4-(1,3-Thia­zolidin-2-yl)phenol

Yang, X.-M.

doi:10.1107/S1600536809042135

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2799

https://doi.org/10.1107/S1600536809042135

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4-(1,3-Thiazolidin-2-yl)phenol

Xue-Mei Yang ^a ^*

^aDepartment of Chemistry, Guangdong Medical College, Dongguan 523808, People's Republic of China
^*Correspondence e-mail: xuemeiyang131@163.com

(Received 16 September 2009; accepted 14 October 2009; online 23 October 2009)

In the title compound, C₉H₁₁NOS, the thiazolidinyl ring is almost perpendicular to the phenyl ring with N—C—C—C torsion angles of 71.7 (2) and 107.1 (2)°. In the crystal, molecules are connected via N—H⋯O and O—H⋯N hydrogen bonds, forming layers.

Related literature

For the cyclization of 2-amino-ethanthiol Schiff bases, see: Al-Sayyab et al. (1968 ); Stacy & Strong (1967 ); Thompson & Busch (1964 ).

Experimental

Crystal data

C₉H₁₁NOS
M_r = 181.25
Orthorhombic, P b c a
a = 12.3638 (6) Å
b = 8.9683 (5) Å
c = 15.8249 (8) Å
V = 1754.7 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 173 K
0.47 × 0.45 × 0.16 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.865, T_max = 0.951
9635 measured reflections
1919 independent reflections
1615 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.07
1919 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.85 (2)	2.28 (2)	3.073 (2)	156 (2)
O1—H1A⋯N1ⁱⁱ	0.82 (2)	1.91 (2)	2.713 (2)	164 (2)
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809042135/im2144sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042135/im2144Isup2.hkl

checkCIF report

Comment top

In our search for a new synthetic route to imipenem, a carbapenem antibiotic, we got a thiazolidine compound from a reaction of p-hydroxybenzaldehyde with 2-amino-ethanthiol, despite of our initial plan to prepare a Schiff base compound. This is consistent with reports that the 2-amino-ethanthiol Schiff base compounds can undergo intromolecular cyclization to form thiazolidines (Al-Sayyab et al., 1968; Thompson & Busch, 1964; Stacy & Strong, 1967).

In the molecular sturcture (Fig. 1), as it is expected the thiazolidinyl ring is not planar, showing a N(1)—C(1)—C(2)—S(1) torsion angle of -33.7 (2)°. Furthermore, the thiazolidinyl ring is almost perpendicular to the phenyl ring, with torsion angles N(1)—C(3)—C(4)—C(9) of 71.7 (2)° and N(1)—C(3)—C(4)—C(5) of 107.1 (2)°. In Fig. 1 the chiral center C(3) adopts R configuation. Nevertheless, due to space group symmetry a reacemate has been formed and both enantiomers are present in the crystal structure.

In the crystal structure two adjacent molecules are connected via N—H···O and O—H···N hydrogen bonds to form centrosymmetric molecule pairs. These pairs are further linked by additional N—H···O and O—H···N intermolecular hydrogen bonds leading to the observed layered supramolecular (Fig. 2).

Related literature top

For the cyclization of 2-amino-ethanthiol Schiff bases, see: Al-Sayyab et al. (1968); Stacy & Strong (1967); Thompson & Busch (1964).

Experimental top

2-Amino-ethanthiol 0.77 g (0.001 mol) was mixed with p-hydroxybenzaldehyde 1.22 g (0.001 mol) in ethanol (10 ml) and the mixture refluxed for 2 h. The solvent was evaporated to dryness under reduced pressure and the remaining residue recrystallized from ethanol to afford 1.5 g of yellow block crystals. (Yield 85%). Crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanolic solution. Spectroscopic analysis: ¹H NMR (DMSO-d₆, δ, p.p.m.): 2.75–2.90 (m, 2H), 2.85–3.05 (m, 2H), 3.50 (m, 1H), 5.35 (s, 1H), 6.70 (d, 2H), 7.25 (d, 2H), 9.35 (s, 1H); elemental analysis, calculated for C₉H₁₁NOS: C, 59.67; H, 6.08; N, 7.73; found: C, 59.33; H, 5.93; N 7.41%.

Structure description top

For the cyclization of 2-amino-ethanthiol Schiff bases, see: Al-Sayyab et al. (1968); Stacy & Strong (1967); Thompson & Busch (1964).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure with thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal lattice along c axis. H atoms not involved in hydrogen bonds have been omitted for clarity.

