3,6-Dibromo-phenanthrene.

The phenanthrene ring in the title compound, C(14)H(8)Br(2), is approximately planar [maximum deviation = 0.039 (3) Å]. In contrast, the two bromo atoms are displaced slightly from the phenanthrene plane [maximum deviation = 0.1637 (3) Å]. In the crystal, the mol-ecules adopt a herringbone-like arrangement and form face-to-face slipped π-π stacking inter-actions along the b axis, with an inter-planar distance of 3.544 (3) Å and slippage of 1.81 Å. The crystal studied was a racemic twin with a minor twin fraction of 0.390 (10).

Related literature

For the synthesis of the title compound using the improved photocyclization of 4,4′-dibromo-trans-stilbene, see: Talele et al. (2009 ▶). For the original synthesis and applications of the title compound, see: Nakamura et al. (1996 ▶).

Experimental

Crystal data

C14H8Br2

M = 336.02

Monoclinic,

a = 6.8697 (5) Å

b = 3.9809 (2) Å

c = 20.5002 (11) Å

β = 93.813 (2)°

V = 559.39 (6) Å3

Z = 2

Mo Kα radiation

μ = 7.21 mm−1

T = 223 K

0.62 × 0.08 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T min = 0.196, T max = 0.793

5372 measured reflections

2267 independent reflections

2084 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.037

S = 1.00

2267 reflections

146 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.46 e Å−3

Absolute structure: Flack (1983 ▶), 831 Friedel pairs

Flack parameter: 0.390 (10)

Data collection: RAPID-AUTO (Rigaku, 1999 ▶); cell refinement: 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812041621/qk2043sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041621/qk2043Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812041621/qk2043Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H8Br2	F(000) = 324
Mr = 336.02	Dx = 1.995 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4191 reflections
a = 6.8697 (5) Å	θ = 3.1–27.5°
b = 3.9809 (2) Å	µ = 7.21 mm−1
c = 20.5002 (11) Å	T = 223 K
β = 93.813 (2)°	Needle, colorless
V = 559.39 (6) Å3	0.62 × 0.08 × 0.03 mm
Z = 2

Rigaku R-AXIS RAPID diffractometer	2267 independent reflections
Radiation source: fine-focus sealed x-ray tube	2084 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −8→8
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −5→4
Tmin = 0.196, Tmax = 0.793	l = −26→26
5372 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018	H-atom parameters constrained
wR(F2) = 0.037	w = 1/[σ2(Fo2) + (0.0175P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.002
2267 reflections	Δρmax = 0.38 e Å−3
146 parameters	Δρmin = −0.46 e Å−3
1 restraint	Absolute structure: Flack (1983), 831 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.390 (10)

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
C1	−0.1808 (4)	0.2590 (6)	0.88179 (11)	0.0315 (7)
H1	−0.2947	0.3158	0.9023	0.038*
C2	−0.0292 (4)	0.1043 (7)	0.91762 (12)	0.0313 (6)
H2	−0.0389	0.0537	0.9621	0.038*
C3	0.1384 (4)	0.0249 (7)	0.88644 (11)	0.0270 (6)
C4	0.1569 (4)	0.0897 (6)	0.82192 (11)	0.0249 (6)
H4	0.2724	0.0318	0.8025	0.03*
C5	0.0013 (4)	0.2449 (6)	0.78399 (11)	0.0243 (6)
C6	0.0120 (3)	0.3192 (8)	0.71506 (10)	0.0236 (5)
C7	0.1731 (4)	0.2289 (6)	0.67943 (11)	0.0241 (6)
H7	0.2806	0.1184	0.7005	0.029*
C8	0.1728 (4)	0.3020 (7)	0.61427 (11)	0.0259 (5)
C9	0.0176 (4)	0.4707 (7)	0.58081 (12)	0.0301 (6)
H9	0.0215	0.522	0.5362	0.036*
C10	−0.1392 (4)	0.5590 (7)	0.61443 (12)	0.0309 (6)
H10	−0.2438	0.6729	0.5924	0.037*
C11	−0.1487 (4)	0.4842 (7)	0.68117 (11)	0.0260 (5)
C12	−0.3169 (4)	0.5686 (7)	0.71513 (13)	0.0325 (7)
H12	−0.4223	0.6774	0.6925	0.039*
C13	−0.3277 (4)	0.4956 (8)	0.77907 (13)	0.0330 (6)
H13	−0.4408	0.5519	0.8001	0.04*
C14	−0.1683 (4)	0.3330 (8)	0.81549 (11)	0.0270 (5)
Br1	0.35013 (4)	−0.17379 (7)	0.937295 (11)	0.03280 (8)
Br2	0.38478 (4)	0.16231 (7)	0.565973 (12)	0.03364 (8)

