9,10-Diiodo­phenanthrene

Abstract

The whole mol­ecule of the title compound, C₁₄H₈I₂, is generated by crystallographic twofold symmetry. The mol­ecule is planar [maximum deviation = 0.0323 (6) Å] with the I atoms displaced from the mean plane of the phenanthrene ring system by only 0.0254 (5) Å. In the crystal, mol­ecules form face-to-face slipped anti­parallel π–π stacking inter­actions along the c axis with an inter­planar distance of 3.499 (7) Å.

Related literature  

For the synthesis of the title compound, see: Rodrígeuz-Lojo et al. (2012 ▶). For a related structure, see: Yokota et al. (2012 ▶).

Experimental  

Crystal data  

• C₁₄H₈I₂

• M _r = 430

• Monoclinic,

• a = 18.094 (2) Å

• b = 9.4557 (14) Å

• c = 7.4187 (10) Å

• β = 111.953 (3)°

• V = 1177.2 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 5.31 mm⁻¹

• T = 223 K

• 0.52 × 0.08 × 0.05 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.388, T _max = 0.869

• 5595 measured reflections

• 1345 independent reflections

• 1077 reflections with I > 2σ(I)

• R _int = 0.030

Refinement  

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.083

• S = 1.12

• 1345 reflections

• 73 parameters

• H-atom parameters constrained

• Δρ_max = 0.92 e Å⁻³

• Δρ_min = −0.92 e Å⁻³

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 ▶).

Supplementary Material

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

supplementary crystallographic information

Comment

o-Diiodoarenes are valuable synthetic intermediates. We were able to obtain suitable single crystals of 9,10-diiodoophenanthrene, the title compound, by the recently published synthetic method of Rodrígeuz-Lojo et al. (2012). We report herein the crystal structure of C₁₄H₈I₂, the title compound.

In the molecular structure of the title compound, (I), the mean plane of the arene ring displays a maximum deviation of 0.0323 (6) Å for I1 (Fig. 1). The molecule possesses C₂ symmetry, and half of the formula unit is crystallographically independent. Bonds lengths and angles are in good agreement with the standard values. Crystal packing is stabilized by face-to-face, slipped, antiparrallel, π-π stacking along the direction of the c axis with an interplanar distance of 3.499 (7) Å (Fig. 2). Very recently, we have reported the crystal structure of 9,10-dibromophenanthrene (Yokota et al., 2012), the bromine analog of (I), which displays a similar packing arrangement.

Experimental

The title compound was prepared according to the literature method (Rodrígeuz-Lojo et al., 2012) Single crystals suitable for X-ray analysis were obtained from a toluene-hexane solution.

Refinement

All the aromatic H atoms were positioned geometrically and refined using a riding model with C—H = 0.94 Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing the atomic numbering and 40% probability displacement ellipsoids. Symmetry code: (i) -x + 1, y, -z + 1.5.

Fig. 2.

The packing diagram of the title compound viewed along the b axis. Hydrogen atoms have been omitted for clarity.

Crystal data

C14H8I2	F(000) = 792
Mr = 430	Dx = 2.426 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3465 reflections
a = 18.094 (2) Å	θ = 3.1–27.5°
b = 9.4557 (14) Å	µ = 5.31 mm−1
c = 7.4187 (10) Å	T = 223 K
β = 111.953 (3)°	Needle, colorless
V = 1177.2 (3) Å3	0.52 × 0.08 × 0.05 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	1345 independent reflections
Radiation source: fine-focus sealed x-ray tube	1077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 10 pixels mm-1	θmax = 27.5°, θmin = 3.5°
ω scans	h = −23→22
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −12→12
Tmin = 0.388, Tmax = 0.869	l = −8→9
5595 measured reflections

