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

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

doi:10.1107/S1600536809030104

organic compounds

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Volume 65| Part 9| September 2009| Page o2159

doi:10.1107/S1600536809030104

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

Narendar Reddy Gade,^a Y. Manjula,^b Javed Iqbal ^a ^* and Peddy Vishweshwar ^b ^*

^aInstitute of Life Sciences, Hyderabad Central University Campus, Gachibowli, Hyderabad 500 046, India, and ^bDepartment of Analytical Research, Discovery Research, Dr Reddy's Laboratories Ltd, Miyapur, Hyderabad 500 049, India
^*Correspondence e-mail: jiqbal@ilsresearch.org, peddy_vishu@yahoo.co.in

(Received 22 July 2009; accepted 29 July 2009; online 15 August 2009)

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.

Related literature

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

Crystal data

C₁₃H₁₅NOS₂
M_r = 265.39
Monoclinic, P 2₁
a = 8.850 (6) Å
b = 7.189 (5) Å
c = 10.595 (7) Å
β = 95.537 (6)°
V = 670.9 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 298 K
0.50 × 0.40 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.831, T_max = 0.925
7301 measured reflections
2734 independent reflections
2361 reflections with F² > 2σ(F²)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.048
S = 0.86
2734 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ), 1138 Friedel pairs
Flack parameter: −0.05 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.95	2.55	3.408 (4)	150
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Pflugrath, 1999 ); cell refinement: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030104/tk2514sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030104/tk2514Isup2.hkl

checkCIF report

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.

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

	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.
	Fig. 2. Crystal packing of (I) showing the formation of helical chains. The C-H···O contacts are shown as dashed lines.
	Fig. 3. Synthesis of (I).

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

Crystal data top

C₁₃H₁₅NOS₂	F(000) = 280
M_r = 265.39	D_x = 1.314 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2yb	Cell parameters from 3674 reflections
a = 8.850 (6) Å	θ = 2.3–27.4°
b = 7.189 (5) Å	µ = 0.38 mm⁻¹
c = 10.595 (7) Å	T = 298 K
β = 95.537 (6)°	Prism, yellow
V = 670.9 (8) Å³	0.50 × 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^-1	R_int = 0.038
ω scans	θ_max = 27.4°
Absorption correction: multi-scan (Jacobson, 1998)	h = −11→11
T_min = 0.831, T_max = 0.925	k = −6→9
7301 measured reflections	l = −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) = 0.048	Δρ_max = 0.32 e Å⁻³
S = 0.86	Δρ_min = −0.35 e Å⁻³
2734 reflections	Absolute structure: Flack (1983), 1138 Friedel pairs
170 parameters	Absolute structure parameter: −0.05 (6)
H-atom parameters constrained

Crystal data top

C₁₃H₁₅NOS₂	V = 670.9 (8) Å³
M_r = 265.39	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.850 (6) Å	µ = 0.38 mm⁻¹
b = 7.189 (5) Å	T = 298 K
c = 10.595 (7) Å	0.50 × 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)
T_min = 0.831, T_max = 0.925	R_int = 0.038
7301 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.048	Δρ_max = 0.32 e Å⁻³
S = 0.86	Δρ_min = −0.35 e Å⁻³
2734 reflections	Absolute structure: Flack (1983), 1138 Friedel pairs
170 parameters	Absolute structure parameter: −0.05 (6)

