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Acta Cryst. (2009). E65, o2159    [ doi:10.1107/S1600536809030104 ]

1-[(4S)-4-Benzyl-2-thioxo-1,3-thiazolidin-3-yl]propan-1-one

N. R. Gade, Y. Manjula, J. Iqbal and P. Vishweshwar

Abstract top

The analysis of the title chiral auxiliary compound, C13H15NOS2, has enabled the determination of the absolute configuration at the benzyl-bearing ring C atom as S. In the crystal structure, molecules aggregate into helical chains along the b axis via C-H...O contacts.

Comment top

N-Acyl thiazolidinethiones, e.g. (I), are versatile chiral auxiliaries for asymmetric aldol reactions Crimmins & Chaudhary (2000). Many complex natural products have been synthesized using these auxiliaries (Crimmins et al. 2005; Crimmins & Haley, 2006; Crimmins & Dechert, 2009). The synthesis of (I) starts from amino alcohol 2 which was converted to thiazolidinethione 3 by reacting with carbon disulfide followed by treatment with propionyl chloride (Fig. 3) (Crimmins & Chaudhary, 2000).

The single crystal analysis of (I), Fig. 1, allowed the determination of the absolute configuration of C1 as S. The crystal structure shows the molecules to aggregate into helical chains along the screw axis via C9—H9···O1 contacts (Fig. 2, Table 1).

Related literature top

For background to the use of N-acyl thiazolidinethiones as versatile chiral auxiliaries for asymmetric aldol reactions, see: Crimmins & Chaudhary (2000); Crimmins et al. (2005); Crimmins & Haley (2006); Crimmins & Dechert (2009). For the synthesis, see: McKennon & Meyer (1993); Delaunay et al. (1995); Lu et al. (2009).

Experimental top

To a solution of β-amino alcohol 2 (10 mmol) (McKennon & Meyer, 1993) in aqueous 1.0 N potassium hydroxide (50 ml) was added carbon disulfide (50 mmol, 3.0 ml) slowly. The reaction mixture was refluxed at 110 °C for 12 h to give the desired thiazolidinethione 3 (Delaunay et al. 1995). To a solution of compound 3 (0.478 mmol) in dichloromethane (DCM, 3 ml) was added triethylamine (0.956 mmol) and the temperature was maintained at -40 to -78 °C. To that mixture was added propionyl chloride (0.574 mmol) drop wise. The mixture was stirred for 1–2 h, diluted with DCM (10 ml), washed with water (2 x 10 ml), dried over anhydrous Na2SO4 and concentrated low vacuum to give (I) as a light-yellow solid; mp. 374–376 K (lit. mp. 374.1 K (Lu et al. 2009)).

Compound (I) (50 mg) was dissolved in 2:1 DCM/EtOAC (1.0 ml) and left in freezer (10 °C) until fine crystals appeared. Crystals were separated from soluton and washed with hexane and dried under vacuum.

