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access2-[(Isopropoxycarbonothioyl)sulfanyl]acetic acid
aDeptartment of Chemical and Biochemical Engineering, Faculty of Engineering, The University of Western Ontario, London, Ontario, Canada N6A 5B9
*Correspondence e-mail: pcharpentier@eng.uwo.ca
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![[Stenzel, M. H., Cummins, L., Roberts, G. E., Davis, T. P., Vana, P. & Barner-Kowollik, C. (2003). Macromol. Chem. Phys. 204, 1160-1168.]](../../../../../../logos/arrows/e_arr.gif "Stenzel, M. H., Cummins, L., Roberts, G. E., Davis, T. P., Vana, P. & Barner-Kowollik, C. (2003). Macromol. Chem. Phys. 204, 1160-1168.")
); Moad et al. (2005, 2008). For applications in polymerization, see: Coote & Radom (2004); Favier et al. (2004).
![[Scheme 1]](ng5039scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; 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
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810041267/ng5039sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041267/ng5039Isup2.hkl
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.
The hydrogen atom positions were calculated geometrically and were included as riding on their respective carbon/oxygen atoms.
In reversible addition-fragmentation chain-transfer (RAFT) polymerization, are used as agents (CTA) for reversible-deactivation (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, 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.
For general background to the synthesis and applications of the title compound, see: Stenzel et al. (2003); Moad et al. (2005, 2008). For applications in polymerization, see: Coote & Radom (2004); Favier et al. (2004).
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).
![[Figure 1]](./ng5039fig1thm.gif) | Fig. 1. View of the title compound (50% probability displacement ellipsoids). |
![[Figure 2]](./ng5039fig2thm.gif) | Fig. 2. Packing diagram of the structure with H-bonds. |
| C6H10O3S2 | F(000) = 408 |
| Mr = 194.26 | Dx = 1.399 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 981 reflections |
| a = 5.0092 (14) Å | θ = 2.8–23.5° |
| b = 7.712 (2) Å | µ = 0.54 mm−1 |
| c = 23.868 (7) Å | T = 150 K |
| β = 90.294 (9)° | Block, colourless |
| V = 922.0 (4) Å3 | 0.05 × 0.02 × 0.02 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 2040 independent reflections |
| Radiation source: fine-focus sealed tube | 1306 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.061 |
| φ and ω scans | θmax = 27.1°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −3→6 |
| Tmin = 0.972, Tmax = 0.992 | k = −9→9 |
| 6469 measured reflections | l = −30→30 |
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.095 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0365P)2 + 0.0157P] where P = (Fo2 + 2Fc2)/3 |
| 2040 reflections | (Δ/σ)max < 0.001 |
| 103 parameters | Δρmax = 0.34 e Å−3 |
| 0 restraints | Δρmin = −0.30 e Å−3 |
| C6H10O3S2 | V = 922.0 (4) Å3 |
| Mr = 194.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 5.0092 (14) Å | µ = 0.54 mm−1 |
| b = 7.712 (2) Å | T = 150 K |
| c = 23.868 (7) Å | 0.05 × 0.02 × 0.02 mm |
| β = 90.294 (9)° |
| Bruker APEXII CCD diffractometer | 2040 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1306 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.992 | Rint = 0.061 |
| 6469 measured reflections |
| R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
| wR(F2) = 0.095 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.34 e Å−3 |
| 2040 reflections | Δρmin = −0.30 e Å−3 |
| 103 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.62574 (14) | 0.49105 (9) | 0.06736 (3) | 0.0265 (2) | |
| S2 | 0.97062 (15) | 0.32368 (10) | 0.15640 (3) | 0.0302 (2) | |
| O1 | 0.9373 (4) | 0.6573 (2) | 0.12779 (8) | 0.0252 (5) | |
| O2 | 0.7271 (4) | −0.0108 (2) | 0.04984 (9) | 0.0311 (5) | |
| H2 | 0.8469 | −0.0692 | 0.0341 | 0.047* | |
| O3 | 0.9230 (4) | 0.2085 (2) | 0.00436 (8) | 0.0288 (5) | |
| C1 | 0.9765 (7) | 0.7333 (4) | 0.22585 (13) | 0.0456 (9) | |
| H1A | 0.8459 | 0.8265 | 0.2205 | 0.068* | |
| H1B | 1.1010 | 0.7651 | 0.2559 | 0.068* | |
| H1C | 0.8835 | 0.6260 | 0.2359 | 0.068* | |
| C2 | 1.1292 (5) | 0.7057 (4) | 0.17223 (12) | 0.0267 (7) | |
| H2A | 1.2634 | 0.6110 | 0.1775 | 0.032* | |
| C3 | 0.8641 (5) | 0.4925 (3) | 0.12137 (11) | 0.0223 (6) | |
| C4 | 0.5442 (5) | 0.2657 (3) | 0.06314 (12) | 0.0246 (7) | |
