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Acta Cryst. (2010). E66, o2633    [ doi:10.1107/S1600536810037396 ]

3-(tert-Butoxycarbonyl)-2-(4-chlorophenyl)-1,3-thiazolidine-4-carboxylic acid

S.-M. Ding

Abstract top

In the title compound, C15H18ClNO4S, the thiazolidine ring adopts a twisted conformation about the S-C(methylene) bond. The dihedral angle between the five- and six-membered rings is 77.2 (3)°. In the crystal, the molecules are linked by O-H...O hydrogen bonds, generating C(7) chains propagating in [100].

Comment top

Recently, 3-tert-butoxycarbonyl-2-arylthiazolidine-4-carboxylic acid derivatives have been reported to possess antimicrobial and antitumor activities (Song et al., 2009; Lu et al., 2010). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). There are intermolecular O—H···O hydrogen bonds in (I).

Related literature top

For background to the biological properties of the title compound, see: Lu et al. (2010); Song et al. (2009). For reference bond-length data, see: Allen et al. (1987). PLATON indicates 0 Frie

Experimental top

A mixture of L-cysteine (1.41 g, 10 mmol) and 4-chlorobenzaldehyde (1.4 g, 10 mmol) in methanol (100 ml) was stirred at room temperature for 10 h, and the separated solid was collected, washed with diethyl ether, and dried to obtain 2-(4-chlorophenyl)thiazolidine-4-carboxylic with yield of 90%. In ice water, 2-(4-chlorophenyl)thiazolidine-4-carboxylic (1 mmol) was dissolved in 1 N NaOH (1 ml) and 1,4-dioxane (10 ml); then di-tert-butyldicarbonate (1 mmol) was added slowly and stirred at room temperature for 6 h. The reaction mixture was concentrated in a vacuum and washed with ethyl acetate (10 ml). The aqueous phase was adjusted to pH 4 by adding 1 N HCl, then extracted with ethyl acetate, dried with magnesium sulfate, filtered, After keeping the filtrate in air for 5 d, colorless block-shaped crystals of (I) were formed.

