organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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3-({[(1-Phenyl­eth­yl)sulfan­yl]methane­thio­yl}sulfan­yl)propanoic acid

aDepartment of Chemistry, IIT Madras, Chennai, Tamil Nadu, India
*Correspondence e-mail: damo@iitm.ac.in

(Received 27 October 2011; accepted 7 November 2011; online 19 November 2011)

In the title compound, C12H14O2S3, a chain transfer agent (CTA) used in polymerization, the dihedral angle between the aromatic ring and the CS3 grouping is 84.20 (10)°. In the crystal, carb­oxy­lic acid inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R22(8) loops.

Related literature

For background to chain transfer agents, see: Chong et al. (1999[Chong, Y. K., Le, T. P. T., Moad, G., Rizzardo, E. & Thang, S. H. (1999). Macromolecules, 32, 2071-2074.]); Coady et al. (2008[Coady, D. J., Norris, B. C., Lynch, V. M. & Bielawski, C. W. (2008). Macromolecules, 41, 3775-3778.]). For a related structure, see: Kannan et al. (2010[Kannan, M., Ramkumar, V. & Dhamodharan, R. (2010). Acta Cryst. E66, o1382.]).

[Scheme 1]

Experimental

Crystal data
  • C12H14O2S3

  • Mr = 286.41

  • Monoclinic, P 21 /c

  • a = 13.6280 (8) Å

  • b = 10.2908 (5) Å

  • c = 10.7299 (5) Å

  • β = 113.039 (2)°

  • V = 1384.77 (12) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.52 mm−1

  • T = 298 K

  • 0.42 × 0.28 × 0.22 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.811, Tmax = 0.894

  • 9109 measured reflections

  • 3020 independent reflections

  • 2224 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.095

  • S = 1.03

  • 3020 reflections

  • 159 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H1O⋯O1i 0.81 (3) 1.85 (3) 2.651 (2) 177 (3)
Symmetry code: (i) -x, -y+3, -z.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound C12H14S3O2 is a carbanotrithioate. It can be used as a chain transfer agent (CTA) in RAFT polymerization (Chong et al., 1999) to control the polymerization and it will produce carbanotrithionate end-terminated polymers. Very few single-crystal XRD data are available for CTAs, because most of them are liquids (Coady et al., 2008). Recently, we have reported the single-crystal data of a multi-functional CTA, which can be used for the synthesis of star polymers. Carbanotrithioate CTA is suitable for the polymerization of styrene, acrylates and methacrylates. With appropriate choice of the CTA (RAFT agent) and reaction conditions, RAFT polymerization can be successfully used to produce polymers of narrow polydispersity with predetermined molecular weights. Moreover, the polymers obtained by the RAFT process can be chain extended or used as precursors to synthesize stimuli responsive block copolymers by the addition of further monomer(s). The title compound will result in carboxylic acid end-terminated polymer; this functionality can be further modified and utilized for making block copolymers by reacting it with another homo-polymer.

The compound C12H14S3O2 is stabilized by a O—H···O interaction with R22(8) graph set motif.

Related literature top

For background to chain transfer agents, see: Chong et al. (1999); Coady et al. (2008). For a related structure, see: Kannan et al. (2010).

Experimental top

The title compound, was prepared by adding 3-mercapto propanoic acid (1.00 g, 7.35 mmol) to a stirred suspension of K3PO4 (1.72 g, 8.09 mmol) in acetone (20 ml) over a period of ten minutes. CS2 (1.68 g, 22.06 mmol) was added upon which the solution turned bright yellow. After stirring for ten minutes 1-bromo ethyl benzene (1.26 g, 7.35 mmol) was added and an instant precipitation of KBr was noted. After stirring for three hours the suspension was filtered and the cake was rinsed with acetone (2 × 20 ml). After removing the solvent from the filtrate under reduced pressure the resulting yellow residue was purified by column chromatography on silica using a petroleum ether/ethyl acetate gradient to yield light yellow solid (96%) that crystallized to form light yellow blocks.

