5,8-Bis(3-hy­droxy-3-methyl­but-1-yn-1-yl)-2,11-dithia­[3.3]paracyclo­phane

Di Wu; Jie Huang

doi:10.1107/S1600536811048446

. 2011 Nov 19;67(Pt 12):o3374. doi: 10.1107/S1600536811048446

5,8-Bis(3-hydroxy-3-methylbut-1-yn-1-yl)-2,11-dithia[3.3]paracyclophane

Di Wu ^a,^*, Jie Huang ^a

PMCID: PMC3239018 PMID: 22199866

Abstract

In the crystal structure of the title compound [systematic name: 2,2′-dimethyl-4,4′-(3,10-dithiatricyclo[10.2.2.2^5,8]octadeca-1(14),5,7,12,15,17-hexaen-6,17-diyl)dibut-3-yn-2-ol], C₂₆H₂₈O₂S₂, molecules are linked by O—H⋯O hydrogen bonds, forming a tubular chain which runs parallel to the b axis. The tubular structure is reinforced by π–π stacking interactions [centroid–centroid distance = 3.6332(16Å].

Related literature

For the preparation of the title compound, see: Jin & Lu (2010 ▶). For molecular building blocks associated with para-cyclophanes see: Xu et al. (2008 ▶).

Experimental

Crystal data

C₂₆H₂₈O₂S₂
M _r = 436.60
Monoclinic,
a = 17.1059 (5) Å
b = 11.8596 (4) Å
c = 24.5073 (10) Å
β = 108.113 (2)°
V = 4725.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.943, T _max = 0.976
14956 measured reflections
4646 independent reflections
2596 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.149
S = 0.92
4646 reflections
277 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811048446/go2035sup1.cif

e-67-o3374-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048446/go2035Isup2.hkl

e-67-o3374-Isup2.hkl^{(227.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811048446/go2035Isup3.cml

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—H1⋯O2ⁱ	0.82	1.99	2.777 (4)	161
O2—H2⋯O1ⁱⁱ	0.82	2.03	2.808 (3)	158

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors are grateful to Professor Sheng-Hua Liu for technical assistance with the structure analysis and Dr Xiang-Gao Meng for the data collection.

supplementary crystallographic information

Comment

The molecular building block associated with para-cyclophanes are widely used in chiral catalysis, the design of new optoelectronic (NLO) materials, electron transfer processes, and molecular electronics, polymer chemistry and materials science, and even organic solar cells.(Xu et al., 2008)

Up to now, the dithia[3.3]paracyclophane building blocks, which are synthetically more accessible, have received less attention. Here we report the crystal structure of the title compound (Fig. 1).

The molecules are linked into pairs by the O1-H1···.O2 hydrogen bond, Table 1. These pairs are then linked together by the O2-H2···O1, Table 1, and a symmetry related hydrogen bond to form a tube which runs parallel to the b-axis.

This tubular structure is re-inforced by π–π stacking between the phenyl ring containing C1 and its symmetry related ring in the molecule at (5/2+x,1/2-y,1/2+z), centroid to centroid distance, 3.6332(16Å, perpendicular 3.4658 (12)Å and a slippage of 1.0901Å.

Within the molecule the two phenyl rings have a centroid to centoid distance of 3.2621 (18)Å, an average perpendicular spacing of 3.2402Å with a slippage of 0.3773Å.

Experimental

To a stirred solution of appropriate 5,8-dibromo-2,11-dithia[3,3]paracyclophane and 2-methylbut-3-yn-2-ol (in the molecular ratio 1: 4) in THF, ⁱPr₂NH, Pd(PPh₃)₂Cl₂(10 mol%) and CuI(10 mol%) was added under N₂, the mixture was refluxed for 48 h. The cooled reaction mixture was filtered, diluted with CH₂Cl₂ and washed with water. The organic phase was dried with Na₂S0₄, filtered, and the solvent was removed from the filtrate in vacuo. The crude products were purified by column chromatography on silica gel to yield diols (Jin and Lu 2010).