Refinement top

All H atoms were positioned geometrically (C—H = 0.93 Å for the aromatic H atoms and C—H = 0.96 Å for the aliphatic H atoms) and were refined as riding, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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
[Figure 1] Fig. 1. The structure of (I) showing 30% probability displacement ellipsoids.
3-(tert-Butoxycarbonyl)-2-(4-chlorophenyl)-1,3-thiazolidine-4-carboxylic acid top
Crystal data top
C15H18ClNO4SF(000) = 360
Mr = 343.81Dx = 1.343 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 25 reflections
a = 6.4600 (13) Åθ = 9–12°
b = 10.641 (2) ŵ = 0.36 mm−1
c = 12.411 (3) ÅT = 293 K
β = 94.52 (3)°Block, colorless
V = 850.5 (3) Å30.30 × 0.20 × 0.10 mm
Z = 2
Data collection top
Enraf–Nonius CAD-4
diffractometer		1363 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
Graphite monochromatorθmax = 25.3°, θmin = 1.7°
ω/2θ scanh = −7→7
Absorption correction: ψ scan
(North et al., 1968)		k = 0→12
Tmin = 0.899, Tmax = 0.965l = 0→14
1638 measured reflections200 standard reflections every 3 reflections
1638 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.159 w = 1/[σ2(Fo2) + (0.0649P)2 + 1.2912P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1638 reflectionsΔρmax = 0.43 e Å−3
185 parametersΔρmin = −0.37 e Å−3
89 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.09 (19)
Crystal data top
C15H18ClNO4SV = 850.5 (3) Å3
Mr = 343.81Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.4600 (13) ŵ = 0.36 mm−1
b = 10.641 (2) ÅT = 293 K
c = 12.411 (3) Å0.30 × 0.20 × 0.10 mm
β = 94.52 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1363 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.899, Tmax = 0.965θmax = 25.3°
1638 measured reflections200 standard reflections every 3 reflections
1638 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.062H-atom parameters constrained
wR(F2) = 0.159Δρmax = 0.43 e Å−3
S = 1.08Δρmin = −0.37 e Å−3
1638 reflectionsAbsolute structure: Flack (1983)
185 parametersFlack parameter: −0.09 (19)
89 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
xyzUiso*/Ueq
C10.3575 (11)0.4607 (7)0.7980 (6)0.0457 (16)
H10.47760.49840.77680.055*
C20.3229 (12)0.3336 (8)0.7816 (6)0.0519 (17)
H20.41830.28630.74650.062*
C30.1505 (12)0.2766 (8)0.8162 (7)0.0555 (18)
C40.0021 (13)0.3440 (8)0.8654 (6)0.0585 (18)
H4−0.11630.30540.88790.070*
C50.0368 (11)0.4720 (7)0.8800 (6)0.0492 (16)
H5−0.06040.51950.91360.059*
C60.2109 (9)0.5308 (6)0.8464 (5)0.0349 (13)
C70.2361 (9)0.6677 (6)0.8692 (4)0.0358 (13)
H70.10360.70230.88870.043*
C80.4770 (9)0.8351 (7)0.8161 (5)0.0409 (14)
H80.43640.91650.78420.049*
O10.8408 (8)0.8639 (5)0.8109 (4)0.060
C90.4827 (11)0.8471 (7)0.9375 (5)0.0494 (16)
H9A0.37600.90430.95830.059*
H9B0.61700.87740.96710.059*
C100.6910 (9)0.8031 (8)0.7835 (5)0.0459 (17)
C110.2163 (9)0.7473 (7)0.6838 (5)0.0373 (14)
C120.2095 (11)0.8500 (8)0.5098 (5)0.0520 (18)
C130.2564 (14)0.7386 (9)0.4443 (8)0.070
H13A0.39990.71610.45860.106*
H13B0.22930.75790.36900.106*
H13C0.17050.66950.46290.106*
C14−0.0195 (13)0.8803 (9)0.4998 (8)0.069
H14A−0.09750.80560.51230.104*
H14B−0.05830.91170.42860.104*
H14C−0.04830.94290.55230.104*
C150.3316 (15)0.9649 (10)0.4750 (7)0.078 (3)
H15A0.29431.03710.51560.116*
H15B0.29920.98020.39930.116*
H15C0.47770.94920.48830.116*
Cl10.1156 (5)0.1156 (2)0.7961 (2)0.0908 (9)
N10.3167 (7)0.7456 (5)0.7848 (4)0.0336 (11)
O20.6980 (6)0.7001 (6)0.7256 (4)0.0534 (12)
H2A0.81850.68580.71310.080*
O30.0721 (6)0.6749 (5)0.6573 (3)0.0398 (10)
O40.2916 (7)0.8324 (5)0.6216 (3)0.0448 (11)
S10.4357 (3)0.68989 (18)0.98363 (12)0.0481 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.047 (4)0.049 (3)0.041 (4)0.001 (3)0.003 (3)0.001 (3)
C20.059 (4)0.055 (4)0.041 (4)0.010 (3)0.001 (3)−0.006 (3)
C30.064 (4)0.047 (4)0.053 (4)−0.006 (3)−0.014 (3)0.007 (3)
C40.060 (4)0.057 (4)0.058 (4)−0.014 (3)0.004 (3)0.004 (4)
C50.046 (3)0.056 (4)0.045 (4)−0.004 (3)0.003 (3)0.011 (3)
C60.039 (3)0.035 (3)0.031 (3)0.000 (2)0.002 (2)0.008 (3)
C70.035 (3)0.043 (4)0.030 (3)0.005 (3)0.003 (2)0.006 (3)
C80.042 (3)0.038 (3)0.042 (3)0.001 (3)−0.004 (3)0.001 (3)
