2-Amino-4-tert-butyl-5-(4-chloro­benz­yl)thia­zole

Wang, Y.-T.; Xia, L.; Hu, A.-X.; Cao, G.; Xu, J.-J.

doi:10.1107/S160053680803715X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2350

doi:10.1107/S160053680803715X

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2-Amino-4-tert-butyl-5-(4-chlorobenzyl)thiazole

Yong-Tao Wang,^a Lin Xia,^a Ai-Xi Hu,^a ^* Gao Cao ^a and Juan-Juan Xu ^a

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

(Received 27 October 2008; accepted 10 November 2008; online 13 November 2008)

In the title compound, C₁₄H₁₇ClN₂S, the dihedral angle between the planes of the thiazole and chlorophenyl rings is 88.86 (3)°. In the crystal, inversion dimers occur, linked by pairs of N—H⋯N hydrogen bonds.

Related literature

For background on 2-amino-4-arylthiazoles and their wide-ranging antifungal activities, see: Hu et al. (2007a ); Marcantonio et al. (2002 ). For related structures, see: Cao et al. (2007 ); He et al. (2006 ); Hu et al. (2007b ); Xu et al. (2007 ).

Experimental

Crystal data

C₁₄H₁₇ClN₂S
M_r = 280.81
Monoclinic, C 2/c
a = 21.1775 (13) Å
b = 5.8544 (4) Å
c = 22.8193 (14) Å
β = 98.5480 (10)°
V = 2797.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 173 (2) K
0.48 × 0.29 × 0.17 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.829, T_max = 0.934
6230 measured reflections
2705 independent reflections
2187 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.120
S = 1.06
2705 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1ⁱ	0.88	2.24	3.032 (2)	150
Symmetry code: (i) -x+1, -y+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 I, global. DOI: 10.1107/S160053680803715X/sg2282sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803715X/sg2282Isup2.hkl

checkCIF report

Comment top

2-Amino-4-arylthiazoles are an important class of heterocyclic compounds in the field of organic pharmaceutial chenistry (Hu et al., 2007a, Marcantonio et al.,2002). Because of their wide-ranging antifungal activities, The structure of 2-amino-4-arylthiazoles were reported before (Cao, et al.,2007, He et al.,2006, Hu et al.,2007b, Xu, et al.,2007). Herein we report the synthesis and crystal structure of 2-amino-4-tert-butyl-5-(4- chlorobenzyl)thiazole(I). The dihedral angle between the planes of thiazole and the chlorophenyl ring is 88.86 °. The molecules are linked by N—H···N hydrogen bonds.

Related literature top

For background on 2-amino-4-arylthiazoles and their wide-ranging antifungal activities, see: Hu et al. (2007a); Marcantonio et al. (2002). For related structures, see: Cao et al. (2007); He et al. (2006); Hu et al. (2007b); Xu et al. (2007).

Experimental top

0.01 mol of 1-(4-Chlorophenyl)-4,4-dimethylpentan-3-one was dissolved in 100 ml e thanol and the mixture was stirred and heated to reflex. 0.012 mol of cupric chloride was added by dropwise. The reaction was monitored by TLC, after it finished, filtered the mixture and concentrated in vacuo. The residue was taken up in dichloromethane, washed with 10% hydrochloric acid, then washed with water until the solution was neutral, dried and concentrated in vacuo to give 4-chloro-1-(4-chlorophenyl)-4,4-dimethylpentan -3-one, yield 87%. Then a solution with 0.005 mol of thiurea and 0.005 mol of 4-chloro-1-(4-chlorophenyl)-4,4-dimethylpentan -3-one in 50 ml of ethanol was refluxed for 10 h. After finishing the reaction, added 10 ml ammonia and continus to stir the sulution 2 h. Then the solution was cooled and the precipitate formed was filtered out, dried, giving white crystals of title compound,yield 73.8%. 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. Molecular structure showing 30% probability displacement ellipsoids.H atoms are drawn as spheres of arbitrary radii. Only the major occupied sites of the disordered tert-butyl group are showen.
	Fig. 2. Packing diagram showing the N—H···N hydrogen bonds.

