syn-5,10,15-Tris(dichloro­meth­yl)-5,10,15-trihy­droxy-5H-diindeno­[1,2-a:1′,2′-c]fluorene dichloro­methane 0.82-solvate

Gregory W Morrison; Frank R Fronczek; Steven F Watkins

doi:10.1107/S1600536812020703

. 2012 May 16;68(Pt 6):o1755–o1756. doi: 10.1107/S1600536812020703

syn-5,10,15-Tris(dichloromethyl)-5,10,15-trihydroxy-5H-diindeno[1,2-a:1′,2′-c]fluorene dichloromethane 0.82-solvate

Gregory W Morrison ^a, Frank R Fronczek ^a,^*, Steven F Watkins ^a

PMCID: PMC3379341 PMID: 22719539

Abstract

The title compound, C₃₀H₁₈Cl₆O₃·0.82CH₂Cl₂, consists of a slightly cup-shaped seven-ring truxene nucleus with hydroxy and dichloromethyl substituents at stereocenters 5R/S, 10R/S and 15R/S. C—Cl distances are in the range 1.759 (4)–1.783 (3) Å. Solvent channels parallel to the b axis appear to be partially occupied by highly disordered dichloromethane solvent molecules, the contribution of which were removed from the refinement with the SQUEEZE procedure in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155]. Only one of the OH groups forms a hydrogen bond, which is intermolecular to another OH group, forming centrosymmetric dimers in the crystal.

Related literature

For further details of the synthesis and information on the synthesis of buckybowls, see: Abdourazak et al. (1995 ▶). For applications of truxenes, see: Diring & Ziessel (2009 ▶). Similar structures have been reported by De Frutos et al. (1999 ▶); Amsharov & Jansen (2007 ▶) and Menard et al. (2011 ▶). graphic file with name e-68-o1755-scheme1.jpg

Experimental

Crystal data

C₃₀H₁₈Cl₆O₃·0.82CH₂Cl₂
M _r = 708.78
Triclinic,
a = 10.9719 (4) Å
b = 11.6186 (3) Å
c = 14.0431 (5) Å
α = 71.009 (2)°
β = 85.291 (2)°
γ = 68.798 (2)°
V = 1576.88 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 90 K
0.38 × 0.13 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.814, T _max = 0.972
10851 measured reflections
5744 independent reflections
3608 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.156
S = 0.97
5744 reflections
356 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: COLLECT (Bruker, 2004 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812020703/kj2201sup1.cif

e-68-o1755-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020703/kj2201Isup2.hkl

e-68-o1755-Isup2.hkl^{(331.6KB, 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
O1—H91⋯O3ⁱ	0.84	2.04	2.834 (3)	158

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Symmetry code: (i) Inline graphic .

Acknowledgments

The purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. We thank A. H. Abdourazak and P. W. Rabideau for providing the sample.

supplementary crystallographic information

Comment

The nucleus of the title compound is truxene (C₂₇H₁₈, CAS: 548–35-6), a nearly planar seven-ring aromatic molecule. Compounds containing this ring system have been previously investigated for use in liquid crystal devices, chiral recognition systems, and fluorescent probes (Diring & Ziessel, 2009). The title compound was synthesized as an intermediate material in the formation of buckybowls (half-buckminsterfullerenes, Abdourazak et al., 1995). Two isomers were separated by chromatography, and the yellow component is herein shown to be the syn isomer, with all three OH groups on the same side of the truxene nucleus. The molecule has a slightly cupped shape, with three hydroxy groups oriented toward the inside of the cup and three dichloromethyl groups on the outside of the cup. Relative to the mean plane of the central 6-ring (which is a slightly puckered crown, δ(r.m.s.) = 0.01 (1) Å), the three pairs of carbon atoms on the outer rim of the molecule average 0.36 (1) (C4, C5), 0.15 (1) (C13, C14) and 0.07 (1) (C22, C23) Å above the plane. Of the three OH groups available for hydrogen bond formation, only O1 forms a hydrogen bond, to OH group O3 at 2 - x, 1 - y, 1 - z, thus there are centrosymmetric dimers about 1, 1/2, 1/2, as shown in Fig. 2. A solvent channel with a unit cell volume of 330 Å³, parallel to the b axis and centered at 1/2a, displays residual electron density which presumably represents remnants of disordered solvent molecules most of which have evaporated from the crystal since the original synthesis. Procedure SQUEEZE, as implemented in PLATON (Spek, 2009), subtracted 69 electrons from the observed structure amplitudes as an approximate solvent contribution.

Experimental

A solution of lithium dicyclohexylamine was prepared by adding 93 mmol dicyclohexeylamine and 93 mmol n-butyllithium to 75 ml of dried tetrahydrofuran (THF). This solution was added dropwise over one hour to a suspension of 7.3 mmol truxenone in 100 ml of THF and 6 ml of dichloromethane (DCM) at 273 K. The solution was stirred for one hour and then quenched with aqueous ammonium chloride. The THF was removed under reduced pressure and the remaining mixture was extracted with DCM. The resulting organic layer was washed with aqueous citric acid, dried and evaporated. Flash chromatography (silica gel, DCM) was used to isolate 5,10,15-tris(dichloromethyl)-5,10,15-trihydroxy-5H-Diindeno[1,2 - a:1',2'-c] fluorene and further chromatography (silica gel, DCM-hexane 3:1) was used to separate the compound into two components. The syn- component reported here crystallized from DCM as yellow blades.