1-Iodo­triptycene

Betz, R.; McCleland, C.; Scheffer, A.

doi:10.1107/S160053681103279X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2368

doi:10.1107/S160053681103279X

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1-Iodotriptycene

Richard Betz,^a ^* Cedric McCleland ^a and André Scheffer ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth, 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 28 July 2011; accepted 12 August 2011; online 17 August 2011)

The title compound, C₂₀H₁₃I, is a halogenated derivative of triptycene. The molecule shows crystallographic as well as non-crystallographic C₃ symmetry. The asymmetric unit comprises one third of the molecule. Dispersive I⋯I contacts [I⋯I = 3.6389 (3) Å] connect the molecules into dimers. The shortest centroid–centroid distance between two π-systems is 3.8403 (12) Å.

Related literature

For the crystal structures of 1-bromotriptycene, 9,10-dibromotriptycene and 10-bromo-9-triptycyl iodoformate, see: Palmer & Templeton (1968 ), Abergel & Dinca (2004 ) and de Wet et al. (1978 ), respectively. For the preparation, see: Bartel et al. (1971 ).

Experimental

Crystal data

C₂₀H₁₃I
M_r = 380.20
Hexagonal, $[R \overline 3]$
a = 11.8820 (4) Å
c = 17.6800 (5) Å
V = 2161.68 (12) Å³
Z = 6
Mo Kα radiation
μ = 2.21 mm⁻¹
T = 200 K
0.56 × 0.51 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.568, T_max = 0.746
4033 measured reflections
1184 independent reflections
1156 reflections with I > 2σ(I)
R_int = 0.011

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.059
S = 1.15
1184 reflections
64 parameters
H-atom parameters constrained
Δρ_max = 1.52 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681103279X/nk2107sup1.cif

Supporting information file. DOI: 10.1107/S160053681103279X/nk2107Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S160053681103279X/nk2107Isup3.hkl

checkCIF report

Comment top

The chemistry of molecules featuring double and triple bonds involving elements from the third row of the periodic system of the elements (or below) is affected by the marked tendency of oligo- and polymerization. The introduction of sterically demanding, "bulky" protective groups in proximity to such bonding systems allowed the isolation and characterization of respective compounds on grounds of steric shielding and, as a consequence, markedly decreased rate of polymerization. It seemed of interest for us to study whether the presence of such aforementioned bonding systems has an influence on the metrical parameters of the applied protection groups as well. Therefore, we determined the crystal structure of the title compound. So far, the molecular and crystal stuctures of 1-bromotriptycene (Palmer & Templeton, 1968), 9,10-dibromotriptycene (Abergel & Dinca, 2004) as well as 10-bromo-9-triptycyl iodoformate (de Wet et al., 1978) are the only examples of structurally characterized triptycene compounds bearing a halogenido substituent on the bridgehead carbon atom present in the literature.

Halogenation took place on one of the bridgehead carbon atoms of the triptycene molecule (Figure 1). The least-squares planes defined by the atoms of the three aromatic moieties enclose angles of 60.03 (4) ° and 60.03 (7), respectively.

In the molecules, dispersive I···I contacts whose range falls by more than 0.3 Å below the sum of van der Waals radii can be observed (Figure 2). These connect two molecules to dimeric units whose I···I vector is pointing along the crystallographic c axis. The aromatic moieties of one molecule in such a dimer adopt a staggered conformation towards the aromatic moieties in the other molecule when projected along the I···I axis. The closest intercentroid distance between two π-systems was measured at 3.8403 (12) Å.

Related literature top

For the crystal structure of 1-bromotriptycene, see: Palmer & Templeton (1968). For the crystal structure of 9,10-dibromotriptycene, see: Abergel & Dinca (2004). For the crystal structure of 10-bromo-9-triptycyl iodoformate, see: de Wet et al. (1978). For the preparation, see: Bartel et al. (1971).

