4-tert-Butyl-5-(1H-1,2,4-triazol-1-yl)thia­zol-2-amine

Xie, A.-Y.; Ye, J.; Qin, Z.; Hu, A.-X.

doi:10.1107/S1600536809029912

organic compounds

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Volume 65| Part 8| August 2009| Page o2057

doi:10.1107/S1600536809029912

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4-tert-Butyl-5-(1H-1,2,4-triazol-1-yl)thiazol-2-amine

An-Yun Xie,^a Jiao Ye,^b Zhi Qin ^b and Ai-Xi Hu ^b ^*

^aHunan Warrant Pharmaceutical Co. Ltd, Changsha 410329, 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 22 July 2009; accepted 28 July 2009; online 31 July 2009)

The dihedral angle between the triazole ring and the thiazole ring in the title compound, C₉H₁₃N₅S, is 64.35 (7)°. The crystal structure is stabilized by intermolecular N—H⋯N hydrogen bonds, which link the molecules into a two-dimensional network.

Related literature

For background and related structures, see: Zhou et al. (2007 ); Shao et al. (2008 ).

Experimental

Crystal data

C₉H₁₃N₅S
M_r = 223.30
Monoclinic, P 2₁ /c
a = 7.7487 (4) Å
b = 14.2240 (8) Å
c = 10.2697 (5) Å
β = 91.452 (1)°
V = 1131.54 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 K
0.47 × 0.43 × 0.37 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.887, T_max = 0.909
6167 measured reflections
2463 independent reflections
2187 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.07
2463 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N5ⁱ	0.88	2.22	3.0049 (16)	148
N2—H2A⋯N1ⁱⁱ	0.88	2.17	3.0392 (14)	168
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -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/S1600536809029912/bt5018sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809029912/bt5018Isup2.hkl

checkCIF report

Comment top

Thiazole derivatives and 1,2,4-triazole derivatives have been found to be active compounds with diversely biological activities (Zhou et al., 2007; Shao et al., 2008). We herein report the synthesis and structures of the title compound, 4-tert-butyl-5-(1H-1,2,4-triazol-1-yl)thiazol-2-amine, which was incorporated 1H-1,2,4-triazole units into the novel thialoyl urea compounds in order to find novel leading compounds with potential anticancer activities.

The title compound (Fig. 1), contains two planar subunits: the thiazole ring and the triazole ring. The dihedral angles between them is 64.35 (7). The crystal structure (Fig. 2) is stabilized by intermolecular hydrogen bonds between the amino group and the nitrogen atoms of the thiazol ring and the triazole ring of the neighbouring molecules.

For related structures, see: Zhou et al. (2007), Shao et al. (2008).

Related literature top

For background and related structures, see: Zhou et al. (2007); Shao et al. (2008).

Experimental top

1-bromo-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (0.01 mol) were refluxed with thiourea (0.01 mol) in ethanol (45 ml) for 1.5 h (monitored by TLC). Then the pH of the mixture was adjusted to 9 with ammonia and filtered to obtain white solid, 4-tert-butyl-5-(1H-1,2,4-triazol-1-yl) thiazol-2-amine. Yield 85.5%, m.p. 451 K.

Crystals suitable 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 50% probability displacement ellipsoids.
	Fig. 2. A packing diagram for the title compound showing intermolecular hydrogen bonds as dashed lines. H atoms bonded to C omitted for clarity.

4-tert-Butyl-5-(1H-1,2,4-triazol-1-yl)thiazol-2-amine top

Crystal data top

C₉H₁₃N₅S	F(000) = 472
M_r = 223.30	D_x = 1.311 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 451 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.7487 (4) Å	Cell parameters from 4587 reflections
b = 14.2240 (8) Å	θ = 2.5–27.1°
c = 10.2697 (5) Å	µ = 0.26 mm⁻¹
β = 91.452 (1)°	T = 173 K
V = 1131.54 (10) Å³	Block, colorless
Z = 4	0.47 × 0.43 × 0.37 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	2463 independent reflections
Radiation source: fine-focus sealed tube	2187 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 27.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→4
T_min = 0.887, T_max = 0.909	k = −18→18
6167 measured reflections	l = −13→13

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0539P)² + 0.2785P] where P = (F_o² + 2F_c²)/3
2463 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₉H₁₃N₅S	V = 1131.54 (10) Å³
M_r = 223.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7487 (4) Å	µ = 0.26 mm⁻¹
b = 14.2240 (8) Å	T = 173 K
c = 10.2697 (5) Å	0.47 × 0.43 × 0.37 mm
β = 91.452 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2463 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2187 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.909	R_int = 0.016
6167 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.07	Δρ_max = 0.24 e Å⁻³
2463 reflections	Δρ_min = −0.31 e Å⁻³
139 parameters

