2-(2-Amino-5-methylthia­zol-4-yl)phenol

He, L.-M.; Cao, G.; Hu, A.-X.

doi:10.1107/S160053680903164X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2161

doi:10.1107/S160053680903164X

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2-(2-Amino-5-methylthiazol-4-yl)phenol

Li-Min He,^a Gao Cao ^a and Ai-Xi Hu ^b ^*

^aCollege of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
^*Correspondence e-mail: axhu0731@yahoo.com.cn

(Received 21 July 2009; accepted 11 August 2009; online 15 August 2009)

In the title compound, C₁₀H₁₀N₂OS, the benzene ring is nearly co-planar with the thiazole ring, making a dihedral angle of 2.1 (2)°. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds. An intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For background to 2-amino-4-arylthiazoles and their wide-ranging antifungal activity, see: Hu et al. (2008 ); Kazzouli et al. (2002 ); Holla et al. (2003 ). For a related structure, see: He et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₀N₂OS
M_r = 206.27
Orthorhombic, P b c a
a = 12.9391 (5) Å
b = 10.3967 (4) Å
c = 14.2938 (6) Å
V = 1922.86 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 173 K
0.48 × 0.42 × 0.39 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.869, T_max = 0.891
11037 measured reflections
1881 independent reflections
1706 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.150
S = 0.98
1881 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.84	1.77	2.521 (3)	148
N2—H2B⋯O1ⁱ	0.88	2.25	2.961 (3)	138
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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: 10.1107/S160053680903164X/xu2563sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903164X/xu2563Isup2.hkl

checkCIF report

Comment top

Compounds containing thiazole are found to exhibit a wide spectrum of biological activities and many of them are well known antiviral, antifungal agents and some are used as pesticides (Kazzouli et al., 2002; Holla et al., 2003; Hu et al., 2008). The structure of 2-amino-4-arylthiazoles was reported before (He et al., 2006). Herein we report the synthesis and crystal structure of the title compound.

The molecular structure of (I) is illustrated in Fig. 1. The molecules are linked by intermolecular hydrogen bonds (N–H···O) and intramolecular hydrogen bonds (O–H···N) (Table 1). The dihedral angle between the planes of thiazole and the benzene ring is 2.1 (2)°.

Related literature top

For background to 2-amino-4-arylthiazoles and their wide-ranging antifungal activity, see: Hu et al. (2008); Kazzouli et al. (2002); Holla et al. (2003). For a related structure, see: He et al. (2006).

Experimental top

A solution with 0.005 mol of thiourea and 0.005 mol of 2-bromo-1-(2-hydroxyphenyl)-1-propanone in 50 ml of ethanol was refluxed for 10 h. After finishing the reaction, added 10 ml ammonia and continues to stir the solution 2 h. Then the solution was cooled and the precipitate formed was filtered out, dried, giving white crystals of title compound, yield 60.3%. m.p. 388–389 K. The crystals for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

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 of (I), showing the atom-labelling scheme and 50% probability displacement ellipsoid (arbitrary spheres for H atoms).

2-(2-Amino-5-methylthiazol-4-yl)phenol top

Crystal data top

C₁₀H₁₀N₂OS	F(000) = 864
M_r = 206.27	D_x = 1.425 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7684 reflections
a = 12.9391 (5) Å	θ = 2.4–27.0°
b = 10.3967 (4) Å	µ = 0.30 mm⁻¹
c = 14.2938 (6) Å	T = 173 K
V = 1922.86 (13) Å³	Block, yellow
Z = 8	0.48 × 0.42 × 0.39 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1881 independent reflections
Radiation source: fine-focus sealed tube	1706 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→14
T_min = 0.869, T_max = 0.891	k = −12→12
11037 measured reflections	l = −17→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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0885P)² + 3.3976P] where P = (F_o² + 2F_c²)/3
1881 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₀H₁₀N₂OS	V = 1922.86 (13) Å³
M_r = 206.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.9391 (5) Å	µ = 0.30 mm⁻¹
b = 10.3967 (4) Å	T = 173 K
c = 14.2938 (6) Å	0.48 × 0.42 × 0.39 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	1881 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1706 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.891	R_int = 0.027
11037 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 0.98	Δρ_max = 1.20 e Å⁻³
1881 reflections	Δρ_min = −0.33 e Å⁻³
129 parameters

Special details top

Experimental. ¹H NMR (CDCl₃, 400 MHz): 2.48 (s, 3H, CH₃), 4.97 (br, 2H, NH₂), 6.86–7.42(m, 4H, phenyl-H).