O10.0600.0600.0600.0000.0050.000
C90.052 (4)0.052 (4)0.043 (3)0.008 (3)−0.006 (3)−0.009 (3)
C100.026 (3)0.074 (5)0.037 (3)−0.015 (3)−0.006 (2)−0.002 (3)
C110.028 (3)0.053 (4)0.031 (3)0.009 (3)−0.002 (2)−0.002 (3)
C120.050 (4)0.070 (5)0.035 (3)−0.008 (4)−0.003 (3)0.019 (4)
C130.0700.0700.0700.0000.0060.000
C140.0700.0700.0700.0000.0060.000
C150.086 (6)0.085 (7)0.061 (5)−0.007 (5)0.006 (4)0.036 (5)
Cl10.115 (2)0.0475 (12)0.1032 (19)−0.0122 (13)−0.0338 (16)0.0021 (13)
N10.030 (2)0.038 (3)0.033 (2)0.004 (2)0.0010 (19)0.001 (2)
O20.032 (2)0.066 (3)0.064 (3)−0.010 (2)0.012 (2)−0.018 (3)
O30.029 (2)0.058 (3)0.0317 (19)−0.007 (2)−0.0026 (15)−0.005 (2)
O40.044 (2)0.055 (3)0.035 (2)−0.015 (2)0.0001 (18)0.016 (2)
S10.0578 (10)0.0564 (10)0.0285 (7)−0.0005 (9)−0.0071 (6)−0.0025 (9)
Geometric parameters (Å, º) top
C1—C61.379 (9)C9—H9A0.9700
C1—C21.384 (11)C9—H9B0.9700
C1—H10.9300C10—O21.313 (9)
C2—C31.367 (11)C11—O31.234 (8)
C2—H20.9300C11—O41.308 (8)
C3—C41.378 (12)C11—N11.365 (8)
C3—Cl11.744 (8)C12—O41.457 (8)
C4—C51.390 (11)C12—C131.483 (12)
C4—H40.9300C12—C141.510 (11)
C5—C61.380 (9)C12—C151.535 (11)
C5—H50.9300C13—H13A0.9600
C6—C71.490 (9)C13—H13B0.9600
C7—N11.464 (8)C13—H13C0.9600
C7—S11.857 (6)C14—H14A0.9600
C7—H70.9800C14—H14B0.9600
C8—N11.437 (8)C14—H14C0.9600
C8—C101.510 (9)C15—H15A0.9600
C8—C91.510 (9)C15—H15B0.9600
C8—H80.9800C15—H15C0.9600
O1—C101.191 (8)O2—H2A0.8200
C9—S11.801 (8)
C6—C1—C2119.0 (7)O1—C10—O2123.2 (6)
C6—C1—H1120.5O1—C10—C8122.8 (7)
C2—C1—H1120.5O2—C10—C8114.0 (5)
C3—C2—C1120.9 (7)O3—C11—O4125.6 (5)
C3—C2—H2119.6O3—C11—N1122.1 (6)
C1—C2—H2119.6O4—C11—N1112.3 (5)
C2—C3—C4121.4 (8)O4—C12—C13110.1 (7)
C2—C3—Cl1119.4 (7)O4—C12—C14112.7 (6)
C4—C3—Cl1119.2 (7)C13—C12—C14111.5 (7)
C3—C4—C5117.2 (8)O4—C12—C15102.4 (6)
C3—C4—H4121.4C13—C12—C15110.5 (6)
C5—C4—H4121.4C14—C12—C15109.2 (7)
C6—C5—C4122.2 (8)C12—C13—H13A109.5
C6—C5—H5118.9C12—C13—H13B109.5
C4—C5—H5118.9H13A—C13—H13B109.5
C1—C6—C5119.3 (6)C12—C13—H13C109.5
C1—C6—C7122.9 (6)H13A—C13—H13C109.5
C5—C6—C7117.8 (6)H13B—C13—H13C109.5
N1—C7—C6117.2 (5)C12—C14—H14A109.5
N1—C7—S1102.2 (4)C12—C14—H14B109.5
C6—C7—S1109.2 (4)H14A—C14—H14B109.5
N1—C7—H7109.3C12—C14—H14C109.5
C6—C7—H7109.3H14A—C14—H14C109.5
S1—C7—H7109.3H14B—C14—H14C109.5
N1—C8—C10115.7 (6)C12—C15—H15A109.5
N1—C8—C9106.7 (5)C12—C15—H15B109.5
C10—C8—C9109.6 (5)H15A—C15—H15B109.5
N1—C8—H8108.2C12—C15—H15C109.5
C10—C8—H8108.2H15A—C15—H15C109.5
C9—C8—H8108.2H15B—C15—H15C109.5
C8—C9—S1104.3 (5)C11—N1—C8121.3 (5)
C8—C9—H9A110.9C11—N1—C7119.6 (5)
S1—C9—H9A110.9C8—N1—C7118.1 (5)
C8—C9—H9B110.9C10—O2—H2A109.5
S1—C9—H9B110.9C11—O4—C12121.8 (5)
H9A—C9—H9B108.9C9—S1—C790.0 (3)
C6—C1—C2—C3−2.5 (11)O3—C11—N1—C8−176.7 (6)
C1—C2—C3—C42.1 (12)O4—C11—N1—C83.6 (8)
C1—C2—C3—Cl1−178.8 (6)O3—C11—N1—C7−8.1 (9)
C2—C3—C4—C5−1.1 (11)O4—C11—N1—C7172.2 (5)
Cl1—C3—C4—C5179.8 (6)C10—C8—N1—C11−83.3 (7)
C3—C4—C5—C60.5 (11)C9—C8—N1—C11154.5 (5)
C2—C1—C6—C51.9 (10)C10—C8—N1—C7107.9 (6)
C2—C1—C6—C7178.9 (6)C9—C8—N1—C7−14.2 (7)
C4—C5—C6—C1−0.9 (10)C6—C7—N1—C1156.7 (7)
C4—C5—C6—C7−178.1 (6)S1—C7—N1—C11176.0 (4)
C1—C6—C7—N142.7 (8)C6—C7—N1—C8−134.4 (6)
C5—C6—C7—N1−140.2 (6)S1—C7—N1—C8−15.1 (6)
C1—C6—C7—S1−72.7 (7)O3—C11—O4—C12−0.4 (10)
C5—C6—C7—S1104.3 (6)N1—C11—O4—C12179.3 (6)
N1—C8—C9—S137.6 (6)C13—C12—O4—C11−67.2 (8)
C10—C8—C9—S1−88.4 (6)C14—C12—O4—C1158.1 (10)
N1—C8—C10—O1−174.4 (6)C15—C12—O4—C11175.3 (6)
C9—C8—C10—O1−53.8 (9)C8—C9—S1—C7−40.6 (5)
N1—C8—C10—O23.4 (8)N1—C7—S1—C931.7 (4)
C9—C8—C10—O2124.0 (6)C6—C7—S1—C9156.5 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O3i0.821.832.638 (6)167
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O3i0.821.832.638 (6)167
Symmetry code: (i) x+1, y, z.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

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Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Lu, Y., Wang, Z., Li, C.-M., Chen, J.-J., Dalton, J. T., Li, W. & Miller, D. D. (2010). Bioorg. Med. Chem. 18, 477–495.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Song, Z.-C., Ma, G.-Y., Lv, P.-C., Li, H.-Q., Xiao, Z.-P. & Zhu, H.-L. (2009). Eur. J. Med. Chem. 44, 3903–3908.