2-Chloro­methyl-2,3-dihydro­thieno[3,4-b][1,4]dioxine

Xu, J.; Xu, H.; Quan, J.; Sha, F.; Yao, C.

doi:10.1107/S1600536809007156

organic compounds

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Volume 65| Part 4| April 2009| Page o668

doi:10.1107/S1600536809007156

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2-Chloromethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine

Jian Xu,^a Hao Xu,^a Ji-cai Quan,^a Fei Sha ^a and Cheng Yao ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: yaocheng@njut.edu.cn

(Received 24 February 2009; accepted 26 February 2009; online 6 March 2009)

In the molecule of the title compound, C₇H₇ClO₂S, the six-membered ring adopts a twisted conformation. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules. There is also a weak C—H⋯π interaction.

Related literature

For a related structure, see: Jose et al. (2005 ). For bond-length data, see: Allen et al. (1987 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₇H₇ClO₂S
M_r = 190.64
Monoclinic, P 2₁ /n
a = 10.227 (2) Å
b = 5.7500 (12) Å
c = 14.376 (3) Å
β = 105.55 (3)°
V = 814.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.825, T_max = 0.936
1565 measured reflections
1479 independent reflections
1065 reflections with I > 2σ(I)
R_int = 0.067
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.185
S = 1.01
1479 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.98	2.45	3.317 (5)	146
C1—H1B⋯Cg1ⁱⁱ	0.97	2.75	3.708 (5)	168
Symmetry codes: (i) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z. Cg1 is the centroid of the S/C4–C7 ring.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007156/hk2630sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007156/hk2630Isup2.hkl

checkCIF report

Comment top

A great deal of interest has been devoted in recent years to the synthesis and investigation of functionalized 3,4-ethylenedioxythiophene (EDOT) systems because of their potential as active materials in applications such as light-emitting diodes (OLEDs), plastic lasers, field-effect transistors and photovoltaic devices (Jose et al., 2005). The title compound is an important intermediate in the synthesis of functionalized 3,4-ethylenedioxy- thiophene (EDOT) systems, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring B (S/C4-C7) is, of course, planar. Ring A (O1/O2/C2-C5) is not planar, having total puckering amplitude, Q_T, of 0.659 (3) Å and twisted conformation [ϕ = -149.80 (3)° and θ = 154.28 (3)°] (Cremer & Pople, 1975).

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. There is also a weak C—H···π interaction (Table 1).

Related literature top

For a related structure, see: Jose et al. (2005). For bond-length data, see: Allen et al. (1987). For ring-puckering parameters, see: Cremer & Pople (1975). Cg1 is the centroid of the S/C4–C7 ring.

Experimental top

For the preparation of the title compound, 3,4-dimethoxythiophene (1.14 g, 7.9 mmol), 3-chloro-1,2-propanediol (2.45 g, 22.2 mmol), p-toluene- sulfonic acid monohydrate (0.151 g, 0.81 mmol) and dry toluene (27 ml) were added into a three necked flask equipped with an argon purge. The mixture was refluxed for 12 h. Then, diol (2.45 g, 22.2 mmol) was added and refluxed for 3 h. It was allowed to cool to room temperature. After removal of the solvent, the remaining crude product was isolated by flash chromatography [silica gel, hexane/dichloromethane (8:2)] to isolate the title compound, as a colorless solid (yield; 58%) (Jose et al., 2005). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.1 g) in hexane (25 ml) and evaporating the solvent slowly at room temperature for about 3 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Chloromethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine top

Crystal data top

C₇H₇ClO₂S	F(000) = 392
M_r = 190.64	D_x = 1.555 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.227 (2) Å	θ = 10–13°
b = 5.7500 (12) Å	µ = 0.67 mm⁻¹
c = 14.376 (3) Å	T = 294 K
β = 105.55 (3)°	Block, colorless
V = 814.4 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1065 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.067
Graphite monochromator	θ_max = 25.4°, θ_min = 2.2°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.825, T_max = 0.936	l = −17→16
1565 measured reflections	3 standard reflections every 120 min
1479 independent reflections	intensity decay: 1%

