7-Nitro-1,2,3,4-tetra­hydro­naphthalene-1-spiro-2′-(1,3-dithiane)

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

doi:10.1107/S1600536809001536

. 2009 Jan 17;65(Pt 2):o347. doi: 10.1107/S1600536809001536

7-Nitro-1,2,3,4-tetrahydronaphthalene-1-spiro-2′-(1,3-dithiane)

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

PMCID: PMC2968322 PMID: 21581948

Abstract

In the title compound, C₁₃H₁₅NO₂S₂, the nitro group is coplanar with the benzene ring to which it is attached, forming a dihedral angle of 1.07 (14)°. The dithiane ring adopts a chair conformation. In the crystal structure, molecules are linked through C—H⋯O and C—H⋯π [C⋯Cg = 3.7164 (15) Å] interactions. The crystal studied was an inversion twin with an 0.134 (5):0.866 (5) domain ratio.

Related literature

For the calculation of ring puckering parameters, see: Cremer & Pople (1975 ▶). For related literature including applications, see: Goswami & Maity (2008 ▶); Fun et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₅NO₂S₂
M _r = 281.38
Orthorhombic,
a = 12.8673 (1) Å
b = 42.2330 (6) Å
c = 9.1819 (1) Å
V = 4989.67 (10) Å³
Z = 16
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 100.0 (1) K
0.41 × 0.30 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.849, T _max = 0.977
54206 measured reflections
6726 independent reflections
5979 reflections with I > 2σ(I)
R _int = 0.067

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.077
S = 1.06
6726 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), 3202 Friedel pairs
Flack parameter: 0.13 (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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001536/tk2351sup1.cif

e-65-0o347-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001536/tk2351Isup2.hkl

e-65-0o347-Isup2.hkl^{(329.5KB, 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—H13A⋯O1ⁱ	0.97	2.58	3.4565 (18)	151
C7—H7A⋯Cg1ⁱⁱ	0.93	2.82	3.7164 (15)	162

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C5–C10 benzene ring.

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the 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. ACM thanks the UGC, Government of India, for a fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant (No. 1001/PFIZIK/811012).

supplementary crystallographic information

Comment

The protection of carbonyl groups to produce dithioketals is now commonly used as an important synthetic technique in the preparation of many organic compounds, including multi-functional complex molecules (Goswami & Maity 2008; Fun et al., 2009). Herein, we report the synthesis of the title compound, (I), from 5-nitro-3,4-dihydro-2H-naphthalen-1-one using boron trifluoride etherate as the catalyst.

In (I), Fig. 1, the nitro group is co-planar with the benzene ring, forming a dihedral angle of 1.07 (14)°. The thiacyclohexane ring adopts a chair conformation with ring puckering parameters of Q = 0.7198 (11) Å, Θ = 8.49 (10)°, and Φ = 79.6 (6)° (Cremer & Pople, 1975). The crystal structure is stabilized by intermolecular C—H···π interactions (Cg1 is the centroid of the C5–C10 benzene ring), see Table 1. Further, neighbouring molecules are linked through C—H···O interactions along the c axis, Fig. 2.

Experimental

A stirred dichloromethane (50 mL) solution of 5-nitro-3,4-dihydro-2H-naphthalen-1-one (500 mg, 2.61 mmol) and boron trifluoride etherate (0.5 mL) in was cooled to 273 K. To this 1,3-propanedithiol (450 mg, 4.1 mmol) was added dropwise over 15 min. The mixture was stirred at room temperature for 3 h and the progress of the reaction was monitored by TLC. After completion of the reaction, NaHCO₃ solution was added carefully to neutralize the mixture at room temperature. This was then extracted with dichloromethane. The organic layer was dried (anhydrous Na₂SO₄) and the solvent removed under reduced pressure. The crude product was purified by column chromatography using silica gel with 10 % ethyl acetate in petroleum ether as eluant to afford (I) (670 mg, 92 %) as a colourless crystalline solid along with other thiane derivatives.