2-Amino-4-tert-butyl-5-(4-chlorobenzyl)thiazole top

Crystal data top

C₁₄H₁₇ClN₂S	F(000) = 1184
M_r = 280.81	D_x = 1.333 Mg m⁻³
Monoclinic, C2/c	Melting point: 390 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.1775 (13) Å	Cell parameters from 3521 reflections
b = 5.8544 (4) Å	θ = 2.8–26.9°
c = 22.8193 (14) Å	µ = 0.41 mm⁻¹
β = 98.548 (1)°	T = 173 K
V = 2797.7 (3) Å³	Block, colourless
Z = 8	0.48 × 0.29 × 0.17 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	2705 independent reflections
Radiation source: fine-focus sealed tube	2187 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −26→23
T_min = 0.829, T_max = 0.934	k = −5→7
6230 measured reflections	l = −19→28

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0686P)² + 2.6543P] where P = (F_o² + 2F_c²)/3
2705 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₄H₁₇ClN₂S	V = 2797.7 (3) Å³
M_r = 280.81	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.1775 (13) Å	µ = 0.41 mm⁻¹
b = 5.8544 (4) Å	T = 173 K
c = 22.8193 (14) Å	0.48 × 0.29 × 0.17 mm
β = 98.548 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2705 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2187 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.934	R_int = 0.022
6230 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.06	Δρ_max = 0.32 e Å⁻³
2705 reflections	Δρ_min = −0.32 e Å⁻³
166 parameters

Special details top

Experimental. ¹H NMR (CDCl₃, 400 MHz) (ppm):1.32(s,9H,3CH₃),4.1(s,2H,CH₂), 4.8(bs,2H,NH₂),7.12(d,J=8.0 Hz,2H,2,6-C₆H₄Cl), 7.26(d,J=8.0Hz,2H,3,5-C₆H₄Cl)

