2-(Pyrene-1-yl)-1,3-dithiane

Hoong-Kun Fun; Samuel Robinson Jebas; Annada C Maity; Nirmal K Das; Shyamaprasad Goswami

doi:10.1107/S1600536809010320

. 2009 Mar 28;65(Pt 4):o891. doi: 10.1107/S1600536809010320

2-(Pyrene-1-yl)-1,3-dithiane

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, Annada C Maity ^b, Nirmal K Das ^b, Shyamaprasad Goswami ^b

PMCID: PMC2969099 PMID: 21582599

Abstract

In the title compound, C₂₀H₁₆S₂, the pyrene ring is planar [maximum deviation 0.0144 (15) Å] and the dithiane ring adopts a chair conformation. The crystal packing is stabilized by C—H⋯π interactions. An intramolecular C—H⋯S hydrogen bond generates an S(5) ring motif.

Related literature

For thionation reactions, see: Goswami & Maity (2008 ▶); Goswami et al. (2009 ▶); Fun et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₀H₁₆S₂
M _r = 320.45
Orthorhombic,
a = 7.1424 (1) Å
b = 8.6016 (1) Å
c = 24.5049 (2) Å
V = 1505.48 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.36 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.885, T _max = 0.962
29712 measured reflections
6424 independent reflections
5501 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.092
S = 1.05
6424 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ▶), 2662 Friedel pairs
Flack parameter: 0.03 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809010320/at2745sup1.cif

e-65-0o891-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010320/at2745Isup2.hkl

e-65-0o891-Isup2.hkl^{(180.7KB, 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
C15—H15A⋯S2	0.93	2.65	3.0416 (13)	106
C9—H9A⋯Cg1ⁱ	0.93	2.68	3.4196 (15)	137
C4—H4A⋯Cg2ⁱⁱ	0.93	2.98	3.8073 (16)	149
C20—H20A⋯Cg3ⁱⁱⁱ	0.97	2.78	3.5339 (15)	135

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 ring, Cg2 is the centroid of the C1/C6–C10 ring and Cg3 is the centroid of the C2/C3/C13–C16 ring.

Acknowledgments

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. ACM, NKD and SG thank the DST [SR/S1/OC-13/2005], Government of India, for financial support. ACM and NKD thank the UGC, Government of India, for awarding them each a fellowship.

supplementary crystallographic information

Comment

Thioacetal protection of carbonyl groups is of paramount importance in synthetic organic chemistry and hence the development of novel thionation reactions remains of great interest (Goswami & Maity, 2008; Fun et al., 2009; Goswami et al., 2009). In addition, thioacetals are also utilized as masked acyl anions or masked methylene functions in carbon-carbon bond forming reactions. Here we report the synthesis of 2-pyrene-1-yl-[1,3]dithiane from pyrene-1-aldehyde using BF₃—Et₂O as catalyst and its crystal structure.

The asymmetric unit of (I), (Fig. 1), consists of one molecule of the title compound. The bond lengths (Allen et al., 1987) and bond angles are found to have normal values. The pyrene ring is essentially planar with the maximum deviation from planarity being 0.0144 (15)Å for atom C15. The dithiane group adopts a chair conformation with the puckering parameters Q = 0.7477 (12) Å, θ = 9.61 (10)° and φ = 66.3 (5)° (Cremer & Pople, 1975).

The crystal packing is stabilized by C—H···π interactions (Table 1). An intramolecular C—H···S hydrogen bonding generates an S(5) ring motif (Bernstein et al., 1995).

Experimental

To a stirred solution of pyrene-1-aldehyde (500 mg., 2.17 mmol) and boron trifluoride etherate (0.5 ml) in dichloromethane (50 ml) cooled at 273 K is added 1,3-propanedithiol (490 mg, 4.5 mmol) dropwise over 15 min with stirring. The mixture is stirred at room temperature for 3 h. The progress of the reaction is monitored by TLC. After completion of the reaction, NaHCO₃ solution is added slowly and carefully to neutralize the mixture at room temperature which is then extracted with dichloromethane. The organic layer is dried (anhydrous Na₂SO₄) and then the solvent is removed under reduced pressure. The crude product was purified by column chromatography using silica gel with 10% ethyl acetate in pet ether as eluant to afford 2-pyrene-1-yl-[1,3]dithiane (620 mg, 89%) as a colourless crystalline solid along with other thiane derivatives.