Refinement top

All hydrogen atoms were fixed geometrically and allowed to ride on the parent carbon atoms, with aromatic C—H = 0.93 Å, methyl C—H = 0.96 Å and methylene C—H = 0.97 Å. The displacement parameters were set for phenyl and methylene H atoms at Uiso(H) = 1.2Ueq(C) and methyl H atoms at Uiso(H) = 1.5Ueq(C).

Structure description top

The title compound C12H14S3O2 is a carbanotrithioate. It can be used as a chain transfer agent (CTA) in RAFT polymerization (Chong et al., 1999) to control the polymerization and it will produce carbanotrithionate end-terminated polymers. Very few single-crystal XRD data are available for CTAs, because most of them are liquids (Coady et al., 2008). Recently, we have reported the single-crystal data of a multi-functional CTA, which can be used for the synthesis of star polymers. Carbanotrithioate CTA is suitable for the polymerization of styrene, acrylates and methacrylates. With appropriate choice of the CTA (RAFT agent) and reaction conditions, RAFT polymerization can be successfully used to produce polymers of narrow polydispersity with predetermined molecular weights. Moreover, the polymers obtained by the RAFT process can be chain extended or used as precursors to synthesize stimuli responsive block copolymers by the addition of further monomer(s). The title compound will result in carboxylic acid end-terminated polymer; this functionality can be further modified and utilized for making block copolymers by reacting it with another homo-polymer.

The compound C12H14S3O2 is stabilized by a O—H···O interaction with R22(8) graph set motif.