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
Cl1	0.13949 (3)	0.57508 (12)	0.24064 (3)	0.0437 (2)
S1	0.33404 (2)	0.74487 (9)	−0.00369 (2)	0.02787 (18)
C1	0.40616 (9)	0.8911 (4)	0.00413 (9)	0.0235 (4)
C2	0.42658 (10)	0.6258 (3)	0.07470 (8)	0.0228 (4)
C3	0.36579 (10)	0.5622 (3)	0.05422 (9)	0.0244 (4)
C4	0.32309 (10)	0.3710 (4)	0.06838 (9)	0.0284 (5)
H4A	0.3504	0.2416	0.0845	0.034*
H4B	0.2975	0.3188	0.0309	0.034*
C5	0.27747 (9)	0.4274 (3)	0.11205 (9)	0.0229 (4)
C6	0.27927 (11)	0.6335 (4)	0.14241 (9)	0.0301 (5)
H6	0.3101	0.7454	0.1361	0.036*
C7	0.23707 (11)	0.6786 (4)	0.18159 (10)	0.0309 (5)
H7	0.2389	0.8202	0.2021	0.037*
C8	0.19240 (10)	0.5176 (4)	0.19071 (9)	0.0287 (5)
C9	0.18919 (10)	0.3095 (4)	0.16165 (9)	0.0296 (5)
H9	0.1587	0.1978	0.1687	0.036*
C10	0.23148 (10)	0.2676 (4)	0.12204 (9)	0.0267 (5)
H10	0.2291	0.1266	0.1012	0.032*
C11	0.47436 (10)	0.5254 (4)	0.12457 (9)	0.0260 (5)
C12	0.50271 (12)	0.7208 (4)	0.16519 (10)	0.0359 (6)
H12A	0.4687	0.7939	0.1833	0.054*
H12B	0.5224	0.8336	0.1418	0.054*
H12C	0.5351	0.6594	0.1964	0.054*
C13	0.52788 (11)	0.4074 (4)	0.09748 (10)	0.0358 (6)
H13A	0.5609	0.3542	0.1292	0.054*
H13B	0.5467	0.5160	0.0723	0.054*
H13C	0.5103	0.2768	0.0736	0.054*
C14	0.44542 (13)	0.3499 (5)	0.16253 (11)	0.0425 (6)
H14A	0.4077	0.4155	0.1763	0.064*
H14B	0.4770	0.3087	0.1968	0.064*
H14C	0.4330	0.2131	0.1388	0.064*
N1	0.44938 (8)	0.8119 (3)	0.04551 (7)	0.0228 (4)
N2	0.41428 (9)	1.0743 (3)	−0.03037 (8)	0.0289 (4)
H2A	0.4509	1.1483	−0.0254	0.035*
H2B	0.3830	1.1191	−0.0577	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0357 (3)	0.0626 (4)	0.0359 (3)	0.0072 (3)	0.0153 (3)	−0.0044 (3)
S1	0.0206 (3)	0.0356 (3)	0.0269 (3)	−0.0032 (2)	0.0018 (2)	0.0018 (2)
C1	0.0205 (10)	0.0295 (11)	0.0213 (10)	−0.0018 (8)	0.0060 (8)	−0.0023 (8)
C2	0.0255 (11)	0.0245 (10)	0.0196 (9)	−0.0025 (8)	0.0076 (8)	−0.0010 (8)
C3	0.0265 (11)	0.0249 (11)	0.0227 (10)	−0.0026 (8)	0.0062 (8)	−0.0009 (8)
C4	0.0279 (11)	0.0287 (11)	0.0297 (11)	−0.0075 (9)	0.0077 (9)	−0.0046 (9)
C5	0.0219 (10)	0.0246 (10)	0.0217 (10)	−0.0012 (8)	0.0016 (8)	0.0023 (8)
C6	0.0337 (12)	0.0275 (11)	0.0293 (11)	−0.0057 (9)	0.0059 (9)	−0.0021 (9)
C7	0.0348 (12)	0.0293 (11)	0.0280 (11)	0.0008 (10)	0.0033 (9)	−0.0067 (9)
C8	0.0246 (11)	0.0404 (12)	0.0215 (10)	0.0054 (9)	0.0044 (8)	0.0026 (9)
C9	0.0246 (11)	0.0363 (12)	0.0280 (11)	−0.0025 (9)	0.0045 (9)	0.0040 (9)
C10	0.0268 (11)	0.0253 (11)	0.0278 (11)	−0.0018 (9)	0.0036 (9)	0.0011 (8)
C11	0.0283 (11)	0.0275 (11)	0.0223 (10)	0.0000 (9)	0.0043 (8)	0.0049 (8)
C12	0.0456 (15)	0.0374 (13)	0.0220 (11)	0.0007 (11)	−0.0043 (10)	−0.0004 (9)
C13	0.0376 (13)	0.0377 (13)	0.0319 (12)	0.0090 (10)	0.0049 (10)	0.0052 (10)
C14	0.0419 (14)	0.0481 (15)	0.0377 (13)	−0.0053 (12)	0.0064 (11)	0.0190 (12)
N1	0.0222 (9)	0.0263 (9)	0.0204 (8)	−0.0008 (7)	0.0044 (7)	0.0030 (7)
N2	0.0248 (9)	0.0323 (10)	0.0285 (9)	−0.0004 (8)	0.0005 (7)	0.0105 (8)

Geometric parameters (Å, º) top

Cl1—C8	1.746 (2)	C8—C9	1.383 (3)
S1—C1	1.737 (2)	C9—C10	1.386 (3)
S1—C3	1.754 (2)	C9—H9	0.9500
C1—N1	1.299 (3)	C10—H10	0.9500
C1—N2	1.356 (3)	C11—C14	1.530 (3)
C2—C3	1.355 (3)	C11—C13	1.534 (3)
C2—N1	1.400 (3)	C11—C12	1.537 (3)
C2—C11	1.524 (3)	C12—H12A	0.9800
C3—C4	1.504 (3)	C12—H12B	0.9800
C4—C5	1.524 (3)	C12—H12C	0.9800
C4—H4A	0.9900	C13—H13A	0.9800
C4—H4B	0.9900	C13—H13B	0.9800
C5—C6	1.389 (3)	C13—H13C	0.9800
C5—C10	1.393 (3)	C14—H14A	0.9800
C6—C7	1.380 (3)	C14—H14B	0.9800
C6—H6	0.9500	C14—H14C	0.9800
C7—C8	1.373 (3)	N2—H2A	0.8800
C7—H7	0.9500	N2—H2B	0.8800