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	0.29069 (5)	0.23322 (6)	0.58881 (4)	0.0269 (2)
C1	0.2598 (2)	0.3782 (2)	0.64120 (16)	0.0242 (5)
C2	0.43091 (18)	0.4000 (2)	0.61774 (16)	0.0232 (5)
C3	0.4199 (2)	0.2792 (2)	0.58181 (17)	0.0266 (6)
C4	0.52468 (18)	0.4802 (2)	0.62670 (16)	0.0241 (5)
C5	0.52103 (19)	0.6026 (2)	0.66966 (17)	0.0263 (5)
C6	0.6103 (2)	0.6770 (3)	0.67875 (18)	0.0315 (6)
H6	0.6066	0.7589	0.7081	0.038*
C7	0.7037 (2)	0.6329 (3)	0.64567 (19)	0.0344 (6)
H7	0.7642	0.6840	0.6526	0.041*
C8	0.7095 (2)	0.5136 (3)	0.6021 (2)	0.0369 (7)
H8	0.7738	0.4829	0.5790	0.044*
C9	0.6212 (2)	0.4398 (3)	0.59266 (18)	0.0314 (6)
H9	0.6261	0.3590	0.5620	0.038*
C10	0.4945 (2)	0.1822 (3)	0.5439 (2)	0.0413 (7)
H10A	0.5252	0.2149	0.4859	0.062*
H10B	0.4579	0.1016	0.5309	0.062*
H10C	0.5491	0.1665	0.5899	0.062*
N1	0.33898 (16)	0.45419 (19)	0.65168 (14)	0.0243 (5)
N2	0.16111 (17)	0.4091 (2)	0.66472 (16)	0.0316 (5)
H2A	0.1473	0.4850	0.6889	0.038*
H2B	0.1110	0.3531	0.6558	0.038*
O1	0.43180 (14)	0.65465 (18)	0.70442 (15)	0.0359 (5)
H1	0.3833	0.6015	0.6985	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0270 (4)	0.0238 (4)	0.0301 (4)	−0.0019 (2)	−0.0005 (2)	−0.0051 (2)
C1	0.0263 (12)	0.0229 (12)	0.0234 (11)	−0.0001 (9)	−0.0006 (9)	−0.0005 (9)
C2	0.0234 (12)	0.0238 (12)	0.0225 (11)	0.0026 (9)	0.0002 (9)	0.0014 (9)
C3	0.0258 (12)	0.0266 (13)	0.0274 (12)	0.0006 (10)	0.0004 (9)	−0.0009 (9)
C4	0.0236 (12)	0.0264 (12)	0.0223 (11)	0.0008 (9)	−0.0014 (9)	0.0036 (9)
C5	0.0243 (12)	0.0270 (12)	0.0277 (12)	0.0022 (10)	−0.0017 (9)	0.0022 (10)
C6	0.0313 (14)	0.0312 (13)	0.0321 (13)	−0.0040 (11)	−0.0043 (11)	0.0010 (10)
C7	0.0285 (14)	0.0421 (16)	0.0328 (13)	−0.0106 (11)	−0.0026 (10)	0.0045 (12)
C8	0.0250 (14)	0.0473 (17)	0.0385 (14)	−0.0006 (12)	0.0061 (11)	0.0019 (13)
C9	0.0274 (13)	0.0335 (14)	0.0333 (13)	0.0010 (11)	0.0047 (10)	−0.0017 (11)
C10	0.0338 (15)	0.0321 (15)	0.0581 (18)	0.0044 (12)	0.0047 (13)	−0.0131 (13)
N1	0.0221 (10)	0.0226 (10)	0.0282 (10)	0.0003 (8)	0.0016 (8)	−0.0015 (8)
N2	0.0228 (11)	0.0298 (11)	0.0422 (12)	−0.0017 (9)	0.0024 (9)	−0.0075 (10)
O1	0.0242 (9)	0.0275 (10)	0.0561 (12)	0.0006 (7)	−0.0007 (8)	−0.0113 (9)

