(S)-1-[(S)-4-Benzyl-2-thioxothia­zolidin-3-yl]-3-hydroxy­butan-1-one

Yang, J.; Lu, C.; Chen, Z.; Yang, G.

doi:10.1107/S1600536807064355

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o228

https://doi.org/10.1107/S1600536807064355

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(S)-1-[(S)-4-Benzyl-2-thioxothiazolidin-3-yl]-3-hydroxybutan-1-one

Jian-hong Yang,^a Cui-fen Lu,^a Zu-xing Chen ^a and Gui-chun Yang ^a ^*

^aKey Laboratory of Synthesis and Application of Organic Functional Molecules of the Education Ministry, Hubei University, Wuhan, Hubei 430062, People's Republic of China
^*Correspondence e-mail: yangguichun@hubu.edu.cn

(Received 13 November 2007; accepted 29 November 2007; online 6 December 2007)

The title compound, C₁₄H₁₇NO₂S₂, was synthesized by asymmetric aldol condensation of N-acylthiazolidinethione with acetaldehyde. In the molecule, the thiazolidine five-membered ring assumes an envelope conformation. Intermolecular C—H⋯O and intramolecular O—H⋯O and C—H⋯S hydrogen bonding helps to stabilize the structure.

Related literature

For related literature, see: Crimmins et al. (2001 ); Drück & Littke (1980 ); Hodge & Olivo (2004 ).

Experimental

Crystal data

C₁₄H₁₇NO₂S₂
M_r = 295.41
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.0278 (4) Å
b = 8.2637 (4) Å
c = 22.0158 (10) Å
V = 1460.51 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
9324 measured reflections
2845 independent reflections
2648 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.099
S = 1.10
2845 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ), 1175 Friedel pairs
Flack parameter: −0.03 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.82	2.16	2.765 (3)	131
C4—H4⋯O2ⁱ	0.93	2.45	3.325 (3)	158
C9—H9B⋯O1ⁱⁱ	0.97	2.48	3.261 (3)	137
C12—H12A⋯S2	0.97	2.64	3.131 (2)	112
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064355/xu2370sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064355/xu2370Isup2.hkl

checkCIF report

Comment top

The acyl thiazolidinethione enolates mediated aldol reaction is a well accepted and useful method for the preparation of β-hydroxy acids and their derivatives in high enantiomeric purity. As an important chiral intermediates in the synthesis of our target products, the title compound was synthesized and its crystal structure was determined. The configuration of (I) is in accordance with the model for diastereoselective aldol reaction of acylated chiral thiazolidinethiones derived from amino acids (Crimmins et al., 2001; Hodge & Olivo, 2004).

In the molecule the thiazolidine five membered ring assumes an envelope conformation (Fig. 1). The carbonyl group and the thiocarbonyl group adopt a a S-shaped conformation. The crystal packing is stabilized by the C—H···O, O—H···O and C—H···S hydrogen bonds (Table 1).

Related literature top

For related literature, see: Crimmins et al. (2001); Drück & Littke (1980); Hodge & Olivo (2004).

Experimental top

A solution of N-acetyl (4S)-benzylthiazolidinethion (1.25 g, 4.98 mmol) in freshly distilled CH₂Cl₂ (30 ml) at 273 K, was treated dropwise with a solution of TiCl₄ (5.5 ml, 1 M solution in CH₂Cl₂, 5.48 mmol) under nitrogen atmosphere, and the solution allowed to stir for 20 min. To the yellow slurry or suspension was added diisopropylethylamine (4.98 mmol, 0.83 ml). The dark red titanium enolate stirred for 40 min at 273 K. A solution of acetaldehyde (5.5 ml, 1.36 M in CH₂Cl₂, 7.47 mmol) was transferred via cannula to the reaction mixture, which was then stirred for 1 h at 273 K. The reaction was quenched with half-saturated ammonium chloride (30 ml), and the layers were separated. The organic layer was dried over sodium sulfate, filtered, and concentrated. Purification of the crude material by column chromatography afforded the major diastereomer (0.78 g, 55.8%).

Structure description top

For related literature, see: Crimmins et al. (2001); Drück & Littke (1980); Hodge & Olivo (2004).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).

Figures top

Fig. 1. A view of the molecular structure of (I), with displacement ellipsoids at the 30% probability.

