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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3103.
Published online 2010 November 6. doi:  10.1107/S1600536810041267
PMCID: PMC3011714

2-[(Isopropoxycarbonothio­yl)sulfanyl]­acetic acid

Abstract

The title compound, C6H10O3S2, features a planar C atom connected to one O and two S atoms, the C—S single bond being distinctly longer than the C–S double bond. Two mol­ecules are linked by an O—H(...)O hydrogen bond about a center of inversion, generating a dimer.

Related literature

For general background to the synthesis and applications of the title compound, see: Stenzel et al. (2003 [triangle]); Moad et al. (2005 [triangle], 2008 [triangle]). For applications in polymerization, see: Coote & Radom (2004 [triangle]); Favier et al. (2004 [triangle]).

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Object name is e-66-o3103-scheme1.jpg

Experimental

Crystal data

  • C6H10O3S2
  • M r = 194.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3103-efi1.jpg
  • a = 5.0092 (14) Å
  • b = 7.712 (2) Å
  • c = 23.868 (7) Å
  • β = 90.294 (9)°
  • V = 922.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.54 mm−1
  • T = 150 K
  • 0.05 × 0.02 × 0.02 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.972, T max = 0.992
  • 6469 measured reflections
  • 2040 independent reflections
  • 1306 reflections with I > 2σ(I)
  • R int = 0.061

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.095
  • S = 1.03
  • 2040 reflections
  • 103 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; 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 global, I. DOI: 10.1107/S1600536810041267/ng5039sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041267/ng5039Isup2.hkl

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

Acknowledgments

This work was supported by the Canadian Natural Sciences and Engineering Research Council (NSERC) Idea to Innovation (I2I) Program. The authors are grateful to Dr Guerman Popov of the Department of Chemistry in The University of Western Ontario for the data acquisition and inter­pretation.

supplementary crystallographic information

Comment

In reversible addition-fragmentation chain-transfer (RAFT) polymerization, xanthates are used as chain transfer agents (CTA) for reversible-deactivation radical polymerization (RDRP) of vinyl acetate (Moad et al., 2005, 2008). Vinyl acetate is one of the typical monomers that cannot be easily polymerized in RDRP, because vinyl acetate radicals are highly unstable. However, xanthates destabilize the intermediate radicals in the RAFT equilibriums, and RDRP can be achieved (Coote & Radom, 2004; Favier et al., 2004). Stenzel et al. (2003) synthesized 2-(isopropoxycarbonothioylthio)acetate as the CTA to mediate the polymerization of vinyl acetate, but lack of functionality limits its applications. Therefore, 2-(isopropoxycarbonothioylthio)acetic acid was synthesized. It was employed in RAFT polymerization of vinyl acetate, with poly(vinyl acetate) having carboxylic acid end groups successfully obtained.

Investigation of the single-crystal of 2-(isopropoxycarbonothioylthio)acetic acid was conducted to understand its structural properties.

Experimental

Potassium hydroxide 5.6 g (50 mmol) and 2-propanol 100 ml were mixed to form a homogeneous solution, after which carbon disulfide 20 ml was added dropwise at room temperature. The mixture was kept stirred for 1 day at 40 °C. Then the solvent and residual carbon disulfide were evaporated to obtrain a light yellow powder. The powder was dissolved in methanol, and mixed with the methanol solution of bromoacetic acid. The reaction was conducted at 40 °C for 20 h. Salts were filtered out and solvents were evaporated. The oil was washed with excess diluted hydrochloric acid and extracted with ethyl ether. The crude product was run through a silica gel column with a solvent mixture of ethyl ether/hexanes (1:2). Colorless crystals of 2-(isopropoxycarbonothioylthio)acetic acid were obtained from recrystalization in hexanes. m.p. 44.3°C (DSC). MS: 194.0078.

Refinement

The hydrogen atom positions were calculated geometrically and were included as riding on their respective carbon/oxygen atoms.

Figures

Fig. 1.
View of the title compound (50% probability displacement ellipsoids).
Fig. 2.
Packing diagram of the structure with H-bonds.

Crystal data

C6H10O3S2F(000) = 408
Mr = 194.26Dx = 1.399 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 981 reflections
a = 5.0092 (14) Åθ = 2.8–23.5°
b = 7.712 (2) ŵ = 0.54 mm1
c = 23.868 (7) ÅT = 150 K
β = 90.294 (9)°Block, colourless
V = 922.0 (4) Å30.05 × 0.02 × 0.02 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer2040 independent reflections
Radiation source: fine-focus sealed tube1306 reflections with I > 2σ(I)
graphiteRint = 0.061
[var phi] and ω scansθmax = 27.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −3→6
Tmin = 0.972, Tmax = 0.992k = −9→9
6469 measured reflectionsl = −30→30