4-(1,3-Thiazolidin-2-yl)phenol top

Crystal data top

C₉H₁₁NOS	F(000) = 768
M_r = 181.25	D_x = 1.372 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4931 reflections
a = 12.3638 (6) Å	θ = 2.6–27.0°
b = 8.9683 (5) Å	µ = 0.32 mm⁻¹
c = 15.8249 (8) Å	T = 173 K
V = 1754.7 (2) Å³	Block, colorless
Z = 8	0.47 × 0.45 × 0.16 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1919 independent reflections
Radiation source: fine-focus sealed tube	1615 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→15
T_min = 0.865, T_max = 0.951	k = −11→8
9635 measured reflections	l = −20→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0611P)² + 0.7197P] where P = (F_o² + 2F_c²)/3
1919 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₉H₁₁NOS	V = 1754.7 (2) Å³
M_r = 181.25	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.3638 (6) Å	µ = 0.32 mm⁻¹
b = 8.9683 (5) Å	T = 173 K
c = 15.8249 (8) Å	0.47 × 0.45 × 0.16 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1919 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1615 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.951	R_int = 0.022
9635 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.37 e Å⁻³
1919 reflections	Δρ_min = −0.17 e Å⁻³
115 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

	x	y	z	U_iso*/U_eq
S1	0.47979 (3)	0.18010 (5)	0.70817 (2)	0.02679 (16)
C1	0.27121 (14)	0.1895 (2)	0.74816 (11)	0.0355 (4)
H1B	0.2501	0.2924	0.7327	0.043*
H1C	0.2046	0.1288	0.7530	0.043*
C2	0.34426 (15)	0.1245 (3)	0.67981 (12)	0.0417 (5)
H2A	0.3245	0.1646	0.6236	0.050*
H2B	0.3381	0.0145	0.6783	0.050*
C3	0.43704 (12)	0.24880 (18)	0.81446 (9)	0.0217 (3)
H3	0.4323	0.3600	0.8119	0.026*
C4	0.51646 (12)	0.20804 (17)	0.88292 (9)	0.0209 (3)
C5	0.55139 (13)	0.31669 (17)	0.93977 (10)	0.0235 (3)
H5	0.5255	0.4159	0.9342	0.028*
C6	0.62307 (13)	0.28297 (18)	1.00422 (10)	0.0248 (4)
H6	0.6461	0.3587	1.0421	0.030*
C7	0.66115 (13)	0.13804 (18)	1.01328 (9)	0.0227 (3)
C8	0.62657 (13)	0.02820 (18)	0.95705 (10)	0.0239 (3)
H8	0.6521	−0.0712	0.9630	0.029*
C9	0.55519 (12)	0.06344 (18)	0.89265 (10)	0.0229 (3)
H9	0.5323	−0.0122	0.8546	0.027*
N1	0.32818 (11)	0.19058 (16)	0.82922 (9)	0.0249 (3)
H1	0.3303 (16)	0.103 (3)	0.8493 (12)	0.030*
O1	0.73103 (10)	0.09658 (14)	1.07553 (7)	0.0302 (3)
H1A	0.7567 (19)	0.172 (3)	1.0971 (13)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0253 (2)	0.0357 (3)	0.0194 (2)	0.00118 (16)	0.00148 (14)	−0.00048 (16)
C1	0.0239 (9)	0.0512 (12)	0.0313 (9)	0.0019 (8)	−0.0045 (7)	−0.0055 (8)
C2	0.0308 (9)	0.0616 (14)	0.0326 (9)	−0.0052 (9)	−0.0028 (8)	−0.0139 (9)
C3	0.0218 (7)	0.0221 (8)	0.0213 (7)	0.0008 (6)	0.0012 (6)	−0.0004 (6)
C4	0.0213 (7)	0.0232 (8)	0.0182 (7)	−0.0019 (6)	0.0023 (6)	0.0005 (6)
C5	0.0265 (8)	0.0188 (7)	0.0252 (8)	−0.0003 (6)	0.0013 (6)	−0.0004 (6)
C6	0.0283 (8)	0.0229 (8)	0.0233 (7)	−0.0042 (6)	−0.0009 (6)	−0.0046 (6)
C7	0.0214 (7)	0.0271 (8)	0.0197 (7)	−0.0034 (6)	0.0012 (6)	0.0013 (6)
C8	0.0259 (8)	0.0204 (7)	0.0254 (8)	0.0011 (6)	0.0009 (6)	−0.0003 (6)
C9	0.0236 (7)	0.0233 (8)	0.0218 (7)	−0.0033 (6)	0.0008 (6)	−0.0027 (6)
N1	0.0219 (7)	0.0266 (7)	0.0262 (7)	0.0003 (5)	0.0013 (5)	0.0001 (6)
O1	0.0337 (7)	0.0275 (6)	0.0293 (6)	−0.0026 (5)	−0.0117 (5)	−0.0012 (5)