(S)-1-[(S)-4-Benzyl-2-thioxothiazolidin-3-yl]-3-hydroxybutan-1-one top

Crystal data top

C₁₄H₁₇NO₂S₂	F(000) = 624
M_r = 295.41	D_x = 1.343 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4884 reflections
a = 8.0278 (4) Å	θ = 2.5–28.0°
b = 8.2637 (4) Å	µ = 0.36 mm⁻¹
c = 22.0158 (10) Å	T = 294 K
V = 1460.51 (12) Å³	Plate, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2648 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 26.0°, θ_min = 1.9°
φ and ω scans	h = −9→8
9324 measured reflections	k = −9→10
2845 independent reflections	l = −27→27

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0502P)² + 0.2097P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.002
2845 reflections	Δρ_max = 0.25 e Å⁻³
174 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1175 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (9)

Crystal data top

C₁₄H₁₇NO₂S₂	V = 1460.51 (12) Å³
M_r = 295.41	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.0278 (4) Å	µ = 0.36 mm⁻¹
b = 8.2637 (4) Å	T = 294 K
c = 22.0158 (10) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2648 reflections with I > 2σ(I)
9324 measured reflections	R_int = 0.059
2845 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.099	Δρ_max = 0.25 e Å⁻³
S = 1.10	Δρ_min = −0.34 e Å⁻³
2845 reflections	Absolute structure: Flack (1983), 1175 Friedel pairs
174 parameters	Absolute structure parameter: −0.03 (9)
0 restraints

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
C1	0.8868 (3)	0.3026 (3)	1.10814 (10)	0.0369 (5)
C2	0.8600 (4)	0.1376 (3)	1.09897 (12)	0.0493 (6)
H2	0.8539	0.0965	1.0597	0.059*
C3	0.8424 (4)	0.0351 (4)	1.14808 (15)	0.0638 (8)
H3	0.8246	−0.0748	1.1416	0.077*
C4	0.8510 (4)	0.0937 (4)	1.20634 (14)	0.0666 (9)
H4	0.8376	0.0243	1.2392	0.080*
C5	0.8794 (4)	0.2547 (5)	1.21564 (11)	0.0665 (9)
H5	0.8868	0.2943	1.2551	0.080*
C6	0.8972 (3)	0.3595 (4)	1.16711 (12)	0.0498 (6)
H6	0.9163	0.4689	1.1742	0.060*
C7	0.9009 (3)	0.4147 (3)	1.05432 (10)	0.0385 (5)
H7A	0.9833	0.3728	1.0262	0.046*
H7B	0.9377	0.5204	1.0679	0.046*
C8	0.7330 (3)	0.4310 (3)	1.02180 (9)	0.0347 (5)
H8	0.6802	0.3241	1.0206	0.042*
C9	0.6146 (3)	0.5474 (3)	1.05289 (11)	0.0462 (6)
H9A	0.6386	0.5542	1.0960	0.055*
