5)
C14—C4—C3—C256.8 (6)C1—C13—C14—C42.6 (8)
Br4—C4—C3—C265.7 (5)C3—C4—C14—C10143.8 (5)
C14—C4—C3—Br366.0 (5)Br4—C4—C14—C1093.9 (5)
Br4—C4—C3—Br3171.5 (2)C3—C4—C14—C1332.0 (7)
C4—C3—C2—C148.5 (7)Br4—C4—C14—C1390.3 (5)
Br3—C3—C2—C169.8 (6)C13—C14—C10—C111.6 (8)
C4—C3—C2—Br2176.7 (4)C4—C14—C10—C11174.2 (5)
Br3—C3—C2—Br258.4 (5)C13—C14—C10—Br10177.5 (4)
C13—C1—C2—C316.0 (7)C4—C14—C10—Br106.7 (7)
Br1—C1—C2—C3139.8 (4)C7—C8—C12—C9177.9 (5)
C13—C1—C2—Br2144.8 (4)C7—C8—C12—C111.3 (9)
Br1—C1—C2—Br291.4 (4)C13—C9—C12—C8179.9 (5)
C6—C7—C8—C120.6 (10)Br9—C9—C12—C81.6 (7)
C11—C5—C6—C71.4 (11)C13—C9—C12—C110.7 (8)
C8—C7—C6—C52.0 (11)Br9—C9—C12—C11179.2 (4)
C12—C9—C13—C141.3 (8)C6—C5—C11—C10178.2 (6)
Br9—C9—C13—C14179.8 (4)C6—C5—C11—C120.6 (10)
C12—C9—C13—C1178.1 (5)C14—C10—C11—C5176.8 (6)
Br9—C9—C13—C13.4 (7)Br10—C10—C11—C54.2 (8)
C2—C1—C13—C9166.1 (5)C14—C10—C11—C120.9 (8)
Br1—C1—C13—C973.5 (6)Br10—C10—C11—C12178.2 (4)
C2—C1—C13—C1410.6 (7)C8—C12—C11—C51.9 (8)
Br1—C1—C13—C14109.8 (5)C9—C12—C11—C5177.4 (5)
C9—C13—C14—C101.7 (8)C8—C12—C11—C10179.7 (5)
C1—C13—C14—C10178.5 (5)C9—C12—C11—C100.4 (8)
C9—C13—C14—C4174.2 (5)

Experimental details

Crystal data
Chemical formulaC14H8Br6
Mr655.60
Crystal system, space groupTriclinic, 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)
V3)827.31 (14)
Z2
Radiation typeMo Kα
µ (mm1)14.55
Crystal size (mm)0.3 × 0.1 × 0.1
Data collection
DiffractometerEnraf-Nonius TurboCAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.190, 0.234
No. of measured, independent and
observed [I > 2σ(I)] reflections
3596, 3347, 2228
Rint0.022
(sin θ/λ)max1)0.623
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.080, 1.02
No. of reflections3347
No. of parameters203
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
C4—Br41.993 (6)C2—Br21.955 (5)
C1—Br11.991 (5)Br9—C91.887 (5)
C3—Br31.967 (6)Br10—C101.899 (5)
C14—C4—Br4109.4 (4)C3—C2—Br2112.0 (4)
C3—C4—Br4109.1 (4)C1—C2—Br2110.9 (4)
C13—C1—Br1111.2 (4)C13—C9—Br9119.7 (4)
C2—C1—Br1104.8 (4)C12—C9—Br9117.0 (4)
C4—C3—Br3106.0 (4)C14—C10—Br10118.1 (4)
C2—C3—Br3113.4 (4)C11—C10—Br10118.2 (4)
Br4—C4—C3—Br3171.5 (2)C13—C14—C10—Br10177.5 (4)
Br3—C3—C2—Br258.4 (5)Br9—C9—C12—C11179.2 (4)
Br1—C1—C2—Br291.4 (4)Br10—C10—C11—C12178.2 (4)
Br9—C9—C13—C14179.8 (4)
 

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