organic compounds
9,10-Dibromophenanthrene
aDepartment of Materials Science and Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan
*Correspondence e-mail: kitamura@eng.u-hyogo.ac.jp
The molecule of the title compound, C14H8Br2, is almost planar [maximum deviation 0.0355 (7) Å] and possesses crystallographic twofold (C2) symmetry. In the crystal, the molecules form face-to-face slipped antiparallel π–π stacking interactions along the c axis with an interplanar distance 3.471 (7) Å, centroid–centroid distances of 3.617 (5)–3.803 (6) Å.
Related literature
For the first synthesis of the title compound, see: Schmidt & Ladner (1904). For the synthesis of 2,2′-bis(dibromomethyl)biphenyl, see: Bacon & Bankhead (1963). For a related structure, see: Yokota et al. (2012).
Experimental
Crystal data
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Data collection: RAPID-AUTO (Rigaku, 1999); cell PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536812042353/rz5013sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042353/rz5013Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042353/rz5013Isup3.cml
2,2'-Bis(dibromomethyl)biphenyl, as a starting material, was prepared according to the method described by Bacon & Bankhead (1963). To an ice-cooled solution of 2,2'-bis(dibromomethyl)biphenyl (300 mg, 0.60 mmol) in DMF (6 ml), pottasium t-butoxide (1.00 g, 9.05 mmol) was added. After stirring for 30 min, the reaction was quenched with 6M HCl. The resulting solid was extracted with toluene, washed with brine, and dried over Na2SO4. After evaporation,
on silica gel (hexane-CH2Cl2) produced the title compound (161 mg, 79%) as a pale yellow solid. Single crystals suitable for X-ray analysis were obtained by slow evaporation from a toluene solution.All the aromatic H atoms were positioned geometrically and refined using a riding model with C—H = 0.94 Å and Uiso(H) = 1.2Ueq(C).
Data collection: RAPID-AUTO (Rigaku, 1999); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C14H8Br2 | F(000) = 648 |
Mr = 336.02 | Dx = 2.022 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3170 reflections |
a = 18.2630 (15) Å | θ = 3.0–27.5° |
b = 9.0963 (8) Å | µ = 7.31 mm−1 |
c = 7.3025 (6) Å | T = 223 K |
β = 114.499 (2)° | Needle, colourless |
V = 1103.91 (16) Å3 | 0.5 × 0.1 × 0.08 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 1257 independent reflections |
Radiation source: fine-focus sealed x-ray tube | 1011 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 10 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ω scans | h = −23→23 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −11→11 |
Tmin = 0.160, Tmax = 0.558 | l = −9→9 |
5151 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0313P)2 + 8.7358P] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max < 0.001 |
1257 reflections | Δρmax = 0.67 e Å−3 |
73 parameters | Δρmin = −1.49 e Å−3 |
0 restraints |
C14H8Br2 | V = 1103.91 (16) Å3 |
Mr = 336.02 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.2630 (15) Å | µ = 7.31 mm−1 |
b = 9.0963 (8) Å | T = 223 K |
c = 7.3025 (6) Å | 0.5 × 0.1 × 0.08 mm |
β = 114.499 (2)° |
Rigaku R-AXIS RAPID diffractometer | 1257 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 1011 reflections with I > 2σ(I) |
Tmin = 0.160, Tmax = 0.558 | Rint = 0.028 |
5151 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.25 | Δρmax = 0.67 e Å−3 |
1257 reflections | Δρmin = −1.49 e Å−3 |
73 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
C1 | 0.3372 (3) | 0.4275 (6) | 0.2001 (7) | 0.0341 (11) | |
H1 | 0.3099 | 0.3382 | 0.1903 | 0.041* | |
C2 | 0.2976 (3) | 0.5571 (7) | 0.1900 (8) | 0.0395 (12) | |
H2 | 0.2438 | 0.5564 | 0.1738 | 0.047* | |
C3 | 0.3375 (3) | 0.6900 (6) | 0.2037 (8) | 0.0388 (12) | |
H3 | 0.3103 | 0.7791 | 0.1962 | 0.047* | |
C4 | 0.4163 (3) | 0.6916 (5) | 0.2284 (7) | 0.0320 (10) | |
H4 | 0.4425 | 0.7822 | 0.2387 | 0.038* | |
C5 | 0.4586 (3) | 0.5595 (5) | 0.2384 (6) | 0.0248 (9) | |
C6 | 0.4168 (3) | 0.4248 (5) | 0.2245 (6) | 0.0257 (9) | |
C7 | 0.4612 (3) | 0.2907 (5) | 0.2373 (7) | 0.0268 (9) | |
Br1 | 0.40654 (4) | 0.11098 (6) | 0.22296 (10) | 0.0491 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.034 (2) | 0.039 (3) | 0.031 (2) | −0.005 (2) | 0.015 (2) | −0.001 (2) |
C2 | 0.025 (2) | 0.058 (3) | 0.036 (3) | 0.011 (2) | 0.013 (2) | 0.001 (2) |
C3 | 0.033 (3) | 0.042 (3) | 0.037 (3) | 0.014 (2) | 0.010 (2) | 0.001 (2) |
