2-[(Isopropoxycarbonothio­yl)sulfanyl]­acetic acid

Xiao, S.; Charpentier, P.A.

doi:10.1107/S1600536810041267

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3103

https://doi.org/10.1107/S1600536810041267

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2-[(Isopropoxycarbonothioyl)sulfanyl]acetic acid

Shude Xiao ^a and Paul A. Charpentier ^a ^*

^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

(Received 29 September 2010; accepted 13 October 2010; online 6 November 2010)

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 ); Moad et al. (2005 , 2008 ). For applications in polymerization, see: Coote & Radom (2004 ); Favier et al. (2004 ).

Experimental

Crystal data

C₆H₁₀O₃S₂
M_r = 194.26
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.046
wR(F²) = 0.095
S = 1.03
2040 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: APEX2 (Bruker, 2009); cell refinement: 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

Crystal structure: 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

checkCIF report

Comment top

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.

Related literature top

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).

Experimental top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

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

2-[(Isopropoxycarbonothioyl)sulfanyl]acetic acid top

Crystal data top

C₆H₁₀O₃S₂	F(000) = 408
M_r = 194.26	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2040 independent reflections
Radiation source: fine-focus sealed tube	1306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 27.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −3→6
T_min = 0.972, T_max = 0.992	k = −9→9
6469 measured reflections	l = −30→30

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0365P)² + 0.0157P] where P = (F_o² + 2F_c²)/3
2040 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₆H₁₀O₃S₂	V = 922.0 (4) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2040 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1306 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.992	R_int = 0.061
6469 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	Δρ_max = 0.34 e Å⁻³
2040 reflections	Δρ_min = −0.30 e Å⁻³
103 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.972, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	6469, 2040, 1306
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.30

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
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

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