For background to chain transfer agents, see: Chong et al. (1999); Coady et al. (2008). For a related structure, see: Kannan et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule with atoms represented as 30% probability ellipsoids.
3-({[(1-Phenylethyl)sulfanyl]methanethioyl}sulfanyl)propanoic acid top
Crystal data top
C12H14O2S3F(000) = 600
Mr = 286.41Dx = 1.374 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4284 reflections
a = 13.6280 (8) Åθ = 2.6–27.2°
b = 10.2908 (5) ŵ = 0.52 mm1
c = 10.7299 (5) ÅT = 298 K
β = 113.039 (2)°Block, light yellow
V = 1384.77 (12) Å30.42 × 0.28 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3020 independent reflections
Radiation source: fine-focus sealed tube2224 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
phi and ω scansθmax = 28.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1718
Tmin = 0.811, Tmax = 0.894k = 1212
9109 measured reflectionsl = 1412
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0372P)2 + 0.5628P]
where P = (Fo2 + 2Fc2)/3
3020 reflections(Δ/σ)max = 0.001
159 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C12H14O2S3V = 1384.77 (12) Å3
Mr = 286.41Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.6280 (8) ŵ = 0.52 mm1
b = 10.2908 (5) ÅT = 298 K
c = 10.7299 (5) Å0.42 × 0.28 × 0.22 mm
β = 113.039 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3020 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
2224 reflections with I > 2σ(I)
Tmin = 0.811, Tmax = 0.894Rint = 0.017
9109 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.095H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.32 e Å3
3020 reflectionsΔρmin = 0.27 e Å3
159 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
xyzUiso*/Ueq
C10.34830 (19)0.5248 (2)0.1937 (3)0.0664 (6)
H10.32250.57850.11800.080*
C20.4227 (2)0.4306 (3)0.2022 (4)0.0874 (9)
H20.44690.42160.13280.105*
C30.4606 (2)0.3509 (3)0.3116 (4)0.0948 (11)
H30.51030.28700.31680.114*
C40.4260 (2)0.3645 (3)0.4129 (4)0.0912 (10)
H40.45190.30950.48750.109*
C50.3523 (2)0.4598 (2)0.4070 (3)0.0684 (6)
H50.33020.46920.47830.082*
C60.31156 (16)0.54066 (18)0.2959 (2)0.0492 (5)
C70.23156 (16)0.64611 (17)0.2845 (2)0.0477 (5)
H70.18060.65040.19010.057*
C80.1697 (2)0.6301 (3)0.3737 (3)0.0832 (8)
H8A0.13300.54820.35460.125*
H8B0.11870.69930.35590.125*
H8C0.21800.63270.46710.125*
C90.21603 (15)0.91964 (17)0.24871 (19)0.0421 (4)
C100.18484 (18)1.18835 (19)0.2244 (2)0.0553 (5)
H10A0.11861.15270.22310.066*
H10B0.20461.26080.28720.066*
C110.16642 (16)1.23796 (18)0.0855 (2)0.0479 (5)
H11A0.23421.26240.08250.057*
H11B0.13591.16920.01990.057*
C120.09317 (15)1.35291 (18)0.0482 (2)0.0444 (4)
O10.04244 (14)1.38506 (15)0.11389 (17)0.0706 (5)
O20.08929 (15)1.41368 (17)0.05809 (18)0.0708 (5)
S10.30835 (4)0.79721 (5)0.32472 (6)0.05737 (18)
S20.09018 (4)0.90297 (6)0.15929 (6)0.06006 (18)
S30.28670 (5)1.06576 (5)0.28523 (7)0.06266 (19)
H1O0.051 (3)1.477 (3)0.073 (3)0.111 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0664 (15)0.0545 (13)0.0817 (17)0.0057 (11)0.0326 (13)0.0060 (12)
C20.0686 (18)0.0723 (18)0.125 (3)0.0037 (14)0.0424 (18)0.0282 (18)
C30.0550 (17)0.0490 (15)0.163 (3)0.0051 (12)0.023 (2)0.0112 (18)
C40.0649 (18)0.0499 (15)0.127 (3)0.0007 (13)0.0035 (18)0.0247 (16)
C50.0650 (15)0.0477 (13)0.0813 (17)0.0060 (11)0.0166 (13)0.0118 (12)
C60.0460 (12)0.0316 (10)0.0666 (14)0.0063 (8)0.0182 (10)0.0023 (9)
C70.0498 (12)0.0357 (10)0.0610 (13)0.0039 (8)0.0256 (10)0.0005 (9)
C80.098 (2)0.0674 (16)0.115 (2)0.0002 (15)0.0750 (19)0.0082 (15)
C90.0449 (11)0.0387 (10)0.0425 (11)0.0042 (8)0.0170 (9)0.0011 (8)
C100.0641 (14)0.0361 (10)0.0645 (14)0.0124 (9)0.0240 (11)0.0065 (9)
C110.0471 (11)0.0399 (10)0.0585 (13)0.0088 (8)0.0228 (10)0.0041 (9)
C120.0457 (11)0.0380 (10)0.0515 (12)0.0057 (8)0.0214 (10)0.0048 (8)
O10.0899 (12)0.0649 (10)0.0778 (11)0.0397 (9)0.0553 (10)0.0286 (8)
O20.0879 (13)0.0675 (11)0.0748 (12)0.0384 (10)0.0510 (10)0.0314 (9)
S10.0441 (3)0.0327 (3)0.0829 (4)0.0021 (2)0.0114 (3)0.0055 (2)
S20.0411 (3)0.0620 (3)0.0680 (4)0.0046 (2)0.0115 (3)0.0083 (3)
S30.0507 (3)0.0354 (3)0.0857 (5)0.0032 (2)0.0092 (3)0.0112 (3)
Geometric parameters (Å, º) top
C1—C21.380 (3)C8—H8B0.9600
C1—C61.383 (3)C8—H8C0.9600
C1—H10.9300C9—S21.614 (2)
C2—C31.357 (5)C9—S11.7415 (19)
C2—H20.9300C9—S31.7455 (19)
C3—C41.351 (5)C10—C111.500 (3)
C3—H30.9300C10—S31.799 (2)
C4—C51.388 (4)C10—H10A0.9700
C4—H40.9300C10—H10B0.9700
C5—C61.380 (3)C11—C121.498 (2)
C5—H50.9300C11—H11A0.9700
C6—C71.509 (3)C11—H11B0.9700
C7—C81.512 (3)C12—O11.211 (2)
C7—S11.8291 (19)C12—O21.283 (2)
C7—H70.9800O2—H1O0.81 (3)
C8—H8A0.9600
C2—C1—C6121.0 (3)H8A—C8—H8B109.5
C2—C1—H1119.5C7—C8—H8C109.5
C6—C1—H1119.5H8A—C8—H8C109.5
C3—C2—C1120.2 (3)H8B—C8—H8C109.5
C3—C2—H2119.9S2—C9—S1127.34 (11)
C1—C2—H2119.9S2—C9—S3126.14 (11)
C4—C3—C2119.9 (3)S1—C9—S3106.51 (11)
C4—C3—H3120.0C11—C10—S3113.87 (14)
C2—C3—H3120.0C11—C10—H10A108.8
C3—C4—C5120.8 (3)S3—C10—H10A108.8
C3—C4—H4119.6C11—C10—H10B108.8
C5—C4—H4119.6S3—C10—H10B108.8
C6—C5—C4120.3 (3)H10A—C10—H10B107.7
C6—C5—H5119.9C12—C11—C10111.69 (16)
C4—C5—H5119.9C12—C11—H11A109.3
C5—C6—C1117.8 (2)C10—C11—H11A109.3
C5—C6—C7122.5 (2)C12—C11—H11B109.3
C1—C6—C7119.66 (19)C10—C11—H11B109.3
C6—C7—C8115.77 (18)H11A—C11—H11B107.9
C6—C7—S1105.29 (13)O1—C12—O2123.36 (18)
C8—C7—S1110.65 (16)O1—C12—C11122.18 (17)
C6—C7—H7108.3O2—C12—C11114.46 (16)
C8—C7—H7108.3C12—O2—H1O112 (2)
S1—C7—H7108.3C9—S1—C7105.23 (9)
C7—C8—H8A109.5C9—S3—C10104.07 (10)
C7—C8—H8B109.5
C6—C1—C2—C30.4 (4)C1—C6—C7—S176.6 (2)
C1—C2—C3—C40.5 (4)S3—C10—C11—C12171.50 (14)
C2—C3—C4—C50.3 (4)C10—C11—C12—O111.6 (3)
C3—C4—C5—C61.2 (4)C10—C11—C12—O2168.19 (19)
C4—C5—C6—C11.3 (3)S2—C9—S1—C71.18 (16)
C4—C5—C6—C7179.8 (2)S3—C9—S1—C7179.94 (9)
C2—C1—C6—C50.5 (3)C6—C7—S1—C9156.85 (14)
C2—C1—C6—C7179.0 (2)C8—C7—S1—C977.38 (19)
C5—C6—C7—C820.6 (3)S2—C9—S3—C108.69 (16)
C1—C6—C7—C8160.9 (2)S1—C9—S3—C10172.41 (10)
C5—C6—C7—S1101.9 (2)C11—C10—S3—C997.04 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O···O1i0.81 (3)1.85 (3)2.651 (2)177 (3)
Symmetry code: (i) x, y+3, z.

