2,5-Dichloro­thio­phene 1,1-dioxide

Briggs, J.B.; Jia, W.; Jazdzyk, M.D.; Miller, G.P.

doi:10.1107/S1600536809050776

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3258

doi:10.1107/S1600536809050776

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2,5-Dichlorothiophene 1,1-dioxide

Jonathan B. Briggs,^a Wenling Jia,^a Mikaël D. Jazdzyk ^a and Glen P. Miller ^a ^*

^aDepartment of Chemistry and Materials Science Program, University of New Hampshire, Durham, NH 03824-3598, USA
^*Correspondence e-mail: glen.miller@unh.edu

(Received 28 September 2009; accepted 25 November 2009; online 28 November 2009)

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 ). For the synthetic utility and related applications of thiophene-1,1-dioxides, see: Moiseev et al. (2006 ); Nakayama & Sugihara (1999 ); Shul'ts et al. (2003 ); Lou et al. (2002 ).

Experimental

Crystal data

C₄H₂Cl₂O₂S
M_r = 185.02
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.12
622 reflections
42 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.52	3.367 (4)	152
Symmetry code: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

2,5-Dichlorothiophene 1,1-dioxide top

Crystal data top

C₄H₂Cl₂O₂S	F(000) = 368
M_r = 185.02	D_x = 1.750 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1863 reflections
a = 7.588 (2) Å	θ = 3.3–24.8°
b = 10.584 (3) Å	µ = 1.14 mm⁻¹
c = 8.745 (3) Å	T = 296 K
β = 90.275 (9)°	Block, colourless
V = 702.4 (3) Å³	0.50 × 0.40 × 0.30 mm
Z = 4

Data collection top

Bruker SMART X2S diffractometer	622 independent reflections
Radiation source: micro-focus sealed tube	549 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	R_int = 0.028
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→8
T_min = 0.590, T_max = 0.726	k = −12→12
3352 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0473P)² + 0.6008P] where P = (F_o² + 2F_c²)/3
622 reflections	(Δ/σ)_max = 0.013
42 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₄H₂Cl₂O₂S	V = 702.4 (3) Å³
M_r = 185.02	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.588 (2) Å	µ = 1.14 mm⁻¹
b = 10.584 (3) Å	T = 296 K
c = 8.745 (3) Å	0.50 × 0.40 × 0.30 mm
β = 90.275 (9)°

Data collection top

Bruker SMART X2S diffractometer	622 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	549 reflections with I > 2σ(I)
T_min = 0.590, T_max = 0.726	R_int = 0.028
3352 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.12	Δρ_max = 0.21 e Å⁻³
622 reflections	Δρ_min = −0.31 e Å⁻³
42 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.32276 (10)	0.08665 (9)	0.07774 (10)	0.0906 (4)
S1	0.0000	0.15554 (8)	0.2500	0.0529 (3)
O1	−0.0844 (3)	0.2242 (2)	0.1299 (2)	0.0779 (6)
C1	0.1415 (3)	0.0379 (3)	0.1743 (3)	0.0582 (6)
C2	0.0827 (4)	−0.0754 (3)	0.2059 (3)	0.0677 (8)
H2	0.1398	−0.1490	0.1757	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0634 (5)	0.1157 (8)	0.0932 (6)	0.0154 (4)	0.0365 (4)	0.0078 (5)
S1	0.0513 (5)	0.0506 (5)	0.0570 (5)	0.000	0.0174 (4)	0.000
O1	0.0812 (13)	0.0728 (12)	0.0799 (13)	0.0258 (11)	0.0188 (10)	0.0181 (10)
C1	0.0518 (14)	0.0674 (15)	0.0553 (14)	0.0134 (12)	0.0115 (11)	0.0005 (12)
C2	0.0788 (19)	0.0587 (15)	0.0657 (17)	0.0167 (14)	0.0042 (14)	−0.0020 (13)

Geometric parameters (Å, º) top

Cl1—C1	1.698 (3)	S1—C1ⁱ	1.774 (2)
S1—O1ⁱ	1.427 (2)	C1—C2	1.310 (4)
S1—O1	1.427 (2)	C2—C2ⁱ	1.476 (6)
S1—C1	1.774 (2)	C2—H2	0.9300

O1ⁱ—S1—O1	118.8 (2)	C2—C1—Cl1	131.4 (2)
O1ⁱ—S1—C1	111.19 (13)	C2—C1—S1	110.9 (2)
O1—S1—C1	110.68 (12)	Cl1—C1—S1	117.74 (16)
O1ⁱ—S1—C1ⁱ	110.68 (12)	C1—C2—C2ⁱ	113.68 (16)
O1—S1—C1ⁱ	111.19 (13)	C1—C2—H2	123.2
C1—S1—C1ⁱ	90.87 (18)	C2ⁱ—C2—H2	123.2

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱⁱ	0.93	2.52	3.367 (4)	152

Symmetry code: (ii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₄H₂Cl₂O₂S
M_r	185.02
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	7.588 (2), 10.584 (3), 8.745 (3)
β (°)	90.275 (9)
V (Å³)	702.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.50 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART X2S diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.590, 0.726
No. of measured, independent and observed [I > 2σ(I)] reflections	3352, 622, 549
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.12
No. of reflections	622
No. of parameters	42
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.31

Computer programs: GIS (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.52	3.367 (4)	152

Symmetry code: (i) x+1/2, y−1/2, z.

π-π stacking interaction geometry (Å, °) top

X···Y	π···π
C1···C2	4.137 (4)

Acknowledgements

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).

References

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