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.92P] where P = (F_o² + 2F_c²)/3
1479 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₇ClO₂S	V = 814.4 (3) Å³
M_r = 190.64	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.227 (2) Å	µ = 0.67 mm⁻¹
b = 5.7500 (12) Å	T = 294 K
c = 14.376 (3) Å	0.30 × 0.20 × 0.10 mm
β = 105.55 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1065 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.067
T_min = 0.825, T_max = 0.936	3 standard reflections every 120 min
1565 measured reflections	intensity decay: 1%
1479 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.01	Δρ_max = 0.41 e Å⁻³
1479 reflections	Δρ_min = −0.29 e Å⁻³
100 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
Cl	−0.37084 (12)	0.1937 (2)	0.51615 (9)	0.0759 (5)
S	0.12047 (12)	0.1840 (2)	0.27636 (9)	0.0740 (5)
O1	−0.1425 (3)	0.6480 (5)	0.29741 (19)	0.0619 (8)
O2	−0.1277 (2)	0.2762 (4)	0.43358 (19)	0.0505 (7)
C1	−0.2959 (4)	0.4560 (8)	0.4923 (3)	0.0569 (10)
H1A	−0.3636	0.5786	0.4805	0.068*
H1B	−0.2238	0.4991	0.5486	0.068*
C2	−0.2397 (4)	0.4363 (7)	0.4079 (3)	0.0524 (9)
H2A	−0.3096	0.3729	0.3531	0.063*
C3	−0.1903 (4)	0.6650 (6)	0.3787 (3)	0.0539 (10)
H3A	−0.2641	0.7765	0.3663	0.065*
H3B	−0.1181	0.7236	0.4320	0.065*
C4	−0.0539 (4)	0.4634 (7)	0.3034 (3)	0.0515 (9)
C5	−0.0507 (4)	0.2828 (6)	0.3683 (3)	0.0477 (9)
C6	0.0309 (4)	0.4363 (8)	0.2481 (3)	0.0632 (11)
H6A	0.0400	0.5405	0.2008	0.076*
C7	0.0424 (4)	0.1179 (7)	0.3626 (3)	0.0591 (10)
H7A	0.0605	−0.0143	0.4012	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0794 (8)	0.0787 (9)	0.0741 (8)	−0.0128 (6)	0.0285 (6)	−0.0007 (6)
S	0.0758 (8)	0.0812 (9)	0.0696 (8)	0.0012 (6)	0.0275 (6)	−0.0095 (6)
O1	0.0693 (18)	0.0601 (18)	0.0461 (16)	0.0112 (14)	−0.0024 (13)	0.0218 (13)
O2	0.0571 (15)	0.0440 (14)	0.0484 (15)	0.0044 (12)	0.0110 (12)	0.0090 (12)
C1	0.061 (2)	0.066 (3)	0.0370 (19)	−0.005 (2)	0.0014 (17)	−0.0062 (18)
C2	0.051 (2)	0.053 (2)	0.042 (2)	−0.0049 (17)	−0.0081 (16)	−0.0067 (17)
C3	0.068 (2)	0.047 (2)	0.040 (2)	0.0146 (18)	0.0034 (17)	0.0132 (17)
C4	0.055 (2)	0.057 (2)	0.0329 (18)	−0.0073 (18)	−0.0059 (16)	0.0042 (17)
C5	0.059 (2)	0.044 (2)	0.0355 (18)	−0.0114 (17)	0.0042 (15)	−0.0069 (16)
C6	0.069 (3)	0.073 (3)	0.044 (2)	−0.004 (2)	0.0078 (19)	0.006 (2)
C7	0.064 (2)	0.051 (2)	0.059 (2)	0.0111 (19)	0.012 (2)	0.001 (2)