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

	x	y	z	U_iso*/U_eq
S1	0.55104 (6)	1.08609 (10)	0.94969 (5)	0.0574 (2)
S2	0.80540 (7)	1.31770 (10)	1.04864 (6)	0.0630 (2)
O1	0.96079 (17)	1.0605 (2)	0.69074 (15)	0.0720 (6)
N1	0.79082 (15)	1.1039 (2)	0.83154 (13)	0.0410 (4)
C1	0.6994 (2)	0.9543 (2)	0.76431 (19)	0.0436 (6)
C2	0.5366 (2)	0.9806 (2)	0.79429 (19)	0.0498 (7)
C3	0.7324 (2)	1.1748 (2)	0.93706 (19)	0.0462 (6)
C4	0.7616 (2)	0.7610 (2)	0.80159 (19)	0.0469 (6)
C5	0.7183 (2)	0.6180 (2)	0.70140 (17)	0.0441 (6)
C6	0.5872 (2)	0.5119 (2)	0.7014 (2)	0.0561 (7)
C7	0.5469 (3)	0.3871 (3)	0.6051 (2)	0.0673 (9)
C8	0.6379 (3)	0.3610 (3)	0.5087 (2)	0.0704 (9)
C9	0.7667 (3)	0.4651 (3)	0.5063 (2)	0.0719 (9)
C10	0.8074 (2)	0.5935 (3)	0.60097 (19)	0.0569 (7)
C11	0.9289 (2)	1.1496 (2)	0.7801 (2)	0.0501 (7)
C12	1.0320 (2)	1.3001 (3)	0.8384 (2)	0.0545 (7)
C13	1.1629 (2)	1.3369 (4)	0.7610 (2)	0.0861 (10)
H1	0.70330	0.96970	0.67560	0.0520*
H6	0.52430	0.52600	0.76860	0.0670*
H7	0.45570	0.31750	0.60530	0.0790*
H8	0.61000	0.27260	0.44400	0.0830*
H9	0.83030	0.44600	0.44020	0.0870*
H10	0.89540	0.66810	0.59680	0.0690*
H21	0.48380	1.06070	0.73390	0.0600*
H22	0.48550	0.86440	0.79480	0.0590*
H41	0.72130	0.72350	0.87750	0.0550*
H42	0.86910	0.76750	0.81570	0.0560*
H121	1.07080	1.26210	0.92110	0.0650*
H122	0.97480	1.41110	0.84380	0.0650*
H131	1.19300	1.46340	0.77050	0.1050*
H132	1.24580	1.25860	0.78930	0.1050*
H133	1.13230	1.31200	0.67430	0.1050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0512 (2)	0.0621 (3)	0.0611 (3)	−0.0066 (3)	0.0167 (2)	−0.0116 (3)
S2	0.0587 (3)	0.0640 (4)	0.0664 (3)	−0.0025 (3)	0.0059 (2)	−0.0247 (3)
O1	0.0664 (9)	0.0751 (11)	0.0796 (10)	−0.0150 (9)	0.0330 (8)	−0.0265 (10)
N1	0.0401 (7)	0.0364 (8)	0.0470 (8)	−0.0001 (7)	0.0062 (6)	−0.0019 (7)
C1	0.0419 (10)	0.0430 (11)	0.0458 (10)	−0.0008 (8)	0.0035 (8)	0.0002 (8)
C2	0.0417 (10)	0.0508 (13)	0.0561 (12)	−0.0027 (9)	0.0011 (8)	−0.0019 (9)
C3	0.0427 (10)	0.0438 (11)	0.0513 (11)	0.0037 (8)	0.0008 (8)	−0.0042 (9)
C4	0.0510 (11)	0.0393 (11)	0.0487 (11)	0.0028 (8)	−0.0031 (8)	−0.0011 (8)
C5	0.0453 (10)	0.0389 (12)	0.0467 (10)	0.0008 (8)	−0.0027 (8)	0.0025 (8)
C6	0.0647 (13)	0.0460 (13)	0.0569 (12)	−0.0083 (10)	0.0017 (10)	0.0087 (9)
C7	0.0828 (17)	0.0465 (14)	0.0678 (15)	−0.0207 (11)	−0.0179 (13)	0.0093 (11)
C8	0.104 (2)	0.0511 (15)	0.0517 (13)	−0.0052 (13)	−0.0146 (13)	−0.0034 (11)
C9	0.0992 (19)	0.0603 (15)	0.0580 (14)	0.0079 (15)	0.0176 (13)	−0.0055 (12)
C10	0.0579 (11)	0.0527 (12)	0.0617 (12)	0.0015 (12)	0.0134 (9)	−0.0026 (12)
C11	0.0415 (11)	0.0480 (13)	0.0617 (12)	0.0026 (8)	0.0095 (9)	−0.0011 (9)
C12	0.0430 (10)	0.0488 (12)	0.0711 (13)	−0.0016 (10)	0.0032 (9)	−0.0073 (11)
C13	0.0543 (13)	0.086 (2)	0.121 (2)	−0.0223 (15)	0.0242 (13)	−0.0216 (19)

Geometric parameters (Å, º) top

S1—C2	1.806 (2)	C12—C13	1.506 (3)
S1—C3	1.744 (2)	C1—H1	0.9500
S2—C3	1.650 (2)	C2—H21	0.9500
O1—C11	1.199 (3)	C2—H22	0.9500
N1—C1	1.486 (2)	C4—H41	0.9500
N1—C3	1.374 (3)	C4—H42	0.9500
N1—C11	1.424 (2)	C6—H6	0.9500
C1—C2	1.517 (3)	C7—H7	0.9500
C1—C4	1.532 (2)	C8—H8	0.9500
C4—C5	1.501 (3)	C9—H9	0.9500
C5—C6	1.389 (3)	C10—H10	0.9500
C5—C10	1.395 (3)	C12—H121	0.9500
C6—C7	1.380 (3)	C12—H122	0.9500
C7—C8	1.373 (3)	C13—H131	0.9500
C8—C9	1.366 (4)	C13—H132	0.9500
C9—C10	1.385 (3)	C13—H133	0.9500
C11—C12	1.509 (3)