Experimental top

The compound was formed through the thermolysis of 9-triptycyl iodoformate according to a published procedure (Bartel et al., 1971).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, anisotropic displacement ellipsoids are drawn at 50% probability level. Symmetry operators: ⁱ -y, x-y, z; ⁱⁱ -x + y, -x, z.
	Fig. 2. Intermolecular I···I contact, viewed along [0 - 1 0]. Symmetry operator: ⁱ -x, -y, -z.

9-iodo-9,10-dihydro-9,10[1',2']-benzenoanthracene top

Crystal data top

C₂₀H₁₃I	D_x = 1.752 Mg m⁻³
M_r = 380.20	Mo Kα radiation, λ = 0.71069 Å
Hexagonal, R3	Cell parameters from 3561 reflections
Hall symbol: -R 3	θ = 4.1–28.3°
a = 11.8820 (4) Å	µ = 2.21 mm⁻¹
c = 17.6800 (5) Å	T = 200 K
V = 2161.68 (12) Å³	Block, colourless
Z = 6	0.56 × 0.51 × 0.25 mm
F(000) = 1116

Data collection top

Bruker APEXII CCD diffractometer	1184 independent reflections
Radiation source: fine-focus sealed tube	1156 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→10
T_min = 0.568, T_max = 0.746	k = −13→15
4033 measured reflections	l = −20→23

Refinement top

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0366P)² + 2.801P] where P = (F_o² + 2F_c²)/3
1184 reflections	(Δ/σ)_max < 0.001
64 parameters	Δρ_max = 1.52 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₂₀H₁₃I	Z = 6
M_r = 380.20	Mo Kα radiation
Hexagonal, R3	µ = 2.21 mm⁻¹
a = 11.8820 (4) Å	T = 200 K
c = 17.6800 (5) Å	0.56 × 0.51 × 0.25 mm
V = 2161.68 (12) Å³

Data collection top

Bruker APEXII CCD diffractometer	1184 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1156 reflections with I > 2σ(I)
T_min = 0.568, T_max = 0.746	R_int = 0.011
4033 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.15	Δρ_max = 1.52 e Å⁻³
1184 reflections	Δρ_min = −0.51 e Å⁻³
64 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.0000	0.0000	0.102907 (11)	0.03354 (10)
C1	0.11904 (15)	0.11668 (15)	0.33674 (10)	0.0219 (3)
C2	0.12090 (15)	0.11714 (15)	0.25794 (10)	0.0207 (3)
C3	0.22522 (17)	0.21626 (17)	0.21950 (11)	0.0264 (3)
H3	0.2274	0.2169	0.1658	0.032*
C4	0.32674 (18)	0.31494 (17)	0.26061 (13)	0.0330 (4)
H4	0.3988	0.3826	0.2346	0.040*
C5	0.32397 (18)	0.31565 (18)	0.33846 (14)	0.0337 (4)
H5	0.3933	0.3842	0.3657	0.040*
C6	0.21961 (18)	0.21594 (17)	0.37755 (12)	0.0284 (4)
H6	0.2174	0.2160	0.4313	0.034*
C7	0.0000	0.0000	0.22412 (15)	0.0188 (5)
C8	0.0000	0.0000	0.37075 (17)	0.0224 (5)
H8	0.0000	0.0000	0.4273	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04045 (12)	0.04045 (12)	0.01971 (13)	0.02022 (6)	0.000	0.000
C1	0.0206 (7)	0.0206 (7)	0.0262 (8)	0.0115 (6)	−0.0022 (6)	−0.0016 (6)
C2	0.0177 (7)	0.0176 (7)	0.0276 (8)	0.0094 (6)	−0.0006 (6)	−0.0004 (6)
C3	0.0230 (7)	0.0231 (7)	0.0318 (9)	0.0107 (6)	0.0039 (6)	0.0044 (6)
C4	0.0212 (8)	0.0203 (8)	0.0530 (12)	0.0071 (6)	0.0005 (7)	0.0042 (8)
C5	0.0238 (8)	0.0206 (7)	0.0538 (12)	0.0089 (7)	−0.0117 (8)	−0.0056 (8)
C6	0.0280 (8)	0.0254 (8)	0.0349 (9)	0.0157 (7)	−0.0098 (7)	−0.0072 (7)
C7	0.0202 (7)	0.0202 (7)	0.0162 (12)	0.0101 (4)	0.000	0.000
C8	0.0242 (8)	0.0242 (8)	0.0189 (13)	0.0121 (4)	0.000	0.000