Refinement top

The H atoms were positioned geometrically and refined in the riding model approximation with C—H = 0.95 Å, and with Uiso(H) set to 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Pflugrath, 1999); cell refinement: CrystalClear (Pflugrath, 1999); data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku, 2006); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: X-SEED (Barbour et al., 2001); software used to prepare material for publication: CrystalStructure (Molecular Structure Corporation & Rigaku, 2006).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.
[Figure 2] Fig. 2. Crystal packing of (I) showing the formation of helical chains. The C-H···O contacts are shown as dashed lines.
[Figure 3] Fig. 3. Synthesis of (I).
1-[(4S)-4-Benzyl-2-thioxo-1,3-thiazolidin-3-yl]propan-1-one top
Crystal data top
C13H15NOS2F(000) = 280
Mr = 265.39Dx = 1.314 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ybCell parameters from 3674 reflections
a = 8.850 (6) Åθ = 2.3–27.4°
b = 7.189 (5) ŵ = 0.38 mm−1
c = 10.595 (7) ÅT = 298 K
β = 95.537 (6)°Prism, yellow
V = 670.9 (8) Å30.50 × 0.40 × 0.20 mm
Z = 2
Data collection top
Rigaku Mercury
diffractometer		2361 reflections with F2 > 2σ(F2)
Detector resolution: 7.31 pixels mm-1Rint = 0.038
ω scansθmax = 27.4°
Absorption correction: multi-scan
(Jacobson, 1998)		h = −11→11
Tmin = 0.831, Tmax = 0.925k = −6→9
7301 measured reflectionsl = −13→13
2734 independent reflections
Refinement top
Refinement on F2 Chebychev polynomial with 3 parameters (Carruthers & Watkin, 1979) 10359.0000 14093.9000 3595.6900
R[F2 > 2σ(F2)] = 0.041(Δ/σ)max < 0.001
wR(F2) = 0.048Δρmax = 0.32 e Å−3
S = 0.86Δρmin = −0.35 e Å−3
2734 reflectionsAbsolute structure: Flack (1983), 1138 Friedel pairs
170 parametersFlack parameter: −0.05 (6)
H-atom parameters constrained
Crystal data top
C13H15NOS2V = 670.9 (8) Å3
Mr = 265.39Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.850 (6) ŵ = 0.38 mm−1
b = 7.189 (5) ÅT = 298 K
c = 10.595 (7) Å0.50 × 0.40 × 0.20 mm
β = 95.537 (6)°
Data collection top
Rigaku Mercury
diffractometer		2734 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		2361 reflections with F2 > 2σ(F2)
Tmin = 0.831, Tmax = 0.925Rint = 0.038
7301 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.048Δρmax = 0.32 e Å−3
S = 0.86Δρmin = −0.35 e Å−3
2734 reflectionsAbsolute structure: Flack (1983), 1138 Friedel pairs
170 parametersFlack parameter: −0.05 (6)
? restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.55104 (6)1.08609 (10)0.94969 (5)0.0574 (2)
S20.80540 (7)1.31770 (10)1.04864 (6)0.0630 (2)
O10.96079 (17)1.0605 (2)0.69074 (15)0.0720 (6)
N10.79082 (15)1.1039 (2)0.83154 (13)0.0410 (4)
C10.6994 (2)0.9543 (2)0.76431 (19)0.0436 (6)
C20.5366 (2)0.9806 (2)0.79429 (19)0.0498 (7)
C30.7324 (2)1.1748 (2)0.93706 (19)0.0462 (6)
C40.7616 (2)0.7610 (2)0.80159 (19)0.0469 (6)
C50.7183 (2)0.6180 (2)0.70140 (17)0.0441 (6)
C60.5872 (2)0.5119 (2)0.7014 (2)0.0561 (7)
C70.5469 (3)0.3871 (3)0.6051 (2)0.0673 (9)
C80.6379 (3)0.3610 (3)0.5087 (2)0.0704 (9)
C90.7667 (3)0.4651 (3)0.5063 (2)0.0719 (9)
C100.8074 (2)0.5935 (3)0.60097 (19)0.0569 (7)
C110.9289 (2)1.1496 (2)0.7801 (2)0.0501 (7)
C121.0320 (2)1.3001 (3)0.8384 (2)0.0545 (7)
C131.1629 (2)1.3369 (4)0.7610 (2)0.0861 (10)
H10.703300.969700.675600.0520*
H60.524300.526000.768600.0670*
H70.455700.317500.605300.0790*
H80.610000.272600.444000.0830*
H90.830300.446000.440200.0870*
H100.895400.668100.596800.0690*
H210.483801.060700.733900.0600*
H220.485500.864400.794800.0590*
H410.721300.723500.877500.0550*
H420.869100.767500.815700.0560*
H1211.070801.262100.921100.0650*
H1220.974801.411100.843800.0650*
H1311.193001.463400.770500.1050*
H1321.245801.258600.789300.1050*
