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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3258.
Published online 2009 November 28. doi:  10.1107/S1600536809050776
PMCID: PMC2972006

2,5-Dichloro­thio­phene 1,1-dioxide

Abstract

The complete mol­ecule of the title compound, C4H2Cl2O2S, is generated by crystallographic twofold symmetry, with the S atom lying on the rotation axis. In the crystal, the molecules are linked by C—H(...)O hydrogen bonds..

Related literature

For a related thio­phene-1,1-dioxide structure, see: Douglas et al. (1993 [triangle]). For the synthetic utility and related applications of thio­phene-1,1-dioxides, see: Moiseev et al. (2006 [triangle]); Nakayama & Sugihara (1999 [triangle]); Shul’ts et al. (2003 [triangle]); Lou et al. (2002 [triangle]).

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Object name is e-65-o3258-scheme1.jpg

Experimental

Crystal data

  • C4H2Cl2O2S
  • M r = 185.02
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3258-efi1.jpg
  • a = 7.588 (2) Å
  • b = 10.584 (3) Å
  • c = 8.745 (3) Å
  • β = 90.275 (9)°
  • V = 702.4 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.14 mm−1
  • T = 296 K
  • 0.50 × 0.40 × 0.30 mm

Data collection

  • Bruker SMART X2S diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.590, T max = 0.726
  • 3352 measured reflections
  • 622 independent reflections
  • 549 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.094
  • S = 1.12
  • 622 reflections
  • 42 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.31 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050776/fl2274sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050776/fl2274Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the National Science Foundation for support of this work through the EPSCoR Research Infrastructure Improvement program (NSF 0432060) and the Center for High-rate Nanomanufacturing (NSF EEC-0425826).

supplementary crystallographic information

Comment

Thiophene 1,1-dioxides are important building blocks in modern organic synthesis and materials chemistry (Moiseev et al., 2006). In particular, thiophene 1,1-dioxides have been utilized as Diels-Alder dienes in the construction of larger molecules (Nakayama & Sugihara, 1999) including biologically active compounds (Shul'ts et al., 2003) and halogenated derivatives (Lou et al., 2002). The crystal structure for tetrachlorothiophene-1,1-dioxide has also been solved (Douglas et al., 1993).

Figure 1 shows the displacement ellipsoid diagram with appropriate atomic labels. Although there is only one unique H-bonding interaction in the crystal structure (Figure 2), each molecule is in fact linked to four others through symmetry related versions of this same H-bond (Table 1). Each sulfone oxygen (O1 and O1A) H-bonds to one hydrogen atom (i.e., O1 – H, 2.520 (2) Å; O1A – H, 2.520 (2) Å). Likewise, each hydrogen atom H-bonds to one sulfone oxygen atom. The sulfone groups do not interdigitate with the methines of an adjacent molecule.

Each unit cell contains two complete molecules. Looking down the a axis of the unit cell (Figure 3), the molecules in the crystal structure are arranged head to tail (with the sulfone end being the head) in horizontal rows, with alternating rows of inverted directionality (i.e., sulfone head groups pointing "right" in one row and pointing "left" in adjacent rows). Likewise, looking down the b axis of the unit cell (Figure 4), the molecules are arranged head to tail in vertical columns, with alternating columns of inverted directionality (i.e., sulfone head groups pointing "forward" in one column and pointing "backward" in adjacent columns). The inverted directionality between adjacent rows in Figure 3 and adjacent columns in Figure 4 is further illustrated upon looking down the c axis (Figure 5) where one observes molecular stacks with alternating up-down orientations of the sulfone head groups. This arrangement of molecules is driven by the 4:1 H-bonding network, as previously noted. However, relatively weak π-π stacking interactions also influence the arrangement of molecules, albeit to a lesser extent. Carbon atoms of closest contact in the molecular stacks are approximately 4.1 Å apart (Table 2) indicating weak π-π stacking interactions (the interlayer spacing in graphite is 3.4 Å) that can only be minimally responsible for the observed ordering of molecules.

Experimental

The title compound was prepared according to a related literature procedure (Lou et al., 2002) as illustrated in Figure 6. Thus, 2,5-dichlorothiophene was oxidized in 58% yield using a mixture of trifluoroacetic anhydride, hydrogen peroxide and sulfuric acid. The title compound was purified by silica gel column chromatography (30% dichloromethane - 70% hexane eluent). 1H NMR (400 MHz, CDCl3) δ 6.74 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 123.45 (CH), 131.08 (CCl). An X-ray grade crystal was obtained by slow evaporation of a dichloromethane-hexane solution.