Geometric parameters (Å, º) top

I1—C7	2.143 (3)	C4—H4	0.9500
C1—C6	1.389 (2)	C5—C6	1.396 (3)
C1—C2	1.393 (2)	C5—H5	0.9500
C1—C8	1.524 (2)	C6—H6	0.9500
C2—C3	1.388 (2)	C7—C2ⁱ	1.5359 (19)
C2—C7	1.5359 (19)	C7—C2ⁱⁱ	1.5359 (19)
C3—C4	1.394 (3)	C8—C1ⁱ	1.524 (2)
C3—H3	0.9500	C8—C1ⁱⁱ	1.524 (2)
C4—C5	1.377 (4)	C8—H8	1.0000

C6—C1—C2	120.71 (16)	C1—C6—C5	119.03 (19)
C6—C1—C8	125.48 (18)	C1—C6—H6	120.5
C2—C1—C8	113.81 (16)	C5—C6—H6	120.5
C3—C2—C1	119.92 (16)	C2—C7—C2ⁱ	105.82 (13)
C3—C2—C7	127.75 (17)	C2—C7—C2ⁱⁱ	105.82 (13)
C1—C2—C7	112.33 (16)	C2ⁱ—C7—C2ⁱⁱ	105.82 (13)
C2—C3—C4	119.24 (18)	C2—C7—I1	112.92 (11)
C2—C3—H3	120.4	C2ⁱ—C7—I1	112.92 (11)
C4—C3—H3	120.4	C2ⁱⁱ—C7—I1	112.92 (11)
C5—C4—C3	120.87 (17)	C1ⁱ—C8—C1ⁱⁱ	105.46 (14)
C5—C4—H4	119.6	C1ⁱ—C8—C1	105.46 (14)
C3—C4—H4	119.6	C1ⁱⁱ—C8—C1	105.46 (14)
C4—C5—C6	120.22 (17)	C1ⁱ—C8—H8	113.2
C4—C5—H5	119.9	C1ⁱⁱ—C8—H8	113.2
C6—C5—H5	119.9	C1—C8—H8	113.2

C6—C1—C2—C3	1.2 (2)	C3—C2—C7—C2ⁱ	122.9 (2)
C8—C1—C2—C3	−178.53 (13)	C1—C2—C7—C2ⁱ	−56.63 (15)
C6—C1—C2—C7	−179.19 (13)	C3—C2—C7—C2ⁱⁱ	−125.1 (2)
C8—C1—C2—C7	1.07 (16)	C1—C2—C7—C2ⁱⁱ	55.38 (16)
C1—C2—C3—C4	−0.4 (2)	C3—C2—C7—I1	−1.06 (17)
C7—C2—C3—C4	−179.98 (14)	C1—C2—C7—I1	179.37 (9)
C2—C3—C4—C5	−0.6 (3)	C6—C1—C8—C1ⁱ	−124.7 (2)
C3—C4—C5—C6	0.9 (3)	C2—C1—C8—C1ⁱ	55.02 (16)
C2—C1—C6—C5	−0.9 (2)	C6—C1—C8—C1ⁱⁱ	124.0 (2)
C8—C1—C6—C5	178.79 (14)	C2—C1—C8—C1ⁱⁱ	−56.30 (16)
C4—C5—C6—C1	−0.1 (3)

Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₃I
M_r	380.20
Crystal system, space group	Hexagonal, R3
Temperature (K)	200
a, c (Å)	11.8820 (4), 17.6800 (5)
V (Å³)	2161.68 (12)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	2.21
Crystal size (mm)	0.56 × 0.51 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.568, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	4033, 1184, 1156
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.059, 1.15
No. of reflections	1184
No. of parameters	64
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.52, −0.51

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SIR97 (Altomare et al., 1999), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Dr Marc van der Vywer for helpful discussions.

References

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