C1—S1—C3	89.44 (10)	C9—C10—C5	121.5 (2)
N1—C1—N2	124.57 (19)	C9—C10—H10	119.2
N1—C1—S1	114.38 (15)	C5—C10—H10	119.2
N2—C1—S1	121.04 (15)	C2—C11—C14	113.86 (19)
C3—C2—N1	115.28 (18)	C2—C11—C13	108.74 (17)
C3—C2—C11	130.02 (19)	C14—C11—C13	107.96 (19)
N1—C2—C11	114.70 (17)	C2—C11—C12	108.64 (17)
C2—C3—C4	134.5 (2)	C14—C11—C12	108.16 (18)
C2—C3—S1	109.30 (15)	C13—C11—C12	109.42 (19)
C4—C3—S1	116.10 (15)	C11—C12—H12A	109.5
C3—C4—C5	116.06 (17)	C11—C12—H12B	109.5
C3—C4—H4A	108.3	H12A—C12—H12B	109.5
C5—C4—H4A	108.3	C11—C12—H12C	109.5
C3—C4—H4B	108.3	H12A—C12—H12C	109.5
C5—C4—H4B	108.3	H12B—C12—H12C	109.5
H4A—C4—H4B	107.4	C11—C13—H13A	109.5
C6—C5—C10	118.02 (19)	C11—C13—H13B	109.5
C6—C5—C4	122.77 (18)	H13A—C13—H13B	109.5
C10—C5—C4	119.21 (18)	C11—C13—H13C	109.5
C7—C6—C5	121.1 (2)	H13A—C13—H13C	109.5
C7—C6—H6	119.4	H13B—C13—H13C	109.5
C5—C6—H6	119.4	C11—C14—H14A	109.5
C8—C7—C6	119.6 (2)	C11—C14—H14B	109.5
C8—C7—H7	120.2	H14A—C14—H14B	109.5
C6—C7—H7	120.2	C11—C14—H14C	109.5
C7—C8—C9	121.2 (2)	H14A—C14—H14C	109.5
C7—C8—Cl1	119.34 (17)	H14B—C14—H14C	109.5
C9—C8—Cl1	119.48 (17)	C1—N1—C2	111.59 (17)
C8—C9—C10	118.6 (2)	C1—N2—H2A	120.0
C8—C9—H9	120.7	C1—N2—H2B	120.0
C10—C9—H9	120.7	H2A—N2—H2B	120.0

C3—S1—C1—N1	0.05 (16)	C6—C7—C8—Cl1	179.63 (17)
C3—S1—C1—N2	−178.88 (18)	C7—C8—C9—C10	−1.1 (3)
N1—C2—C3—C4	175.9 (2)	Cl1—C8—C9—C10	179.78 (16)
C11—C2—C3—C4	−3.8 (4)	C8—C9—C10—C5	1.4 (3)
N1—C2—C3—S1	−1.0 (2)	C6—C5—C10—C9	−1.0 (3)
C11—C2—C3—S1	179.30 (18)	C4—C5—C10—C9	179.46 (19)
C1—S1—C3—C2	0.54 (16)	C3—C2—C11—C14	−10.1 (3)
C1—S1—C3—C4	−177.02 (16)	N1—C2—C11—C14	170.24 (19)
C2—C3—C4—C5	96.2 (3)	C3—C2—C11—C13	110.3 (2)
S1—C3—C4—C5	−87.0 (2)	N1—C2—C11—C13	−69.4 (2)
C3—C4—C5—C6	−6.9 (3)	C3—C2—C11—C12	−130.7 (2)
C3—C4—C5—C10	172.63 (18)	N1—C2—C11—C12	49.7 (2)
C10—C5—C6—C7	0.4 (3)	N2—C1—N1—C2	178.26 (18)
C4—C5—C6—C7	179.9 (2)	S1—C1—N1—C2	−0.6 (2)
C5—C6—C7—C8	−0.2 (3)	C3—C2—N1—C1	1.1 (3)
C6—C7—C8—C9	0.5 (3)	C11—C2—N1—C1	−179.18 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1ⁱ	0.88	2.24	3.032 (2)	150

Symmetry code: (i) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇ClN₂S
M_r	280.81
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	21.1775 (13), 5.8544 (4), 22.8193 (14)
β (°)	98.548 (1)
V (Å³)	2797.7 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.48 × 0.29 × 0.17

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.829, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	6230, 2705, 2187
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.120, 1.06
No. of reflections	2705
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.32

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
N2—H2A···N1ⁱ	0.88	2.24	3.032 (2)	149.8

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

The work was funded by the National Key Technology R&D Program, China (NO: 2006 BAE01A01–4).

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