| H4A | 0.5113 | 0.2220 | 0.1015 | 0.030* | |
| H4B | 0.3758 | 0.2532 | 0.0416 | 0.030* | |
| C5 | 0.7540 (5) | 0.1537 (4) | 0.03631 (11) | 0.0226 (6) | |
| C6 | 1.2649 (6) | 0.8665 (4) | 0.15058 (15) | 0.0408 (9) | |
| H6A | 1.3543 | 0.8400 | 0.1152 | 0.061* | |
| H6B | 1.3971 | 0.9064 | 0.1781 | 0.061* | |
| H6C | 1.1315 | 0.9576 | 0.1444 | 0.061* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0297 (4) | 0.0200 (4) | 0.0297 (4) | 0.0018 (3) | −0.0059 (3) | −0.0032 (4) |
| S2 | 0.0362 (4) | 0.0214 (4) | 0.0330 (4) | 0.0034 (3) | −0.0032 (3) | 0.0049 (4) |
| O1 | 0.0320 (11) | 0.0181 (11) | 0.0255 (11) | −0.0002 (8) | −0.0079 (9) | −0.0033 (9) |
| O2 | 0.0313 (11) | 0.0196 (11) | 0.0426 (13) | −0.0001 (9) | 0.0099 (10) | −0.0015 (11) |
| O3 | 0.0268 (11) | 0.0223 (11) | 0.0375 (12) | −0.0038 (9) | 0.0091 (10) | −0.0040 (10) |
| C1 | 0.052 (2) | 0.052 (2) | 0.0323 (19) | −0.0011 (18) | −0.0065 (18) | −0.0151 (18) |
| C2 | 0.0212 (14) | 0.0253 (16) | 0.0334 (17) | 0.0003 (13) | −0.0074 (13) | −0.0061 (15) |
| C3 | 0.0252 (14) | 0.0200 (14) | 0.0218 (15) | 0.0024 (13) | 0.0043 (12) | −0.0025 (14) |
| C4 | 0.0203 (15) | 0.0236 (16) | 0.0299 (16) | −0.0029 (12) | 0.0013 (13) | −0.0061 (13) |
| C5 | 0.0201 (14) | 0.0205 (16) | 0.0270 (16) | −0.0027 (12) | −0.0053 (13) | −0.0052 (14) |
| C6 | 0.0362 (18) | 0.0232 (17) | 0.063 (2) | −0.0052 (14) | −0.0075 (17) | −0.0075 (18) |
| S1—C3 | 1.753 (3) | C1—H1B | 0.9800 |
| S1—C4 | 1.788 (3) | C1—H1C | 0.9800 |
| S2—C3 | 1.635 (3) | C2—C6 | 1.506 (4) |
| O1—C3 | 1.331 (3) | C2—H2A | 1.0000 |
| O1—C2 | 1.476 (3) | C4—C5 | 1.506 (4) |
| O2—C5 | 1.316 (3) | C4—H4A | 0.9900 |
| O2—H2 | 0.8400 | C4—H4B | 0.9900 |
| O3—C5 | 1.218 (3) | C6—H6A | 0.9800 |
| C1—C2 | 1.509 (4) | C6—H6B | 0.9800 |
| C1—H1A | 0.9800 | C6—H6C | 0.9800 |
| C3—S1—C4 | 101.66 (13) | S2—C3—S1 | 126.18 (17) |
| C3—O1—C2 | 120.2 (2) | C5—C4—S1 | 114.94 (19) |
| C5—O2—H2 | 109.5 | C5—C4—H4A | 108.5 |
| C2—C1—H1A | 109.5 | S1—C4—H4A | 108.5 |
| C2—C1—H1B | 109.5 | C5—C4—H4B | 108.5 |
| H1A—C1—H1B | 109.5 | S1—C4—H4B | 108.5 |
| C2—C1—H1C | 109.5 | H4A—C4—H4B | 107.5 |
| H1A—C1—H1C | 109.5 | O3—C5—O2 | 124.1 (3) |
| H1B—C1—H1C | 109.5 | O3—C5—C4 | 123.8 (3) |
| O1—C2—C6 | 104.8 (2) | O2—C5—C4 | 112.1 (2) |
| O1—C2—C1 | 108.3 (2) | C2—C6—H6A | 109.5 |
| C6—C2—C1 | 114.0 (3) | C2—C6—H6B | 109.5 |
| O1—C2—H2A | 109.9 | H6A—C6—H6B | 109.5 |
| C6—C2—H2A | 109.9 | C2—C6—H6C | 109.5 |
| C1—C2—H2A | 109.9 | H6A—C6—H6C | 109.5 |
| O1—C3—S2 | 127.8 (2) | H6B—C6—H6C | 109.5 |
| O1—C3—S1 | 106.06 (19) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3i | 0.84 | 1.83 | 2.664 (3) | 174 |
| Symmetry code: (i) −x+2, −y, −z. |
Experimental details
| Crystal data | |
| Chemical formula | C6H10O3S2 |
| Mr | 194.26 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 150 |
| a, b, c (Å) | 5.0092 (14), 7.712 (2), 23.868 (7) |
| β (°) | 90.294 (9) |
| V (Å3) | 922.0 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.54 |
| Crystal size (mm) | 0.05 × 0.02 × 0.02 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
| Tmin, Tmax | 0.972, 0.992 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6469, 2040, 1306 |
| Rint | 0.061 |
| (sin θ/λ)max (Å−1) | 0.641 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.095, 1.03 |
| No. of reflections | 2040 |
| No. of parameters | 103 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.34, −0.30 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O3i | 0.84 | 1.83 | 2.664 (3) | 173.5 |
| Symmetry code: (i) −x+2, −y, −z. |
Acknowledgements
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.
References
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coote, M. L. & Radom, L. (2004). Macromolecules, 37, 590–596. Web of Science CrossRef CAS Google Scholar
Favier, A., Barner-Kowollik, C., Davis, T. P. & Stenzel, M. H. (2004). Macromol. Chem. Phys. 205, 925–936. Web of Science CrossRef CAS Google Scholar
Moad, G., Rizzardo, E. & Thang, S. H. (2005). Aust. J. Chem. 58, 379–410. Web of Science CrossRef CAS Google Scholar
Moad, G., Rizzardo, E. & Thang, S. H. (2008). Polymer, 49, 1079–1131. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stenzel, M. H., Cummins, L., Roberts, G. E., Davis, T. P., Vana, P. & Barner-Kowollik, C. (2003). Macromol. Chem. Phys. 204, 1160–1168. Web of Science CrossRef CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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.