2-(1,3-Dithian-2-yl)-1,3-dithiane-2-carbaldehyde

Hoong-Kun Fun; Reza Kia; Annada C Maity; Shyamaprosad Goswami

doi:10.1107/S1600536808042864

. 2008 Dec 20;65(Pt 1):o173. doi: 10.1107/S1600536808042864

2-(1,3-Dithian-2-yl)-1,3-dithiane-2-carbaldehyde

Hoong-Kun Fun ^a,^*, Reza Kia ^a, Annada C Maity ^b, Shyamaprosad Goswami ^b

PMCID: PMC2968084 PMID: 21581630

Abstract

The asymmetric unit of the title compound, C₉H₁₄OS₄, comprises two crystallographically independent molecules with similar conformations. In each molecule, an intramolecular C—H⋯O hydrogen bond generates a six-membered ring, producing an S(6) ring motif. All of the six-membered dithiacyclohexane rings adopt chair conformations. The crystal structure is stabilized by four intermolecular C—H⋯O and one C—H⋯S interaction.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For related literature, see: Goswami & Maity (2008 ▶); Rubin & Gleiter (2000 ▶); Wasserman & Parr (2004 ▶).

Experimental

Crystal data

C₉H₁₄OS₄
M _r = 266.44
Monoclinic,
a = 13.0028 (2) Å
b = 13.6790 (2) Å
c = 13.4244 (2) Å
β = 91.873 (1)°
V = 2386.46 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 100.0 (1) K
0.39 × 0.28 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.754, T _max = 0.871
68856 measured reflections
12473 independent reflections
9371 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.087
S = 1.07
12473 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.38 e Å⁻³

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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808042864/is2376sup1.cif

e-65-0o173-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042864/is2376Isup2.hkl

e-65-0o173-Isup2.hkl^{(609.8KB, 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
C2A—H2AB⋯O1Aⁱ	0.97	2.51	3.3530 (15)	146
C3A—H3AB⋯O1A	0.97	2.48	3.1024 (16)	122
C6A—H6AB⋯O1Bⁱⁱ	0.97	2.51	3.4292 (15)	159
C1B—H1BA⋯O1B	0.97	2.44	3.0508 (16)	121
C2B—H2BA⋯O1Bⁱⁱⁱ	0.97	2.54	3.1913 (16)	124
C3B—H3BA⋯S2A^iv	0.97	2.81	3.5932 (12)	138
C7B—H7BA⋯O1A^v	0.97	2.54	3.3436 (17)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

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

supplementary crystallographic information

Comment

Vicinal tricarbonyl compounds are powerful electrophiles with widespread applications in organic synthesis (Rubin & Gleiter, 2000; Wasserman & Parr, 2004). They act as useful precursors to synthesis of elaborate heterocylic compounds and numerous novel biologically important substances such as FK-506, rapamycin and related immunosuppressants. They are also used to develop protease inhibitors derived from peptide carboxylic acids. Thioacetalization of carbonyl compounds (Goswami & Maity, 2008) plays an important role in organic synthesis. Dithioacetals have become widely used tools for C—C bond formation. Here we reported the first synthesis of 2,2'-bis(1,3-dithianyl)-2-carbaldehyde from the smallest vicinal tricarbonyl compound, 2-oxo-1,3-propandial.

In the title compound (I), Fig. 1, intramolecular C—H···O hydrogen bonds (Table 1) generate six-membered rings, producing S(6) ring motifs (Bernstein et al., 1995). The S1A/C1A–C3A/S2A/C4A, S3A/C5A/S4A/C8A/C7A/C6A, S1B/C1B–C3B/S2B/C4B, and S3B/C5B/S4B/C8B/C7B/C6B rings adopt chair conformations with the ring puckering parameters (Cremer & Pople, 1975) of Q = 0.6979 (10) Å, Θ = 5.43 (8)°, Φ = 3.4 (9)°; Q = 0.7467 (10) Å, Θ = 171.28 (8)°, Φ = 246.6 (5)°; Q = 0.6967 (11) Å, Θ = 7.22 (9)°, Φ = 247.2 (7)°; Q = 0.7475 (11) Å, Θ = 170.82 (9)°, Φ = 248.2 (5)°, respectively. The crystal structure is stabilized by intermolecular C—H···O (× 4) and C—H···S interactions (Fig. 2).

Experimental

To a stirred solution of 2-oxo-1,3-propandial (250 mg, 0.34 mmol) and boron trifluoride etherate (0.5 mL) in dichloromethane (50 mL) cooled at 0 °C is added propane dithiol (450 mg, 4.1 mmol) dropwise over 15 min with stirring. The mixture is stirred at room temperature for 3h. 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 20% ethyl acetate in petroleum ether as eluant to afford 2,2'-bis(1,3-dithianyl)-2-carbaldehyde (247 mg, 32%) as a colorless crystalline solid along with other thiane derivatives.