H9B	0.5000	0.5130	1.0476	0.055*
C10	0.7229 (3)	0.6529 (3)	0.94970 (10)	0.0331 (5)
C11	0.8081 (3)	0.3718 (3)	0.91621 (10)	0.0387 (5)
C12	0.8266 (3)	0.4103 (3)	0.85002 (10)	0.0416 (6)
H12A	0.8955	0.5060	0.8456	0.050*
H12B	0.7178	0.4345	0.8331	0.050*
C13	0.9047 (3)	0.2712 (3)	0.81438 (10)	0.0409 (5)
H13	1.0170	0.2505	0.8299	0.049*
C14	0.9151 (4)	0.3145 (4)	0.74761 (13)	0.0630 (8)
H14A	0.9682	0.2281	0.7258	0.094*
H14B	0.9788	0.4120	0.7429	0.094*
H14C	0.8049	0.3308	0.7318	0.094*
N1	0.7527 (2)	0.4893 (2)	0.95819 (7)	0.0320 (4)
O1	0.8358 (3)	0.2380 (2)	0.93639 (8)	0.0578 (5)
O2	0.8091 (3)	0.1270 (2)	0.81833 (9)	0.0568 (5)
H2A	0.7974	0.1018	0.8541	0.085*
S1	0.65019 (9)	0.74034 (8)	1.01625 (3)	0.04757 (18)
S2	0.74822 (9)	0.76653 (7)	0.88919 (3)	0.04718 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0316 (11)	0.0443 (13)	0.0348 (11)	0.0028 (9)	0.0001 (9)	0.0052 (10)
C2	0.0572 (15)	0.0449 (14)	0.0459 (14)	0.0026 (13)	−0.0003 (12)	0.0050 (11)
C3	0.0629 (18)	0.0514 (16)	0.077 (2)	0.0004 (15)	0.0006 (16)	0.0263 (15)
C4	0.0532 (16)	0.090 (3)	0.0562 (18)	0.0013 (17)	0.0018 (14)	0.0398 (17)
C5	0.0554 (16)	0.111 (3)	0.0331 (12)	−0.003 (2)	−0.0005 (11)	0.0098 (16)
C6	0.0465 (15)	0.0622 (17)	0.0408 (13)	−0.0039 (13)	−0.0024 (11)	0.0038 (12)
C7	0.0402 (12)	0.0407 (13)	0.0347 (11)	−0.0045 (11)	0.0017 (10)	0.0029 (10)
C8	0.0369 (12)	0.0323 (11)	0.0349 (11)	−0.0029 (9)	0.0003 (10)	0.0053 (9)
C9	0.0474 (14)	0.0459 (14)	0.0455 (13)	0.0038 (12)	0.0112 (11)	0.0064 (11)
C10	0.0335 (11)	0.0288 (11)	0.0369 (11)	−0.0006 (9)	−0.0035 (9)	−0.0008 (8)
C11	0.0486 (14)	0.0305 (12)	0.0370 (11)	−0.0002 (10)	−0.0043 (10)	−0.0009 (9)
C12	0.0526 (15)	0.0340 (12)	0.0381 (12)	0.0019 (11)	0.0000 (11)	−0.0004 (9)
C13	0.0426 (12)	0.0385 (13)	0.0417 (11)	−0.0012 (11)	0.0040 (10)	−0.0058 (11)
C14	0.087 (2)	0.0565 (17)	0.0458 (15)	0.0036 (16)	0.0170 (16)	−0.0079 (13)
N1	0.0394 (10)	0.0258 (8)	0.0309 (8)	0.0002 (8)	−0.0015 (8)	0.0029 (7)
O1	0.1009 (15)	0.0318 (9)	0.0407 (8)	0.0148 (11)	−0.0024 (9)	0.0020 (8)
O2	0.0795 (14)	0.0428 (10)	0.0479 (10)	−0.0154 (10)	0.0071 (10)	−0.0102 (8)
S1	0.0624 (4)	0.0364 (3)	0.0439 (3)	0.0114 (3)	0.0089 (3)	−0.0010 (3)
S2	0.0714 (4)	0.0304 (3)	0.0397 (3)	0.0015 (3)	−0.0005 (3)	0.0067 (2)