H1331.132301.312000.674300.1050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0512 (2)0.0621 (3)0.0611 (3)−0.0066 (3)0.0167 (2)−0.0116 (3)
S20.0587 (3)0.0640 (4)0.0664 (3)−0.0025 (3)0.0059 (2)−0.0247 (3)
O10.0664 (9)0.0751 (11)0.0796 (10)−0.0150 (9)0.0330 (8)−0.0265 (10)
N10.0401 (7)0.0364 (8)0.0470 (8)−0.0001 (7)0.0062 (6)−0.0019 (7)
C10.0419 (10)0.0430 (11)0.0458 (10)−0.0008 (8)0.0035 (8)0.0002 (8)
C20.0417 (10)0.0508 (13)0.0561 (12)−0.0027 (9)0.0011 (8)−0.0019 (9)
C30.0427 (10)0.0438 (11)0.0513 (11)0.0037 (8)0.0008 (8)−0.0042 (9)
C40.0510 (11)0.0393 (11)0.0487 (11)0.0028 (8)−0.0031 (8)−0.0011 (8)
C50.0453 (10)0.0389 (12)0.0467 (10)0.0008 (8)−0.0027 (8)0.0025 (8)
C60.0647 (13)0.0460 (13)0.0569 (12)−0.0083 (10)0.0017 (10)0.0087 (9)
C70.0828 (17)0.0465 (14)0.0678 (15)−0.0207 (11)−0.0179 (13)0.0093 (11)
C80.104 (2)0.0511 (15)0.0517 (13)−0.0052 (13)−0.0146 (13)−0.0034 (11)
C90.0992 (19)0.0603 (15)0.0580 (14)0.0079 (15)0.0176 (13)−0.0055 (12)
C100.0579 (11)0.0527 (12)0.0617 (12)0.0015 (12)0.0134 (9)−0.0026 (12)
C110.0415 (11)0.0480 (13)0.0617 (12)0.0026 (8)0.0095 (9)−0.0011 (9)
C120.0430 (10)0.0488 (12)0.0711 (13)−0.0016 (10)0.0032 (9)−0.0073 (11)
C130.0543 (13)0.086 (2)0.121 (2)−0.0223 (15)0.0242 (13)−0.0216 (19)
Geometric parameters (Å, °) top
S1—C21.806 (2)C12—C131.506 (3)
S1—C31.744 (2)C1—H10.9500
S2—C31.650 (2)C2—H210.9500
O1—C111.199 (3)C2—H220.9500
N1—C11.486 (2)C4—H410.9500
N1—C31.374 (3)C4—H420.9500
N1—C111.424 (2)C6—H60.9500
C1—C21.517 (3)C7—H70.9500
C1—C41.532 (2)C8—H80.9500
C4—C51.501 (3)C9—H90.9500
C5—C61.389 (3)C10—H100.9500
C5—C101.395 (3)C12—H1210.9500
C6—C71.380 (3)C12—H1220.9500
C7—C81.373 (3)C13—H1310.9500
C8—C91.366 (4)C13—H1320.9500
C9—C101.385 (3)C13—H1330.9500
C11—C121.509 (3)
C2—S1—C393.92 (9)C1—C2—H21110.00
C1—N1—C3115.36 (14)C1—C2—H22111.00
C1—N1—C11115.55 (14)H21—C2—H22109.00
C3—N1—C11129.05 (14)C1—C4—H41109.00
N1—C1—C2107.08 (13)C1—C4—H42109.00
N1—C1—C4111.56 (15)C5—C4—H41108.00
C2—C1—C4112.58 (14)C5—C4—H42109.00
S1—C2—C1104.96 (13)H41—C4—H42109.00
S1—C3—S2118.18 (11)C5—C6—H6119.00
S1—C3—N1110.37 (12)C7—C6—H6120.00
S2—C3—N1131.43 (14)C6—C7—H7120.00
C1—C4—C5112.21 (15)C8—C7—H7119.00
C4—C5—C6122.19 (16)C7—C8—H8120.00
C4—C5—C10120.09 (16)C9—C8—H8121.00
C6—C5—C10117.67 (16)C8—C9—H9119.00
C5—C6—C7120.91 (19)C10—C9—H9120.00
C6—C7—C8120.7 (2)C5—C10—H10119.00
C7—C8—C9119.3 (2)C9—C10—H10120.00
C8—C9—C10120.7 (2)C11—C12—H121109.00
C5—C10—C9120.65 (18)C11—C12—H122109.00
O1—C11—N1117.07 (15)C13—C12—H121109.00
O1—C11—C12121.82 (17)C13—C12—H122109.00
N1—C11—C12121.09 (16)H121—C12—H122109.00
C11—C12—C13111.70 (18)C12—C13—H131109.00
N1—C1—H1109.00C12—C13—H132110.00
C2—C1—H1109.00C12—C13—H133109.00
C4—C1—H1108.00H131—C13—H132109.00
S1—C2—H21110.00H131—C13—H133110.00
S1—C2—H22111.00H132—C13—H133109.00
C3—S1—C2—C122.91 (12)C4—C1—C2—S193.51 (15)
C2—S1—C3—S2171.92 (11)N1—C1—C4—C5−155.93 (15)
C2—S1—C3—N1−9.64 (13)C2—C1—C4—C583.7 (2)
C3—N1—C1—C225.15 (19)C1—C4—C5—C6−91.3 (2)
C3—N1—C1—C4−98.44 (17)C1—C4—C5—C1086.0 (2)
C11—N1—C1—C2−156.77 (15)C4—C5—C6—C7177.20 (17)
C11—N1—C1—C479.65 (19)C10—C5—C6—C7−0.1 (3)
C1—N1—C3—S1−7.69 (18)C4—C5—C10—C9−178.46 (18)
C1—N1—C3—S2170.47 (14)C6—C5—C10—C9−1.1 (3)
C11—N1—C3—S1174.53 (14)C5—C6—C7—C81.9 (3)
C11—N1—C3—S2−7.3 (3)C6—C7—C8—C9−2.4 (3)
C1—N1—C11—O1−2.2 (2)C7—C8—C9—C101.2 (3)
C1—N1—C11—C12179.47 (16)C8—C9—C10—C50.6 (3)
C3—N1—C11—O1175.56 (17)O1—C11—C12—C137.3 (3)
C3—N1—C11—C12−2.8 (3)N1—C11—C12—C13−174.42 (17)
N1—C1—C2—S1−29.44 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.952.553.408 (4)150
Symmetry codes: (i) −x+2, y−1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O1i0.952.553.408 (4)150
Symmetry codes: (i) −x+2, y−1/2, −z+1.
Acknowledgements top

NRG thanks the Institute of Life Sciences for allowing him to pursue this work as part of his PhD thesis.

references
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