Geometric parameters (Å, º) top

S1—C2	1.8049 (19)	C4—C5	1.395 (2)
S1—C3	1.8676 (15)	C5—C6	1.385 (2)
C1—N1	1.463 (2)	C5—H5	0.9500
C1—C2	1.525 (3)	C6—C7	1.390 (2)
C1—H1B	0.9900	C6—H6	0.9500
C1—H1C	0.9900	C7—O1	1.3620 (19)
C2—H2A	0.9900	C7—C8	1.395 (2)
C2—H2B	0.9900	C8—C9	1.385 (2)
C3—N1	1.462 (2)	C8—H8	0.9500
C3—C4	1.507 (2)	C9—H9	0.9500
C3—H3	1.0000	N1—H1	0.85 (2)
C4—C9	1.391 (2)	O1—H1A	0.82 (2)

C2—S1—C3	93.00 (8)	C5—C4—C3	119.73 (14)
N1—C1—C2	109.83 (14)	C6—C5—C4	121.38 (15)
N1—C1—H1B	109.7	C6—C5—H5	119.3
C2—C1—H1B	109.7	C4—C5—H5	119.3
N1—C1—H1C	109.7	C5—C6—C7	119.81 (14)
C2—C1—H1C	109.7	C5—C6—H6	120.1
H1B—C1—H1C	108.2	C7—C6—H6	120.1
C1—C2—S1	105.55 (12)	O1—C7—C6	123.01 (14)
C1—C2—H2A	110.6	O1—C7—C8	117.59 (14)
S1—C2—H2A	110.6	C6—C7—C8	119.40 (14)
C1—C2—H2B	110.6	C9—C8—C7	120.25 (15)
S1—C2—H2B	110.6	C9—C8—H8	119.9
H2A—C2—H2B	108.8	C7—C8—H8	119.9
N1—C3—C4	113.46 (13)	C8—C9—C4	120.91 (14)
N1—C3—S1	106.65 (10)	C8—C9—H9	119.5
C4—C3—S1	112.52 (11)	C4—C9—H9	119.5
N1—C3—H3	108.0	C3—N1—C1	107.78 (13)
C4—C3—H3	108.0	C3—N1—H1	111.2 (14)
S1—C3—H3	108.0	C1—N1—H1	109.8 (13)
C9—C4—C5	118.25 (14)	C7—O1—H1A	108.7 (15)
C9—C4—C3	122.01 (14)

N1—C1—C2—S1	−33.3 (2)	C5—C6—C7—O1	−179.46 (15)
C3—S1—C2—C1	10.32 (15)	C5—C6—C7—C8	0.1 (2)
C2—S1—C3—N1	14.01 (13)	O1—C7—C8—C9	179.74 (14)
C2—S1—C3—C4	139.03 (13)	C6—C7—C8—C9	0.2 (2)
N1—C3—C4—C9	71.65 (19)	C7—C8—C9—C4	−0.2 (2)
S1—C3—C4—C9	−49.55 (18)	C5—C4—C9—C8	0.0 (2)
N1—C3—C4—C5	−107.07 (17)	C3—C4—C9—C8	−178.77 (14)
S1—C3—C4—C5	131.73 (13)	C4—C3—N1—C1	−159.92 (14)
C9—C4—C5—C6	0.3 (2)	S1—C3—N1—C1	−35.47 (15)
C3—C4—C5—C6	179.05 (14)	C2—C1—N1—C3	45.7 (2)
C4—C5—C6—C7	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (2)	2.28 (2)	3.073 (2)	156 (2)
O1—H1A···N1ⁱⁱ	0.82 (2)	1.91 (2)	2.713 (2)	164 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₁NOS
M_r	181.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	12.3638 (6), 8.9683 (5), 15.8249 (8)
V (Å³)	1754.7 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.47 × 0.45 × 0.16

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.865, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	9635, 1919, 1615
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.07
No. of reflections	1919
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.17

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (2)	2.28 (2)	3.073 (2)	156 (2)
O1—H1A···N1ⁱⁱ	0.82 (2)	1.91 (2)	2.713 (2)	164 (2)

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

Acknowledgements

The author thanks the National Science Foundation of China for financial support.

References

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Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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