Geometric parameters (Å, º) top

C1—C6	1.383 (3)	C9—H9A	0.9700
C1—C2	1.395 (4)	C9—H9B	0.9700
C1—C7	1.508 (3)	C10—N1	1.386 (3)
C2—C3	1.381 (4)	C10—S2	1.643 (2)
C2—H2	0.9300	C10—S1	1.735 (2)
C3—C4	1.373 (5)	C11—O1	1.212 (3)
C3—H3	0.9300	C11—N1	1.412 (3)
C4—C5	1.365 (5)	C11—C12	1.499 (3)
C4—H4	0.9300	C12—C13	1.526 (3)
C5—C6	1.383 (4)	C12—H12A	0.9700
C5—H5	0.9300	C12—H12B	0.9700
C6—H6	0.9300	C13—O2	1.421 (3)
C7—C8	1.532 (3)	C13—C14	1.515 (4)
C7—H7A	0.9700	C13—H13	0.9800
C7—H7B	0.9700	C14—H14A	0.9600
C8—N1	1.489 (2)	C14—H14B	0.9600
C8—C9	1.515 (3)	C14—H14C	0.9600
C8—H8	0.9800	O2—H2A	0.8200
C9—S1	1.809 (2)

C6—C1—C2	118.5 (2)	C8—C9—H9B	110.7
C6—C1—C7	121.6 (2)	S1—C9—H9B	110.7
C2—C1—C7	119.9 (2)	H9A—C9—H9B	108.8
C3—C2—C1	120.1 (3)	N1—C10—S2	130.26 (17)
C3—C2—H2	119.9	N1—C10—S1	110.52 (16)
C1—C2—H2	119.9	S2—C10—S1	119.22 (13)
C4—C3—C2	120.6 (3)	O1—C11—N1	116.4 (2)
C4—C3—H3	119.7	O1—C11—C12	122.1 (2)
C2—C3—H3	119.7	N1—C11—C12	121.4 (2)
C5—C4—C3	119.5 (3)	C11—C12—C13	112.4 (2)
C5—C4—H4	120.2	C11—C12—H12A	109.1
C3—C4—H4	120.2	C13—C12—H12A	109.1
C4—C5—C6	120.8 (3)	C11—C12—H12B	109.1
C4—C5—H5	119.6	C13—C12—H12B	109.1
C6—C5—H5	119.6	H12A—C12—H12B	107.9
C5—C6—C1	120.4 (3)	O2—C13—C14	106.7 (2)
C5—C6—H6	119.8	O2—C13—C12	112.25 (19)
C1—C6—H6	119.8	C14—C13—C12	110.1 (2)
C1—C7—C8	110.84 (18)	O2—C13—H13	109.2
C1—C7—H7A	109.5	C14—C13—H13	109.2
C8—C7—H7A	109.5	C12—C13—H13	109.2
C1—C7—H7B	109.5	C13—C14—H14A	109.5
C8—C7—H7B	109.5	C13—C14—H14B	109.5
H7A—C7—H7B	108.1	H14A—C14—H14B	109.5
N1—C8—C9	106.63 (17)	C13—C14—H14C	109.5
N1—C8—C7	112.01 (18)	H14A—C14—H14C	109.5
C9—C8—C7	113.4 (2)	H14B—C14—H14C	109.5
N1—C8—H8	108.2	C10—N1—C11	129.54 (18)
C9—C8—H8	108.2	C10—N1—C8	115.08 (17)
C7—C8—H8	108.2	C11—N1—C8	115.27 (17)
C8—C9—S1	105.01 (15)	C13—O2—H2A	109.5
C8—C9—H9A	110.7	C10—S1—C9	93.58 (11)
S1—C9—H9A	110.7

C6—C1—C2—C3	0.7 (4)	C11—C12—C13—C14	178.1 (2)
C7—C1—C2—C3	−178.2 (3)	S2—C10—N1—C11	−2.5 (4)
C1—C2—C3—C4	0.0 (5)	S1—C10—N1—C11	178.28 (19)
C2—C3—C4—C5	−0.9 (5)	S2—C10—N1—C8	173.37 (18)
C3—C4—C5—C6	0.9 (5)	S1—C10—N1—C8	−5.8 (2)
C4—C5—C6—C1	−0.1 (4)	O1—C11—N1—C10	174.9 (2)
C2—C1—C6—C5	−0.7 (4)	C12—C11—N1—C10	−6.8 (4)
C7—C1—C6—C5	178.2 (2)	O1—C11—N1—C8	−1.0 (3)
C6—C1—C7—C8	−110.2 (3)	C12—C11—N1—C8	177.3 (2)
C2—C1—C7—C8	68.7 (3)	C9—C8—N1—C10	24.8 (3)
C1—C7—C8—N1	−159.54 (18)	C7—C8—N1—C10	−99.7 (2)
C1—C7—C8—C9	79.7 (2)	C9—C8—N1—C11	−158.7 (2)
N1—C8—C9—S1	−30.8 (2)	C7—C8—N1—C11	76.8 (2)
C7—C8—C9—S1	92.89 (19)	N1—C10—S1—C9	−11.90 (18)
O1—C11—C12—C13	−7.6 (4)	S2—C10—S1—C9	168.79 (15)
N1—C11—C12—C13	174.2 (2)	C8—C9—S1—C10	25.09 (19)
C11—C12—C13—O2	59.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	2.16	2.765 (3)	131
C4—H4···O2ⁱ	0.93	2.45	3.325 (3)	158
C9—H9B···O1ⁱⁱ	0.97	2.48	3.261 (3)	137
C12—H12A···S2	0.97	2.64	3.131 (2)	112

Symmetry codes: (i) −x+3/2, −y, z+1/2; (ii) x−1/2, −y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇NO₂S₂
M_r	295.41
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	8.0278 (4), 8.2637 (4), 22.0158 (10)
V (Å³)	1460.51 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9324, 2845, 2648
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.10
No. of reflections	2845
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.34
Absolute structure	Flack (1983), 1175 Friedel pairs
Absolute structure parameter	−0.03 (9)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	2.16	2.765 (3)	131.2
C4—H4···O2ⁱ	0.93	2.45	3.325 (3)	157.7
C9—H9B···O1ⁱⁱ	0.97	2.48	3.261 (3)	137.0
C12—H12A···S2	0.97	2.64	3.131 (2)	111.9

Symmetry codes: (i) −x+3/2, −y, z+1/2; (ii) x−1/2, −y+1/2, −z+2.

Acknowledgements

This work was supported financially by the Science Foundation of China (grant No. 20772026).

References

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