Figures

Fig. 1.
The molecular structure showing the crystallographic labelling scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.
Fig. 2.
Perspective view of the title compound showing sets of identical H-bonds.
Fig. 3.
Perspective view of the title compound looking down the a axis of the unit cell.
Fig. 4.
Perspective view of the title compound looking down the b axis of the unit cell.
Fig. 5.
Perspective view of the title compound looking down the c axis of the unit cell.
Fig. 6.
Synthesis of the title compound, 2,5-dichlorothiophene-1,1-dioxide.

Crystal data

C4H2Cl2O2SF(000) = 368
Mr = 185.02Dx = 1.750 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1863 reflections
a = 7.588 (2) Åθ = 3.3–24.8°
b = 10.584 (3) ŵ = 1.14 mm1
c = 8.745 (3) ÅT = 296 K
β = 90.275 (9)°Block, colourless
V = 702.4 (3) Å30.50 × 0.40 × 0.30 mm
Z = 4

Data collection

Bruker SMART X2S diffractometer622 independent reflections
Radiation source: micro-focus sealed tube549 reflections with I > 2σ(I)
doubly curved silicon crystalRint = 0.028
ω scansθmax = 25.0°, θmin = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −9→8
Tmin = 0.590, Tmax = 0.726k = −12→12
3352 measured reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.0473P)2 + 0.6008P] where P = (Fo2 + 2Fc2)/3
622 reflections(Δ/σ)max = 0.013
42 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.31 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.32276 (10)0.08665 (9)0.07774 (10)0.0906 (4)
S10.00000.15554 (8)0.25000.0529 (3)
O1−0.0844 (3)0.2242 (2)0.1299 (2)0.0779 (6)
C10.1415 (3)0.0379 (3)0.1743 (3)0.0582 (6)
C20.0827 (4)−0.0754 (3)0.2059 (3)0.0677 (8)
H20.1398−0.14900.17570.081*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0634 (5)0.1157 (8)0.0932 (6)0.0154 (4)0.0365 (4)0.0078 (5)
S10.0513 (5)0.0506 (5)0.0570 (5)0.0000.0174 (4)0.000
O10.0812 (13)0.0728 (12)0.0799 (13)0.0258 (11)0.0188 (10)0.0181 (10)
C10.0518 (14)0.0674 (15)0.0553 (14)0.0134 (12)0.0115 (11)0.0005 (12)
C20.0788 (19)0.0587 (15)0.0657 (17)0.0167 (14)0.0042 (14)−0.0020 (13)

Geometric parameters (Å, °)

Cl1—C11.698 (3)S1—C1i1.774 (2)
S1—O1i1.427 (2)C1—C21.310 (4)
S1—O11.427 (2)C2—C2i1.476 (6)
S1—C11.774 (2)C2—H20.9300
O1i—S1—O1118.8 (2)C2—C1—Cl1131.4 (2)
O1i—S1—C1111.19 (13)C2—C1—S1110.9 (2)
O1—S1—C1110.68 (12)Cl1—C1—S1117.74 (16)
O1i—S1—C1i110.68 (12)C1—C2—C2i113.68 (16)
O1—S1—C1i111.19 (13)C1—C2—H2123.2
C1—S1—C1i90.87 (18)C2i—C2—H2123.2

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O1ii0.932.523.367 (4)152

Symmetry codes: (ii) x+1/2, y−1/2, z.

Table 2 π-π stacking interaction geometry (Å, °)

X···Yπ···π
C1···C24.137 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2274).

References

  • Bruker (2007). GIS, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Douglas, G., Frampton, C. S. & Muir, K. W. (1993). Acta Cryst. C49, 1197–1199.
  • Lou, Y., Chang, J., Jorgensen, J. & Lemal, D. M. (2002). J. Am. Chem. Soc. 124, 15302–15307. [PubMed]
  • Moiseev, A. M., Balenkova, E. S. & Nenajdenko, V. K. (2006). Russ. Chem. Rev. 75, 1015–1048.
  • Nakayama, J. & Sugihara, Y. (1999). Top. Curr. Chem. 205,131–195.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shul’ts, E. E., Vafina, G. V., Andreev, G. N. & &Tolstikov, G. A. (2003). Kislorod I Serusoderzhashchie Geterotsikly, 1, 478–487.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography