organic papers
o2144
Kos¸aret al. C8H9ClOS doi:10.1107/S1600536806015698 Acta Cryst.(2006). E62, o2144–o2145
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
6-Chloro-8-thia-1,4-epoxybicyclo[4.3.0]non-2-ene
Bas¸ak Kos¸ar,aErsen Go¨ktu¨rk,b Cavit Kazaz,c
Orhan Bu¨yu¨kgu¨ngo¨raand Aydın Demircanb*
aDepartment of Physics, Ondokuz Mayıs
University, TR-55139 Samsun, Turkey,
bDepartment of Chemistry, Nigde University,
TR-51100 Nigde, Turkey, andcDepartment of
Chemistry, Ataturk University, TR-25250 Erzurum, Turkey
Correspondence e-mail: bkosar@omu.edu.tr
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.047
wRfactor = 0.127
Data-to-parameter ratio = 11.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 25 April 2006 Accepted 28 April 2006
#2006 International Union of Crystallography All rights reserved
In the structure of the title compound, C8H9ClOS, the
six-membered ring has a boat conformation and the S-containing five-membered ring has an envelope conformation. The molecules are linked only by weak van der Waals interactions.
Comment
Five-membered heteroaromatic compounds such as furans, thiophenes and pyroles possess dienic reactivity and have been well documented in the literature (Lipshutz, 1986; Kappe
et al., 1997). Furans, in particular, take part in inter- and intramolecular Diels–Alder reactions with a variety of dienophiles. The intramolecular Diels–Alder (IMDA) reac-tions of furan is particularly attractive as two, three or more rings can be constructed in a single step with high regio- and stereocontrol, providing convenient entry into natural products and the synthesis of polycyclic structures (Keay & Hunt, 1999; Demircan & Parsons, 2002; Williams, 2002). We have recently described and reported a bromo Diels–Alder cycloadduct (Bu¨yu¨kgu¨ngo¨ret al., 2005). Now we outline the synthesis and crystal structure of the title compound, (2), isolated from the thermal cycloaddition of (1) in toluene in reasonably good yield. The IMDA reaction of furans under-goes a retro-cycloaddition; when the reaction is cooled to room temperature, part of the cycloadduct, (2), transforms back to (1).
In general, reactions were conducted in hot toluene and the cycloaddition process is promoted by the Thorpe–Ingold (Scissor) effect. The relative stereochemistry of the cyclo-adduct, (2), is expected to be that of the previous examples,i.e.
arising from an ‘exo’ (the substituent on the dienophile is directed away from the diene) orientation 0.94(4)-1.06(4)of the dienophile side chain (Sammes & Weller, 1995; Parkeret al., 1978).
Experimental
Simple furanyl sulfides have been preparedviaalkylation of furfuryl mercaptan; a sodium hydride suspension (0.03 g, 1.2 mmol) dehy-drogenated the mercaptanol (0.09 g, 0.8 mmol); dropwise addition of 2,3-dichloropropene (0.09 g, 0.8 mmol) in tetrahydrofuran (10 ml) at 273 K afforded the precursor (1) quantitatively (yield 0.12 g, 78%). Compound (1) (0.12 g, 0.6 mmol) was then refluxed in 10 ml toluene (383 K) for 4 d. The reaction was monitored by thin layer chroma-tography and halted when no further change of (1) to cycloadduct (2) was noted. The ratio of furan starting material and cycloadduct was calculated after purification by flash column chromatography. The yield of cycloaddition can increase to 70% when the recovered starting material is repeatedly used for the same reaction.
Crystal data
C8H9ClOS
Mr= 188.66
Triclinic,P1
a= 6.651 (3) A˚
b= 7.971 (3) A˚
c= 8.048 (3) A˚
= 80.33 (3)
= 89.07 (3)
= 81.43 (3)
V= 415.9 (3) A˚3
Z= 2
Dx= 1.507 Mg m 3
MoKradiation
= 0.64 mm 1
T= 293 (2) K Prism, colorless 0.430.340.17 mm
Data collection
Stoe IPDS-2 diffractometer
!scans
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)
Tmin= 0.769,Tmax= 0.896
3731 measured reflections 1624 independent reflections 1330 reflections withI> 2(I)
Rint= 0.106
max= 26.0
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.047
wR(F2) = 0.127
S= 1.06 1624 reflections 136 parameters
All H-atom parameters refined
w= 1/[2
(Fo2) + (0.0578P)2
+ 0.0767P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.30 e A˚ 3
[image:2.610.63.274.73.226.2]min= 0.50 e A˚ 3
Table 1
Selected geometric parameters (A˚ ,).
C1—Cl1 1.805 (2) C7—S1 1.823 (3)
C8—S1 1.812 (3)
C1—C2—C3—C4 73.0 (3) C2—C3—C4—C5 72.9 (3)
C3—C4—C5—C6 1.0 (3) C4—C5—C6—C1 71.2 (3)
All H-atom parameters were freely refined.Uisovalues are in the range 0.47–0.80 A˚2. The C—H distances are in the range 0.94 (4)– 1.06 (4) A˚ .
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement:
X-AREA; data reduction:X-RED32(Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).
The authors thank TUBITAK (PN: 103 T121) and the State Planning Organization (DPT) (PN: 03 K120880–1) for finan-cial support of this project.
References
Bu¨yu¨kgu¨ngo¨r, O., Kos¸ar, B., Demircan, A. & Turac¸, E. (2005).Acta Cryst.E61, o1441–o1442.
Demircan, A. & Parsons, P. J. (2002). Heterocycl. Commun. 8, 531– 536.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Kappe, C. O., Murphree, S. S. & Padwa, A. (1997).Tetrahedron,53, 14179– 14233.
Keay, B. A. & Hunt, I. R. (1999).Adv. Cycloaddit.6, 173–210. Lipshutz, B. H. (1986).Chem. Rev.86, 795–819.
Parker, K. A. & Adamchuk, M. R. (1978). Tetrahedron Lett. 19, 1689– 1692.
Sammes, P. G. & Weller, D. J. (1995).Synthesis, pp. 1205–1222.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Go¨ttingen, Germany.
Stoe & Cie (2002).X-AREAandX-RED32. Stoe & Cie, Darmstadt, Germany. Williams, R. M. (2002).Chem. Pharm. Bull.50, 711–740.
Figure 1
supporting information
sup-1 Acta Cryst. (2006). E62, o2144–o2145
supporting information
Acta Cryst. (2006). E62, o2144–o2145 [https://doi.org/10.1107/S1600536806015698]
6-Chloro-8-thia-1,4-epoxybicyclo[4.3.0]non-2-ene
Başak Koşar, Ersen Göktürk, Cavit Kazaz, Orhan Büyükgüngör and Aydın Demircan
6-Chloro-8-thia-1,4-epoxybicyclo[4.3.0]non-2-ene
Crystal data C8H9ClOS
Mr = 188.66
Triclinic, P1 a = 6.651 (3) Å b = 7.971 (3) Å c = 8.048 (3) Å α = 80.33 (3)° β = 89.07 (3)° γ = 81.43 (3)° V = 415.9 (3) Å3
Z = 2 F(000) = 196 Dx = 1.507 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5795 reflections θ = 2.6–27.9°
µ = 0.64 mm−1
T = 293 K Prism, colorless 0.43 × 0.34 × 0.17 mm
Data collection Stoe IPDS-2
diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 6.67 pixels mm-1
ω scans
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) Tmin = 0.769, Tmax = 0.896
3731 measured reflections 1624 independent reflections 1330 reflections with I > 2σ(I) Rint = 0.106
θmax = 26.0°, θmin = 3.1°
h = −8→8 k = −9→9 l = −9→9
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.127
S = 1.06 1624 reflections 136 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined w = 1/[σ2(F
o2) + (0.0578P)2 + 0.0767P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.30 e Å−3
Δρmin = −0.50 e Å−3
Special details
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)
x y z Uiso*/Ueq