C4 | 0.036 (2) | 0.027 (2) | 0.032 (2) | 0.0076 (19) | 0.012 (2) | −0.0008 (19) |
C5 | 0.028 (2) | 0.025 (2) | 0.020 (2) | 0.0015 (17) | 0.0090 (18) | −0.0012 (16) |
C6 | 0.027 (2) | 0.028 (2) | 0.020 (2) | 0.0002 (17) | 0.0083 (18) | 0.0004 (17) |
C7 | 0.033 (2) | 0.021 (2) | 0.029 (2) | −0.0036 (17) | 0.015 (2) | −0.0008 (17) |
Br1 | 0.0552 (4) | 0.0270 (3) | 0.0752 (5) | −0.0125 (2) | 0.0373 (3) | −0.0035 (3) |
C1—C2 | 1.369 (7) | C4—C5 | 1.415 (6) |
C1—C6 | 1.389 (6) | C4—H4 | 0.94 |
C1—H1 | 0.94 | C5—C6 | 1.424 (6) |
C2—C3 | 1.393 (8) | C5—C5i | 1.449 (9) |
C2—H2 | 0.94 | C6—C7 | 1.447 (6) |
C3—C4 | 1.375 (7) | C7—C7i | 1.349 (9) |
C3—H3 | 0.94 | C7—Br1 | 1.896 (4) |
C2—C1—C6 | 121.5 (5) | C5—C4—H4 | 119.4 |
C2—C1—H1 | 119.2 | C4—C5—C6 | 117.5 (4) |
C6—C1—H1 | 119.2 | C4—C5—C5i | 121.8 (3) |
C1—C2—C3 | 119.7 (5) | C6—C5—C5i | 120.7 (3) |
C1—C2—H2 | 120.2 | C1—C6—C5 | 119.7 (4) |
C3—C2—H2 | 120.2 | C1—C6—C7 | 123.5 (4) |
C4—C3—C2 | 120.4 (5) | C5—C6—C7 | 116.8 (4) |
C4—C3—H3 | 119.8 | C7i—C7—C6 | 122.5 (2) |
C2—C3—H3 | 119.8 | C7i—C7—Br1 | 120.42 (14) |
C3—C4—C5 | 121.2 (5) | C6—C7—Br1 | 117.1 (3) |
C3—C4—H4 | 119.4 | ||
C6—C1—C2—C3 | 0.2 (8) | C5i—C5—C6—C1 | −179.3 (5) |
C1—C2—C3—C4 | −0.3 (8) | C4—C5—C6—C7 | −179.3 (4) |
C2—C3—C4—C5 | 0.6 (7) | C5i—C5—C6—C7 | 0.8 (7) |
C3—C4—C5—C6 | −0.8 (7) | C1—C6—C7—C7i | −179.4 (5) |
C3—C4—C5—C5i | 179.2 (5) | C5—C6—C7—C7i | 0.5 (8) |
C2—C1—C6—C5 | −0.4 (7) | C1—C6—C7—Br1 | −0.9 (6) |
C2—C1—C6—C7 | 179.6 (5) | C5—C6—C7—Br1 | 179.1 (3) |
C4—C5—C6—C1 | 0.6 (6) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H8Br2 |
Mr | 336.02 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 223 |
a, b, c (Å) | 18.2630 (15), 9.0963 (8), 7.3025 (6) |
β (°) | 114.499 (2) |
V (Å3) | 1103.91 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.31 |
Crystal size (mm) | 0.5 × 0.1 × 0.08 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.160, 0.558 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5151, 1257, 1011 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.116, 1.25 |
No. of reflections | 1257 |
No. of parameters | 73 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −1.49 |
Computer programs: RAPID-AUTO (Rigaku, 1999), PROCESS-AUTO (Rigaku, 1998), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Acknowledgements
This work was supported by Grants-in-Aid for Scientific Research from the JSPS and MEXT.
References
Bacon, R. G. R. & Bankhead, R. (1963). J. Chem. Soc. pp. 839–845. CrossRef Web of Science Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1999). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Schmidt, J. & Ladner, G. (1904). Chem. Ber. 37, 4402–4405. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yokota, R., Kitamura, C. & Kawase, T. (2012). Acta Cryst. E68, o3100. CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Phenanthrene is a polycylic aromatic hydrocarbon (PAH) as well as an important starting material toward fuctionalized π-conjugated molecules. The title compound, 9,10-dibromophenanthrene, was first prepared by Schmidt & Ladner (1904). However, the method involved relatively vigorous reaction conditions, and the title compound was not easily accessible. Therefore, the development of milder methods was pursued. Recently, we established a new method for the preparation of the title compound. Thus, treatment of 2,2'-bis(dibromomethyl)biphenyl (Bacon & Bankhead, 1963) with potassium t-butoxide yielded the title compound in a high yield. Securement of the title compound let to obtain single crystals suitable for X-ray analysis. We report herein the crystal structure of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The molecule possesses C2 symmetry, and half of the formula unit is crystallographically independent. The molecule is almost planar with the maximum deviation of 0.0355 (7) Å for Br1. The bonds lengths and angles are in good agreement with the standard values. As shown in Fig. 2, the molecules form face-to-face slipped antiparrallel π-π stacking along the direction of the c axis. The interplanar distance is 3.471 (7) Å and controid–centroid distances of 3.617 (5)-3.803 (6) Å. Recently, we have reported the crystal structure of 3,6-dibromophenanthrene (Yokota et al., 2012), whose feature was a herrinbone-like arrangement, indicating the difference in packing arrangement depending on the positions of bromo substituents.