Refinement

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) = 0.083	w = 1/[σ2(Fo2) + (0.0077P)2 + 13.1956P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
1345 reflections	Δρmax = 0.92 e Å−3
73 parameters	Δρmin = −0.92 e Å−3
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3399 (3)	0.4417 (6)	0.4793 (7)	0.0368 (12)
H1	0.3127	0.3564	0.4332	0.044*
C2	0.3020 (3)	0.5667 (8)	0.4155 (8)	0.0470 (15)
H2	0.2488	0.5669	0.3275	0.056*
C3	0.3408 (3)	0.6927 (7)	0.4781 (9)	0.0467 (15)
H3	0.3146	0.7786	0.4306	0.056*
C4	0.4171 (4)	0.6931 (6)	0.6089 (8)	0.0424 (13)
H4	0.4426	0.78	0.6529	0.051*
C5	0.4587 (3)	0.5675 (5)	0.6798 (7)	0.0289 (10)
C6	0.4192 (3)	0.4383 (5)	0.6137 (7)	0.0261 (9)
C7	0.4618 (3)	0.3079 (5)	0.6846 (7)	0.0281 (10)
I1	0.40244 (3)	0.11933 (4)	0.58098 (7)	0.05783 (18)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.029 (2)	0.051 (3)	0.029 (3)	0.003 (2)	0.008 (2)	0.001 (2)
C2	0.026 (3)	0.078 (4)	0.034 (3)	0.012 (3)	0.007 (2)	0.010 (3)
C3	0.038 (3)	0.057 (4)	0.048 (3)	0.024 (3)	0.019 (3)	0.020 (3)
C4	0.048 (3)	0.040 (3)	0.048 (3)	0.012 (2)	0.028 (3)	0.008 (3)
C5	0.030 (2)	0.030 (2)	0.031 (3)	0.0021 (19)	0.017 (2)	0.0012 (19)
C6	0.023 (2)	0.035 (2)	0.024 (2)	0.0010 (18)	0.0126 (18)	0.0001 (18)
C7	0.033 (2)	0.026 (2)	0.025 (2)	−0.0029 (18)	0.010 (2)	−0.0020 (18)
I1	0.0670 (3)	0.0402 (2)	0.0526 (3)	−0.01527 (19)	0.0067 (2)	−0.00726 (18)

Geometric parameters (Å, º)

C1—C2	1.359 (8)	C4—C5	1.399 (7)
C1—C6	1.409 (7)	C4—H4	0.94
C1—H1	0.94	C5—C6	1.408 (7)
C2—C3	1.372 (9)	C5—C5i	1.467 (10)
C2—H2	0.94	C6—C7	1.445 (6)
C3—C4	1.359 (8)	C7—C7i	1.360 (9)
C3—H3	0.94	C7—I1	2.075 (5)
C2—C1—C6	120.9 (5)	C5—C4—H4	119.1
C2—C1—H1	119.6	C4—C5—C6	118.2 (5)
C6—C1—H1	119.6	C4—C5—C5i	121.9 (3)
C1—C2—C3	120.7 (5)	C6—C5—C5i	119.8 (3)
C1—C2—H2	119.7	C5—C6—C1	118.5 (5)
C3—C2—H2	119.7	C5—C6—C7	118.7 (4)
C4—C3—C2	119.9 (5)	C1—C6—C7	122.8 (5)
C4—C3—H3	120.1	C7i—C7—C6	121.5 (3)
C2—C3—H3	120.1	C7i—C7—I1	120.77 (13)
C3—C4—C5	121.8 (6)	C6—C7—I1	117.8 (3)
C3—C4—H4	119.1
C6—C1—C2—C3	1.1 (8)	C5i—C5—C6—C7	−0.9 (8)
C1—C2—C3—C4	−1.6 (9)	C2—C1—C6—C5	−0.4 (7)
C2—C3—C4—C5	1.4 (9)	C2—C1—C6—C7	−179.6 (5)
C3—C4—C5—C6	−0.7 (8)	C5—C6—C7—C7i	1.2 (8)
C3—C4—C5—C5i	179.7 (6)	C1—C6—C7—C7i	−179.6 (6)
C4—C5—C6—C1	0.2 (7)	C5—C6—C7—I1	−179.0 (3)
C5i—C5—C6—C1	179.8 (5)	C1—C6—C7—I1	0.2 (6)
C4—C5—C6—C7	179.5 (5)

Symmetry code: (i) −x+1, y, −z+3/2.