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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0365P)2 + 0.0157P] where P = (Fo2 + 2Fc2)/3
2040 reflections(Δ/σ)max < 0.001
103 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.30 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
S10.62574 (14)0.49105 (9)0.06736 (3)0.0265 (2)
S20.97062 (15)0.32368 (10)0.15640 (3)0.0302 (2)
O10.9373 (4)0.6573 (2)0.12779 (8)0.0252 (5)
O20.7271 (4)−0.0108 (2)0.04984 (9)0.0311 (5)
H20.8469−0.06920.03410.047*
O30.9230 (4)0.2085 (2)0.00436 (8)0.0288 (5)
C10.9765 (7)0.7333 (4)0.22585 (13)0.0456 (9)
H1A0.84590.82650.22050.068*
H1B1.10100.76510.25590.068*
H1C0.88350.62600.23590.068*
C21.1292 (5)0.7057 (4)0.17223 (12)0.0267 (7)
H2A1.26340.61100.17750.032*
C30.8641 (5)0.4925 (3)0.12137 (11)0.0223 (6)
C40.5442 (5)0.2657 (3)0.06314 (12)0.0246 (7)
H4A0.51130.22200.10150.030*
H4B0.37580.25320.04160.030*
C50.7540 (5)0.1537 (4)0.03631 (11)0.0226 (6)
C61.2649 (6)0.8665 (4)0.15058 (15)0.0408 (9)
H6A1.35430.84000.11520.061*
H6B1.39710.90640.17810.061*
H6C1.13150.95760.14440.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0297 (4)0.0200 (4)0.0297 (4)0.0018 (3)−0.0059 (3)−0.0032 (4)
S20.0362 (4)0.0214 (4)0.0330 (4)0.0034 (3)−0.0032 (3)0.0049 (4)
O10.0320 (11)0.0181 (11)0.0255 (11)−0.0002 (8)−0.0079 (9)−0.0033 (9)
O20.0313 (11)0.0196 (11)0.0426 (13)−0.0001 (9)0.0099 (10)−0.0015 (11)
O30.0268 (11)0.0223 (11)0.0375 (12)−0.0038 (9)0.0091 (10)−0.0040 (10)
C10.052 (2)0.052 (2)0.0323 (19)−0.0011 (18)−0.0065 (18)−0.0151 (18)
C20.0212 (14)0.0253 (16)0.0334 (17)0.0003 (13)−0.0074 (13)−0.0061 (15)
C30.0252 (14)0.0200 (14)0.0218 (15)0.0024 (13)0.0043 (12)−0.0025 (14)
C40.0203 (15)0.0236 (16)0.0299 (16)−0.0029 (12)0.0013 (13)−0.0061 (13)
C50.0201 (14)0.0205 (16)0.0270 (16)−0.0027 (12)−0.0053 (13)−0.0052 (14)
C60.0362 (18)0.0232 (17)0.063 (2)−0.0052 (14)−0.0075 (17)−0.0075 (18)

Geometric parameters (Å, °)

S1—C31.753 (3)C1—H1B0.9800
S1—C41.788 (3)C1—H1C0.9800
S2—C31.635 (3)C2—C61.506 (4)
O1—C31.331 (3)C2—H2A1.0000
O1—C21.476 (3)C4—C51.506 (4)
O2—C51.316 (3)C4—H4A0.9900
O2—H20.8400C4—H4B0.9900
O3—C51.218 (3)C6—H6A0.9800
C1—C21.509 (4)C6—H6B0.9800
C1—H1A0.9800C6—H6C0.9800
C3—S1—C4101.66 (13)S2—C3—S1126.18 (17)
C3—O1—C2120.2 (2)C5—C4—S1114.94 (19)
C5—O2—H2109.5C5—C4—H4A108.5
C2—C1—H1A109.5S1—C4—H4A108.5
C2—C1—H1B109.5C5—C4—H4B108.5
H1A—C1—H1B109.5S1—C4—H4B108.5
C2—C1—H1C109.5H4A—C4—H4B107.5
H1A—C1—H1C109.5O3—C5—O2124.1 (3)
H1B—C1—H1C109.5O3—C5—C4123.8 (3)
O1—C2—C6104.8 (2)O2—C5—C4112.1 (2)
O1—C2—C1108.3 (2)C2—C6—H6A109.5
C6—C2—C1114.0 (3)C2—C6—H6B109.5
O1—C2—H2A109.9H6A—C6—H6B109.5
C6—C2—H2A109.9C2—C6—H6C109.5
C1—C2—H2A109.9H6A—C6—H6C109.5
O1—C3—S2127.8 (2)H6B—C6—H6C109.5
O1—C3—S1106.06 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.841.832.664 (3)174

Symmetry codes: (i) −x+2, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG5039).

References

  • Bruker (2009). APEX2, SADABS and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Coote, M. L. & Radom, L. (2004). Macromolecules, 37, 590–596.
  • Favier, A., Barner-Kowollik, C., Davis, T. P. & Stenzel, M. H. (2004). Macromol. Chem. Phys.205, 925–936.
  • Moad, G., Rizzardo, E. & Thang, S. H. (2005). Aust. J. Chem.58, 379–410.
  • Moad, G., Rizzardo, E. & Thang, S. H. (2008). Polymer, 49, 1079–1131.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stenzel, M. H., Cummins, L., Roberts, G. E., Davis, T. P., Vana, P. & Barner-Kowollik, C. (2003). Macromol. Chem. Phys.204, 1160–1168.

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