Experimental details

Crystal data
Chemical formulaC12H14O2S3
Mr286.41
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)13.6280 (8), 10.2908 (5), 10.7299 (5)
β (°) 113.039 (2)
V3)1384.77 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.52
Crystal size (mm)0.42 × 0.28 × 0.22
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.811, 0.894
No. of measured, independent and
observed [I > 2σ(I)] reflections
9109, 3020, 2224
Rint0.017
(sin θ/λ)max1)0.671
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.095, 1.03
No. of reflections3020
No. of parameters159
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.27

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1O···O1i0.81 (3)1.85 (3)2.651 (2)177 (3)
Symmetry code: (i) x, y+3, z.
 

Acknowledgements

The authors acknowledge the Department of Chemistry, IIT Madras, for the data collection. MK thanks the CSIR, India, for a fellowship.

References

First citationBruker (2004). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChong, Y. K., Le, T. P. T., Moad, G., Rizzardo, E. & Thang, S. H. (1999). Macromolecules, 32, 2071–2074.  CrossRef CAS Google Scholar
First citationCoady, D. J., Norris, B. C., Lynch, V. M. & Bielawski, C. W. (2008). Macromolecules, 41, 3775–3778.  Web of Science CSD CrossRef CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationKannan, M., Ramkumar, V. & Dhamodharan, R. (2010). Acta Cryst. E66, o1382.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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