Geometric parameters (Å, º) top

Cl—C1	1.766 (4)	C2—C3	1.508 (5)
S—C7	1.688 (4)	C2—H2A	0.9800
S—C6	1.706 (5)	C3—H3A	0.9700
O1—C4	1.384 (5)	C3—H3B	0.9700
O1—C3	1.386 (5)	C4—C6	1.333 (5)
O2—C5	1.377 (5)	C4—C5	1.391 (5)
O2—C2	1.439 (5)	C5—C7	1.362 (5)
C1—C2	1.480 (5)	C6—H6A	0.9300
C1—H1A	0.9700	C7—H7A	0.9300
C1—H1B	0.9700

C7—S—C6	92.1 (2)	C2—C3—H3A	108.9
C4—O1—C3	112.0 (3)	O1—C3—H3B	108.9
C5—O2—C2	111.6 (3)	C2—C3—H3B	108.9
C2—C1—Cl	112.2 (3)	H3A—C3—H3B	107.8
C2—C1—H1A	109.2	C6—C4—O1	124.9 (4)
Cl—C1—H1A	109.2	C6—C4—C5	114.3 (4)
C2—C1—H1B	109.2	O1—C4—C5	120.8 (3)
Cl—C1—H1B	109.2	C7—C5—O2	124.0 (3)
H1A—C1—H1B	107.9	C7—C5—C4	111.7 (4)
O2—C2—C1	107.2 (3)	O2—C5—C4	124.3 (3)
O2—C2—C3	109.0 (3)	C4—C6—S	110.5 (3)
C1—C2—C3	113.2 (3)	C4—C6—H6A	124.7
O2—C2—H2A	109.1	S—C6—H6A	124.7
C1—C2—H2A	109.1	C5—C7—S	111.3 (3)
C3—C2—H2A	109.1	C5—C7—H7A	124.3
O1—C3—C2	113.2 (3)	S—C7—H7A	124.3
O1—C3—H3A	108.9

C5—O2—C2—C1	−167.2 (3)	C6—C4—C5—C7	1.5 (5)
C5—O2—C2—C3	−44.3 (4)	O1—C4—C5—C7	179.5 (3)
Cl—C1—C2—O2	−66.6 (3)	C6—C4—C5—O2	178.7 (3)
Cl—C1—C2—C3	173.1 (3)	O1—C4—C5—O2	−3.2 (5)
C4—O1—C3—C2	−48.0 (4)	O1—C4—C6—S	−178.8 (3)
O2—C2—C3—O1	63.1 (4)	C5—C4—C6—S	−0.8 (5)
C1—C2—C3—O1	−177.6 (3)	C7—S—C6—C4	0.0 (3)
C3—O1—C4—C6	−163.6 (4)	O2—C5—C7—S	−178.7 (3)
C3—O1—C4—C5	18.6 (5)	C4—C5—C7—S	−1.4 (4)
C2—O2—C5—C7	−165.2 (4)	C6—S—C7—C5	0.8 (3)
C2—O2—C5—C4	17.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.98	2.45	3.317 (5)	146
C1—H1B···Cg1ⁱⁱ	0.97	2.75	3.708 (5)	169

Symmetry codes: (i) −x−1/2, y−1/2, −z+1/2; (ii) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₇H₇ClO₂S
M_r	190.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	10.227 (2), 5.7500 (12), 14.376 (3)
β (°)	105.55 (3)
V (Å³)	814.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.825, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	1565, 1479, 1065
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.185, 1.01
No. of reflections	1479
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.98	2.45	3.317 (5)	146.00
C1—H1B···Cg1ⁱⁱ	0.97	2.75	3.708 (5)	168.45

Symmetry codes: (i) −x−1/2, y−1/2, −z+1/2; (ii) −x+1, −y+2, −z.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jose, L. S., Rafael, G., Egon, R. & Peter, B. (2005). Org. Lett. 7, 2345–2348. Web of Science PubMed Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o668

doi:10.1107/S1600536809007156

Open

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