Crystal structure of 5-(1,3-di­thian-2-yl)-2H-1,3-benzodioxole

Julio Zukerman-Schpector; Ignez Caracelli; Hélio A Stefani; Olga Gozhina; Edward R T Tiekink

doi:10.1107/S2056989015002455

. 2015 Feb 13;71(Pt 3):o167–o168. doi: 10.1107/S2056989015002455

Crystal structure of 5-(1,3-dithian-2-yl)-2H-1,3-benzodioxole

Julio Zukerman-Schpector ^a,^*, Ignez Caracelli ^b, Hélio A Stefani ^c, Olga Gozhina ^c, Edward R T Tiekink ^d

PMCID: PMC4350690 PMID: 25844230

Abstract

In the title compound, C₁₁H₁₂O₂S₂, two independent but virtually superimposable molecules, A and B, comprise the asymmetric unit. In each molecule, the 1,3-dithiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the plane through the remaining four atoms. The substituted benzene ring occupies an equatorial position in each case and forms dihedral angles of 85.62 (9) (molecule A) and 85.69 (8)° (molecule B) with the least-squares plane through the 1,3-dithiane ring. The difference between the molecules rests in the conformation of the five-membered 1,3-dioxole ring which is an envelope in molecule A (the methylene C atom is the flap) and almost planar in molecule B (r.m.s. deviation = 0.046 Å). In the crystal, molecules of A self-associate into supramolecular zigzag chains (generated by glide symmetry along the c axis) via methylene C—H⋯π interactions. Molecules of B form similar chains. The chains pack with no specific directional intermolecular interactions between them.

Keywords: crystal structure; 1,3-dithiane; conformation; 1,3-benzodioxole; C—H⋯π interactions

Related literature

The title compound has been prepared previously, see: Ballesteros et al. (2005 ▸). For the structure of a related compound containing the same molecular skeleton as in the title compound, i.e. (19R,21R,25S)-(−)-2-(2-menthyloxycarbonyl-3,4-methylenedioxyphenyl)1,3-dithiane, see: Ratajczak-Sitarz et al. (1996 ▸). graphic file with name e-71-0o167-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₂O₂S₂
M _r = 240.33
Monoclinic,
a = 11.4765 (3) Å
b = 17.5504 (4) Å
c = 11.6397 (2) Å
β = 104.275 (1)°
V = 2272.05 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 296 K
0.59 × 0.40 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T _min = 0.702, T _max = 0.745
14839 measured reflections
4164 independent reflections
3759 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.092
S = 1.03
4164 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2014 (Burla et al., 2015 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸), QMOL (Gans & Shalloway, 2001 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002455/hb7361sup1.cif

e-71-0o167-sup1.cif^{(457.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002455/hb7361Isup2.hkl

e-71-0o167-Isup2.hkl^{(228.4KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015002455/hb7361Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015002455/hb7361fig1.tif

The molecular structures of the two independent molecules in title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.

Click here for additional data file.^{(2.5MB, tif)}

A B . DOI: 10.1107/S2056989015002455/hb7361fig2.tif

Superimposition of the two independent molecules. Molecule A is shown in red and B in blue. The molecules have been superimposed such that the benzene rings are overlapped.

Click here for additional data file.^{(1.1MB, tif)}

A c . DOI: 10.1107/S2056989015002455/hb7361fig3.tif

A view of the zigzag supramolecular chain comprising molecules of A along the c axis (glide symmetry) mediated by C—H⋯π interactions are shown as purple dashed lines.

Click here for additional data file.^{(2.2MB, tif)}

c . DOI: 10.1107/S2056989015002455/hb7361fig4.tif

A view in projection down the c axis of the unit-cell contents. The C—H⋯π interactions are shown as purple dashed lines.

CCDC reference: 1047484

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the C5C11 and C16C21 rings, respectively.

DHA	DH	HA	D A	DHA
C4H4bCg1ⁱ	0.97	2.77	3.731(2)	170
C13H13aCg2ⁱⁱ	0.97	2.54	3.4841(19)	165

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

Acknowledgments

We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013-2 to JZS, 306121/2013-2 to IC and 308320/2010-7 to HAS), FAPESP (2012/00424-2 and 2013/21925-2) and CAPES are acknowledged for financial support.

supplementary crystallographic information

S1. Experimental

A solution of the corresponding 2H-1,3-benzodioxole-5-carbaldehyde (0.037 mol, 1 equiv.) in chloroform (20 ml) was combined with an equimolar amount of propane-1,3-dithiol (3.7 ml, 0.037 mol) at room temperature. The solution was stirred for 1 h at this temperature, then cooled to -20 °C after which BF₃ etherate (0.46 ml, 0.0037 mol, 0.1 equiv.) was added drop-wise. The reaction solution was allowed to warm to room temperature and stirred overnight. After this time, the solution was washed three times each with water, 10% aqueous KOH, then water followed by drying over MgSO₄. Evaporation of the solvent furnishes a pure product as colourless crystals in 97% yield. To obtain crystals suitable for X-ray analysis, the product was crystallized from CH₃OH. The spectroscopic data matched those reported in the literature (Ballesteros et al., 2005).