C2—S1—C3	93.92 (9)	C1—C2—H21	110.00
C1—N1—C3	115.36 (14)	C1—C2—H22	111.00
C1—N1—C11	115.55 (14)	H21—C2—H22	109.00
C3—N1—C11	129.05 (14)	C1—C4—H41	109.00
N1—C1—C2	107.08 (13)	C1—C4—H42	109.00
N1—C1—C4	111.56 (15)	C5—C4—H41	108.00
C2—C1—C4	112.58 (14)	C5—C4—H42	109.00
S1—C2—C1	104.96 (13)	H41—C4—H42	109.00
S1—C3—S2	118.18 (11)	C5—C6—H6	119.00
S1—C3—N1	110.37 (12)	C7—C6—H6	120.00
S2—C3—N1	131.43 (14)	C6—C7—H7	120.00
C1—C4—C5	112.21 (15)	C8—C7—H7	119.00
C4—C5—C6	122.19 (16)	C7—C8—H8	120.00
C4—C5—C10	120.09 (16)	C9—C8—H8	121.00
C6—C5—C10	117.67 (16)	C8—C9—H9	119.00
C5—C6—C7	120.91 (19)	C10—C9—H9	120.00
C6—C7—C8	120.7 (2)	C5—C10—H10	119.00
C7—C8—C9	119.3 (2)	C9—C10—H10	120.00
C8—C9—C10	120.7 (2)	C11—C12—H121	109.00
C5—C10—C9	120.65 (18)	C11—C12—H122	109.00
O1—C11—N1	117.07 (15)	C13—C12—H121	109.00
O1—C11—C12	121.82 (17)	C13—C12—H122	109.00
N1—C11—C12	121.09 (16)	H121—C12—H122	109.00
C11—C12—C13	111.70 (18)	C12—C13—H131	109.00
N1—C1—H1	109.00	C12—C13—H132	110.00
C2—C1—H1	109.00	C12—C13—H133	109.00
C4—C1—H1	108.00	H131—C13—H132	109.00
S1—C2—H21	110.00	H131—C13—H133	110.00
S1—C2—H22	111.00	H132—C13—H133	109.00

C3—S1—C2—C1	22.91 (12)	C4—C1—C2—S1	93.51 (15)
C2—S1—C3—S2	171.92 (11)	N1—C1—C4—C5	−155.93 (15)
C2—S1—C3—N1	−9.64 (13)	C2—C1—C4—C5	83.7 (2)
C3—N1—C1—C2	25.15 (19)	C1—C4—C5—C6	−91.3 (2)
C3—N1—C1—C4	−98.44 (17)	C1—C4—C5—C10	86.0 (2)
C11—N1—C1—C2	−156.77 (15)	C4—C5—C6—C7	177.20 (17)
C11—N1—C1—C4	79.65 (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—S2	170.47 (14)	C6—C5—C10—C9	−1.1 (3)
C11—N1—C3—S1	174.53 (14)	C5—C6—C7—C8	1.9 (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—C10	1.2 (3)
C1—N1—C11—C12	179.47 (16)	C8—C9—C10—C5	0.6 (3)
C3—N1—C11—O1	175.56 (17)	O1—C11—C12—C13	7.3 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95	2.55	3.408 (4)	150

Symmetry code: (i) −x+2, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅NOS₂
M_r	265.39
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	8.850 (6), 7.189 (5), 10.595 (7)
β (°)	95.537 (6)
V (Å³)	670.9 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.831, 0.925
No. of measured, independent and observed [F² > 2σ(F²)] reflections	7301, 2734, 2361
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.048, 0.86
No. of reflections	2734
No. of parameters	170
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.35
Absolute structure	Flack (1983), 1138 Friedel pairs
Absolute structure parameter	−0.05 (6)

Computer programs: CrystalClear (Pflugrath, 1999), CrystalStructure (Molecular Structure Corporation & Rigaku, 2006), SIR2004 (Burla et al., 2005), CRYSTALS (Betteridge et al., 2003), X-SEED (Barbour et al., 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95	2.55	3.408 (4)	150

Symmetry code: (i) −x+2, y−1/2, −z+1.

Footnotes

†ILS Publication No. ILS-MCO-0904.

Acknowledgements

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

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