Geometric parameters (Å, º) top

S1—C1	1.730 (2)	C6—H6	0.9500
S1—C3	1.742 (3)	C7—C8	1.390 (4)
C1—N1	1.302 (3)	C7—H7	0.9500
C1—N2	1.359 (3)	C8—C9	1.382 (4)
C2—C3	1.364 (4)	C8—H8	0.9500
C2—N1	1.403 (3)	C9—H9	0.9500
C2—C4	1.477 (3)	C10—H10A	0.9800
C3—C10	1.498 (4)	C10—H10B	0.9800
C4—C9	1.405 (3)	C10—H10C	0.9800
C4—C5	1.414 (4)	N2—H2A	0.8800
C5—O1	1.368 (3)	N2—H2B	0.8800
C5—C6	1.397 (4)	O1—H1	0.8400
C6—C7	1.376 (4)

C1—S1—C3	90.41 (12)	C6—C7—H7	120.1
N1—C1—N2	124.6 (2)	C8—C7—H7	120.1
N1—C1—S1	113.39 (19)	C7—C8—C9	119.6 (3)
N2—C1—S1	121.98 (19)	C7—C8—H8	120.2
C3—C2—N1	114.3 (2)	C9—C8—H8	120.2
C3—C2—C4	129.6 (2)	C8—C9—C4	122.4 (3)
N1—C2—C4	116.1 (2)	C8—C9—H9	118.8
C2—C3—C10	133.6 (2)	C4—C9—H9	118.8
C2—C3—S1	109.35 (19)	C3—C10—H10A	109.5
C10—C3—S1	117.0 (2)	C3—C10—H10B	109.5
C9—C4—C5	116.7 (2)	H10A—C10—H10B	109.5
C9—C4—C2	122.1 (2)	C3—C10—H10C	109.5
C5—C4—C2	121.2 (2)	H10A—C10—H10C	109.5
O1—C5—C6	116.4 (2)	H10B—C10—H10C	109.5
O1—C5—C4	122.8 (2)	C1—N1—C2	112.6 (2)
C6—C5—C4	120.8 (2)	C1—N2—H2A	120.0
C7—C6—C5	120.6 (3)	C1—N2—H2B	120.0
C7—C6—H6	119.7	H2A—N2—H2B	120.0
C5—C6—H6	119.7	C5—O1—H1	109.5
C6—C7—C8	119.9 (2)

C3—S1—C1—N1	0.48 (19)	C9—C4—C5—C6	−1.2 (3)
C3—S1—C1—N2	177.9 (2)	C2—C4—C5—C6	179.3 (2)
N1—C2—C3—C10	−175.7 (3)	O1—C5—C6—C7	−179.8 (2)
C4—C2—C3—C10	3.6 (5)	C4—C5—C6—C7	0.3 (4)
N1—C2—C3—S1	1.0 (3)	C5—C6—C7—C8	0.5 (4)
C4—C2—C3—S1	−179.6 (2)	C6—C7—C8—C9	−0.2 (4)
C1—S1—C3—C2	−0.85 (19)	C7—C8—C9—C4	−0.8 (4)
C1—S1—C3—C10	176.5 (2)	C5—C4—C9—C8	1.5 (4)
C3—C2—C4—C9	3.0 (4)	C2—C4—C9—C8	−179.0 (2)
N1—C2—C4—C9	−177.7 (2)	N2—C1—N1—C2	−177.3 (2)
C3—C2—C4—C5	−177.6 (2)	S1—C1—N1—C2	0.0 (3)
N1—C2—C4—C5	1.8 (3)	C3—C2—N1—C1	−0.7 (3)
C9—C4—C5—O1	178.9 (2)	C4—C2—N1—C1	179.9 (2)
C2—C4—C5—O1	−0.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84	1.77	2.521 (3)	148
N2—H2B···O1ⁱ	0.88	2.25	2.961 (3)	138

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂OS
M_r	206.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	12.9391 (5), 10.3967 (4), 14.2938 (6)
V (Å³)	1922.86 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.48 × 0.42 × 0.39

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.869, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	11037, 1881, 1706
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.150, 0.98
No. of reflections	1881
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −0.33

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
O1—H1···N1	0.84	1.77	2.521 (3)	148.3
N2—H2B···O1ⁱ	0.88	2.25	2.961 (3)	138.1

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

This research was performed with the support of the start-up fund for doctoral research of Guangdong Pharmaceutical University.

References

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