	U11	U22	U33	U12	U13	U23
C1	0.0312 (15)	0.0336 (18)	0.0310 (12)	0.0016 (11)	0.0128 (11)	−0.0049 (11)
C2	0.0392 (16)	0.0317 (16)	0.0237 (11)	−0.0038 (12)	0.0084 (11)	0.0023 (12)
C3	0.0291 (15)	0.0259 (12)	0.0256 (12)	−0.0017 (11)	0.0000 (11)	−0.0018 (11)
C4	0.0248 (14)	0.0252 (15)	0.0251 (11)	−0.0008 (10)	0.0054 (10)	−0.0017 (10)
C5	0.0248 (13)	0.0239 (15)	0.0245 (11)	−0.0031 (9)	0.0029 (10)	−0.0029 (10)
C6	0.0229 (12)	0.0214 (10)	0.0262 (11)	−0.0041 (13)	0.0002 (9)	−0.0010 (13)
C7	0.0222 (12)	0.0258 (15)	0.0241 (11)	0.0026 (9)	−0.0001 (9)	0.0001 (10)
C8	0.0265 (13)	0.0248 (12)	0.0268 (11)	−0.0043 (12)	0.0047 (10)	−0.0039 (12)
C9	0.0363 (16)	0.0281 (13)	0.0255 (12)	−0.0004 (13)	−0.0007 (11)	0.0012 (12)
C10	0.0296 (16)	0.0299 (14)	0.0324 (13)	0.0032 (11)	−0.0053 (11)	0.0001 (12)
C11	0.0247 (14)	0.0228 (12)	0.0301 (12)	−0.0018 (11)	−0.0009 (10)	−0.0032 (12)
C12	0.0223 (15)	0.0348 (16)	0.0396 (14)	0.0064 (11)	−0.0028 (12)	−0.0063 (13)
C13	0.0237 (15)	0.0344 (14)	0.0416 (14)	0.0030 (13)	0.0071 (11)	−0.0080 (14)
C14	0.0255 (13)	0.0244 (11)	0.0315 (11)	−0.0029 (14)	0.0040 (10)	−0.0012 (14)
Br1	0.03496 (16)	0.03660 (14)	0.02647 (12)	0.00097 (14)	−0.00083 (10)	0.00312 (13)
Br2	0.03388 (15)	0.04005 (15)	0.02791 (12)	0.00275 (14)	0.00893 (10)	0.00034 (13)

C1—C2	1.379 (4)	C7—C8	1.367 (3)
C1—C14	1.399 (3)	C7—H7	0.94
C1—H1	0.94	C8—C9	1.400 (3)
C2—C3	1.390 (4)	C8—Br2	1.898 (2)
C2—H2	0.94	C9—C10	1.363 (4)
C3—C4	1.362 (3)	C9—H9	0.94
C3—Br1	1.904 (2)	C10—C11	1.406 (3)
C4—C5	1.420 (3)	C10—H10	0.94
C4—H4	0.94	C11—C12	1.428 (4)
C5—C14	1.413 (3)	C12—C13	1.350 (4)
C5—C6	1.450 (3)	C12—H12	0.94
C6—C7	1.412 (3)	C13—C14	1.437 (4)
C6—C11	1.426 (3)	C13—H13	0.94
C2—C1—C14	121.2 (2)	C7—C8—C9	122.2 (2)
C2—C1—H1	119.4	C7—C8—Br2	119.72 (19)
C14—C1—H1	119.4	C9—C8—Br2	118.07 (17)
C1—C2—C3	118.4 (2)	C10—C9—C8	118.5 (2)
C1—C2—H2	120.8	C10—C9—H9	120.7
C3—C2—H2	120.8	C8—C9—H9	120.7
C4—C3—C2	122.5 (2)	C9—C10—C11	121.8 (2)
C4—C3—Br1	119.6 (2)	C9—C10—H10	119.1
C2—C3—Br1	117.94 (17)	C11—C10—H10	119.1
C3—C4—C5	119.9 (2)	C6—C11—C10	119.1 (2)
C3—C4—H4	120	C6—C11—C12	119.8 (2)
C5—C4—H4	120	C10—C11—C12	121.1 (2)
C14—C5—C4	118.1 (2)	C13—C12—C11	121.4 (2)
C14—C5—C6	119.4 (2)	C13—C12—H12	119.3
C4—C5—C6	122.5 (2)	C11—C12—H12	119.3
C7—C6—C11	118.3 (2)	C12—C13—C14	120.8 (3)
C7—C6—C5	123.0 (2)	C12—C13—H13	119.6
C11—C6—C5	118.7 (2)	C14—C13—H13	119.6
C8—C7—C6	120.0 (2)	C5—C14—C1	119.8 (2)
C8—C7—H7	120	C5—C14—C13	119.8 (2)
C6—C7—H7	120	C1—C14—C13	120.4 (2)
C14—C1—C2—C3	0.5 (4)	C7—C6—C11—C10	−1.7 (4)
C1—C2—C3—C4	−1.0 (4)	C5—C6—C11—C10	179.6 (2)
C1—C2—C3—Br1	177.77 (19)	C7—C6—C11—C12	177.8 (2)
C2—C3—C4—C5	0.2 (4)	C5—C6—C11—C12	−0.8 (4)
Br1—C3—C4—C5	−178.56 (17)	C9—C10—C11—C6	1.6 (4)
C3—C4—C5—C14	1.1 (3)	C9—C10—C11—C12	−177.9 (3)
C3—C4—C5—C6	−179.8 (2)	C6—C11—C12—C13	0.0 (4)
C14—C5—C6—C7	−177.7 (3)	C10—C11—C12—C13	179.5 (3)
C4—C5—C6—C7	3.2 (4)	C11—C12—C13—C14	0.7 (5)
C14—C5—C6—C11	0.9 (4)	C4—C5—C14—C1	−1.6 (4)
C4—C5—C6—C11	−178.2 (2)	C6—C5—C14—C1	179.3 (3)
C11—C6—C7—C8	0.5 (4)	C4—C5—C14—C13	179.0 (2)
C5—C6—C7—C8	179.0 (2)	C6—C5—C14—C13	−0.2 (4)
C6—C7—C8—C9	1.0 (4)	C2—C1—C14—C5	0.8 (4)
C6—C7—C8—Br2	−177.3 (2)	C2—C1—C14—C13	−179.7 (3)
C7—C8—C9—C10	−1.1 (4)	C12—C13—C14—C5	−0.6 (5)
Br2—C8—C9—C10	177.1 (2)	C12—C13—C14—C1	179.9 (3)
C8—C9—C10—C11	−0.2 (4)