C1 0.1559 (4) 0.1993 (3) 0.7146 (3) 0.0389 (5) C2 0.0671 (5) 0.2975 (4) 0.8531 (4) 0.0535 (7) C3 0.2251 (5) 0.4229 (4) 0.8537 (4) 0.0551 (7) C4 0.4166 (5) 0.3190 (5) 0.9338 (4) 0.0617 (8) C5 0.4960 (4) 0.2269 (4) 0.8226 (4) 0.0518 (7) C6 0.3569 (3) 0.2748 (3) 0.6707 (3) 0.0386 (5) C7 0.4288 (4) 0.2466 (4) 0.4992 (4) 0.0492 (6) C8 0.0336 (4) 0.2329 (4) 0.5525 (4) 0.0461 (6) O1 0.2791 (3) 0.4507 (2) 0.6782 (2) 0.0467 (5) S1 0.21149 (13) 0.21040 (11) 0.38192 (9) 0.0601 (3) Cl1 0.20835 (11) −0.03010 (8) 0.78573 (9) 0.0523 (2) H1 0.482 (6) 0.345 (5) 0.446 (5) 0.070 (10)* H2 0.053 (6) 0.226 (5) 0.964 (6) 0.080 (12)* H3 0.162 (6) 0.530 (5) 0.876 (5) 0.075 (11)* H4 −0.058 (5) 0.143 (4) 0.552 (4) 0.050 (8)* H5 0.536 (5) 0.148 (4) 0.510 (4) 0.056 (9)* H6 −0.070 (6) 0.354 (4) 0.823 (4) 0.052 (8)* H7 −0.038 (5) 0.347 (4) 0.532 (4) 0.047 (8)* H8 0.617 (7) 0.144 (5) 0.838 (5) 0.078 (12)* H10 0.460 (6) 0.314 (4) 1.060 (5) 0.065 (9)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0338 (11) 0.0347 (11) 0.0471 (14) −0.0095 (9) 0.0042 (9) −0.0006 (10) C2 0.0487 (16) 0.0581 (16) 0.0572 (18) −0.0151 (13) 0.0139 (13) −0.0146 (14) C3 0.0606 (17) 0.0544 (17) 0.0565 (18) −0.0145 (13) 0.0122 (14) −0.0223 (14) C4 0.0664 (19) 0.0711 (19) 0.0542 (18) −0.0264 (15) −0.0059 (15) −0.0141 (15) C5 0.0406 (14) 0.0589 (17) 0.0578 (17) −0.0157 (12) −0.0078 (12) −0.0069 (13) C6 0.0334 (11) 0.0361 (11) 0.0464 (14) −0.0104 (9) 0.0047 (10) −0.0033 (10) C7 0.0480 (14) 0.0539 (15) 0.0499 (16) −0.0191 (12) 0.0126 (12) −0.0112 (13) C8 0.0401 (13) 0.0472 (14) 0.0488 (15) −0.0074 (11) −0.0040 (10) −0.0006 (11) O1 0.0499 (10) 0.0361 (9) 0.0551 (12) −0.0113 (7) 0.0075 (8) −0.0072 (8) S1 0.0642 (5) 0.0781 (6) 0.0397 (4) −0.0195 (4) −0.0008 (3) −0.0067 (3) Cl1 0.0603 (4) 0.0406 (4) 0.0541 (4) −0.0169 (3) −0.0030 (3) 0.0062 (3)
Geometric parameters (Å, º)
supporting information
sup-3 Acta Cryst. (2006). E62, o2144–o2145
C1—C6 1.558 (3) C5—H8 0.96 (4) C1—Cl1 1.805 (2) C6—O1 1.432 (3) C2—C3 1.555 (4) C6—C7 1.495 (4) C2—H2 0.98 (4) C7—S1 1.823 (3) C2—H6 0.97 (4) C7—H1 0.94 (4) C3—O1 1.441 (4) C7—H5 0.97 (3) C3—C4 1.502 (5) C8—S1 1.812 (3) C3—H3 0.94 (4) C8—H4 1.01 (3) C4—C5 1.307 (5) C8—H7 0.95 (3)
C8—C1—C2 115.8 (2) C4—C5—H8 126 (3) C8—C1—C6 106.2 (2) C6—C5—H8 128 (3) C2—C1—C6 102.5 (2) O1—C6—C7 113.2 (2) C8—C1—Cl1 108.65 (19) O1—C6—C5 101.8 (2) C2—C1—Cl1 112.67 (19) C7—C6—C5 121.8 (2) C6—C1—Cl1 110.64 (16) O1—C6—C1 97.47 (18) C1—C2—C3 99.9 (2) C7—C6—C1 110.9 (2) C1—C2—H2 115 (2) C5—C6—C1 108.6 (2) C3—C2—H2 113 (3) C6—C7—S1 107.76 (19) C1—C2—H6 110 (2) C6—C7—H1 109 (2) C3—C2—H6 114.0 (19) S1—C7—H1 111 (2) H2—C2—H6 104 (3) C6—C7—H5 109 (2) O1—C3—C4 101.8 (2) S1—C7—H5 111 (2) O1—C3—C2 100.8 (2) H1—C7—H5 109 (3) C4—C3—C2 107.3 (3) C1—C8—S1 107.43 (18) O1—C3—H3 106 (3) C1—C8—H4 110.8 (18) C4—C3—H3 127 (3) S1—C8—H4 106.6 (18) C2—C3—H3 111 (2) C1—C8—H7 111 (2) C5—C4—C3 105.7 (3) S1—C8—H7 107.7 (18) C5—C4—H10 129 (2) H4—C8—H7 113 (3) C3—C4—H10 124 (2) C6—O1—C3 96.1 (2) C4—C5—C6 106.3 (3) C8—S1—C7 94.61 (13)
