4,10-Diall­yloxy-1,2,3,6b,7,8,9,12b-octa­hydro­perylene

Terrill D Smith; Mathew P D Mahindaratne; Mark A Penick; George R Negrete; Lee M Daniels; Edward R T Tiekink

doi:10.1107/S160053680905243X

. 2009 Dec 9;66(Pt 1):o96. doi: 10.1107/S160053680905243X

4,10-Diallyloxy-1,2,3,6b,7,8,9,12b-octahydroperylene

Terrill D Smith ^a, Mathew P D Mahindaratne ^a, Mark A Penick ^a, George R Negrete ^a,^‡, Lee M Daniels ^b, Edward R T Tiekink ^c,^*

PMCID: PMC2980038 PMID: 21580191

Abstract

In the title compound, C₂₆H₂₈O₂, the central atoms are coplanar, with the –CH₂—CH₂– links of the cyclohexene groups lying to either side of the plane and with the diallyloxy residues twisted out of this plane [C—C—O—C torsion angles = 16.6 (3) and −13.9 (3)°]. In the crystal structure, molecules are connected into chains propagating in [100] via C—H⋯π interactions.

Related literature

For the preparation of oxygenated perylenes and their use as photosensitizing organic dyes in solar harvesting techniques, see: Penick et al. (2008 ▶).

Experimental

Crystal data

C₂₆H₂₈O₂
M _r = 372.48
Monoclinic,
a = 4.5883 (1) Å
b = 14.9171 (3) Å
c = 13.9203 (3) Å
β = 95.153 (1)°
V = 948.92 (3) Å³
Z = 2
Cu Kα radiation
μ = 0.63 mm⁻¹
T = 100 K
0.50 × 0.19 × 0.11 mm

Data collection

Rigaku RAXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.745, T _max = 0.935
8967 measured reflections
3243 independent reflections
2616 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.104
S = 1.26
3243 reflections
254 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: PROCESS-AUTO (Rigaku, 1998 ▶); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680905243X/hb5266sup1.cif

e-66-00o96-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905243X/hb5266Isup2.hkl

e-66-00o96-Isup2.hkl^{(155.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯Cg1ⁱ	1.00	2.78	3.671 (3)	148
C20—H20⋯Cg4ⁱⁱ	1.00	2.82	3.702 (3)	148

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 and Cg4 are the centroids of the C4–C9 and C14–C19 rings, respectively.

Acknowledgments

This research was supported by a grant to GRN from the UTSA Collaborative Research Seed Grant Program (CRSGP).

supplementary crystallographic information

Comment

Our laboratory has been investigating the preparation of oxygenated perylenes and their use as photosensitizing organic dyes in solar harvesting techniques (Penick et al., 2008). The commercially available starting material 1,2,3,4-tetrahydronaphthalen-1,5-diol (1), Fig. 1, was allylated selectively at the phenolic-OH using equimolar amounts of allyl bromide and K₂CO₃ in refluxing acetone. The resulting 5-allyloxy-1,2,3,4-tetrahydronaphthalen-1-ol (2), Fig. 2, was subjected to tandem Friedel-Crafts annulation (Penick et al., 2008) in acetonitrile at room temperature using BF₃ as the Lewis acid catalyst. The product (3), Fig. 1, precipitated and was purified by trituration with acetone to produce a white solid. Product 3 was crystallized using a slow evaporation method from chloroform to obtain single crystals for spectroscopic and X-ray crystallographic analysis.

The molecular structure of the title compound, Fig. 2, features an essentially planar core. Thus, the maximum deviations from the least-squares plane through the benzene rings (atoms C4–C9 and C14–C19) as well as the sp³ O1, O2, C10, C13, C20, and C23 atoms are 0.0509 (23) Å for atom C10 and -0.0389 (21) Å for atom C8 (r.m.s. = 0.0242 Å). The C11 and C12, and C21 and C22 atoms of the cyclohexene rings lie to either side of this plane. The planarity in the molecule does not extend to the terminal diallyloxy residues as seen in the magnitudes of the C5–C4–O1–O3 and C16–C17–O2–C24 torsion angles of 16.6 (3) and -13.9 (3) °, respectively.

The most prominent feature of the crystal packing is the presence of C–H···π interactions that link molecules into supramolecular chains along [1 0 0], Fig. 3. The geometric parameters associated with these interactions are C13–H13···Cg(C4–C9)ⁱ = 2.78 Å, C13···Cg(C4–C9)ⁱ = 3.671 (3) Å with an angle of 148° at H13 for symmetry operation i: -1 + x, y, z; and C20–H20···Cg(C14–C19)ⁱⁱ = 2.82 Å, C20···Cg(C14–C19)ⁱⁱ = 3.702 (3) Å with an angle of 148° at H20 for ii: 1 + x, y, z. Supramolecular chains are consolidated in the crystal structure by hydrophobic interactions, Fig. 4.

Experimental

Referring to Fig. 1, diol 1 was converted to allyl aryl ether 2via conventional phenolic alkylation (allyl bromide/K₂CO₃/acetone). Octahydroperylene 3 was prepared upon treatment of allyl aryl ether 2 (173 mg, 0.85 mmol) in acetonitrile (5 ml) with BF₃.Et₂O (0.5 ml) by dropwise addition over one minute and the mixture was stirred for 43 h at room temperature. An off-white solid was collected by filtration, triturated with acetone, and dried under vacuum. The solid was crystallized by slowly evaporating its CHCl₃ solution to yield off-white small rods (84 mg, 53%), M. pt. = 458–461 K; ¹H NMR (CDCl₃, 500 MHz): δ 1.51 (tt, J = 12.2, 8.3 Hz, 2H), 1.69–1.79 (m, 2H), 2.00–2.10 (m, 2H), 2.53 (dt, J = 16.1, 7.8 Hz, 2H), 2.51–2.58 (m, 2H), 3.15 (ddd, J = 16.1, 6.8, 5.4 Hz, 2H), 3.73 (dd, J = 11.7, 4.4 Hz, 2H), 4.51–4.59 (m, two ABX patterns, 4H), 5.27 (dq, J = 10.8, 1.5 Hz, 2H), 5.44 (dq, J = 17.1, 1.5 Hz, 2H), 6.95 (ddt, J = 17.1, 10.8, 5.4 Hz, 2H), 6.82 (d, J = 7.8 Hz, 2H), 7.23 (d, J = 8.3 Hz, 2H) p.p.m. ¹³C NMR (CDCl₃, 125 MHz): δ 20.9 (t), 21.19 (t), 29.89 (t), 36.09 (d), 69.29 (t), 110.1 (d), 116.9 (dd), 124.5 (d), 126.7 (s), 128.2 (s), 133.9 (d), 136.9 (s), 153.5 (s) p.p.m. IR (ν_max, cm^-1): 2933, 2913, 2857, 1486, 1464, 1420, 1258, 1071, 1033, 997. 924, 797. MS (APCI, m/z): 373.4 (52, M⁺+1), 372.4 (34, M⁺), 371.4 (100, M⁺-1), 330.4 (33, M⁺-C₃H₆).