Special details top

Experimental. 1H NMR (CDCl₃, 400 MHz) δ: 1.11 (s, 9H, (CH₃)₃), 4.38 (s, 2H, NH₂), 8.06 (s, 1H, C₂H₂N₃ 3-H), 8.23 (s, 1H, C₂H₂N₃ 5-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	0.10734 (4)	0.36412 (2)	0.12795 (3)	0.02144 (11)
C1	0.28446 (15)	0.42187 (8)	0.06301 (12)	0.0208 (2)
C2	0.38251 (15)	0.27348 (8)	0.06564 (11)	0.0194 (2)
C3	0.22378 (16)	0.25969 (8)	0.11582 (11)	0.0200 (2)
C4	0.52048 (16)	0.19969 (9)	0.03942 (13)	0.0248 (3)
C5	0.69774 (19)	0.24700 (11)	0.0350 (2)	0.0490 (5)
H5A	0.6994	0.2911	−0.0382	0.073*
H5B	0.7869	0.1990	0.0239	0.073*
H5C	0.7203	0.2811	0.1166	0.073*
C6	0.4799 (2)	0.15274 (11)	−0.09224 (15)	0.0392 (4)
H6A	0.4739	0.2008	−0.1606	0.059*
H6B	0.3689	0.1200	−0.0885	0.059*
H6C	0.5711	0.1075	−0.1117	0.059*
C7	0.5268 (2)	0.12361 (10)	0.14558 (16)	0.0368 (3)
H7A	0.6247	0.0816	0.1312	0.055*
H7B	0.4193	0.0873	0.1420	0.055*
H7C	0.5404	0.1534	0.2313	0.055*
C8	0.01671 (17)	0.04703 (9)	0.15964 (13)	0.0267 (3)
H8	−0.0313	−0.0113	0.1318	0.032*
C9	0.09146 (17)	0.15830 (9)	0.28121 (12)	0.0267 (3)
H9	0.1101	0.1985	0.3541	0.032*
N1	0.41461 (13)	0.36685 (7)	0.03390 (10)	0.0210 (2)
N2	0.27815 (14)	0.51513 (7)	0.04483 (12)	0.0285 (3)
H2A	0.3661	0.5445	0.0108	0.034*
H2B	0.1860	0.5469	0.0670	0.034*
N3	0.14376 (13)	0.17666 (7)	0.16036 (10)	0.0206 (2)
N4	0.09397 (14)	0.10478 (8)	0.07907 (10)	0.0254 (2)
N5	0.01069 (15)	0.07679 (8)	0.28504 (11)	0.0299 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01973 (17)	0.01734 (17)	0.02758 (18)	−0.00120 (10)	0.00713 (12)	−0.00005 (10)
C1	0.0194 (6)	0.0182 (6)	0.0251 (6)	−0.0023 (4)	0.0045 (4)	0.0005 (4)
C2	0.0198 (6)	0.0165 (5)	0.0221 (5)	−0.0009 (4)	0.0003 (4)	0.0011 (4)
C3	0.0218 (6)	0.0155 (5)	0.0229 (5)	−0.0016 (4)	0.0023 (4)	0.0011 (4)
C4	0.0203 (6)	0.0167 (5)	0.0374 (7)	0.0019 (5)	0.0031 (5)	0.0018 (5)
C5	0.0202 (7)	0.0241 (7)	0.1029 (15)	0.0024 (6)	0.0083 (8)	0.0026 (8)
C6	0.0457 (9)	0.0356 (8)	0.0366 (8)	0.0134 (7)	0.0078 (6)	−0.0056 (6)
C7	0.0380 (8)	0.0275 (7)	0.0447 (8)	0.0103 (6)	−0.0008 (6)	0.0090 (6)
C8	0.0292 (6)	0.0194 (6)	0.0317 (6)	−0.0069 (5)	0.0017 (5)	0.0008 (5)
C9	0.0316 (7)	0.0254 (6)	0.0234 (6)	−0.0073 (5)	0.0042 (5)	0.0014 (5)
N1	0.0187 (5)	0.0164 (5)	0.0282 (5)	−0.0009 (4)	0.0043 (4)	0.0015 (4)
N2	0.0242 (5)	0.0149 (5)	0.0471 (7)	0.0002 (4)	0.0136 (5)	0.0022 (5)
N3	0.0222 (5)	0.0173 (5)	0.0223 (5)	−0.0038 (4)	0.0016 (4)	0.0008 (4)
N4	0.0294 (6)	0.0197 (5)	0.0271 (5)	−0.0062 (4)	0.0031 (4)	−0.0029 (4)
N5	0.0328 (6)	0.0277 (6)	0.0293 (6)	−0.0095 (5)	0.0052 (5)	0.0045 (4)

Geometric parameters (Å, º) top

S1—C3	1.7441 (12)	C6—H6B	0.9800
S1—C1	1.7464 (12)	C6—H6C	0.9800
C1—N1	1.3169 (16)	C7—H7A	0.9800
C1—N2	1.3403 (16)	C7—H7B	0.9800
C2—C3	1.3598 (17)	C7—H7C	0.9800
C2—N1	1.3914 (14)	C8—N4	1.3202 (16)
C2—C4	1.5270 (16)	C8—N5	1.3575 (18)
C3—N3	1.4153 (15)	C8—H8	0.9500
C4—C5	1.5312 (19)	C9—N5	1.3187 (17)
C4—C6	1.533 (2)	C9—N3	1.3410 (16)
C4—C7	1.5360 (18)	C9—H9	0.9500
C5—H5A	0.9800	N2—H2A	0.8800
C5—H5B	0.9800	N2—H2B	0.8800
C5—H5C	0.9800	N3—N4	1.3692 (14)
C6—H6A	0.9800

C3—S1—C1	87.73 (6)	C4—C6—H6C	109.5
N1—C1—N2	125.59 (11)	H6A—C6—H6C	109.5
N1—C1—S1	114.89 (9)	H6B—C6—H6C	109.5
N2—C1—S1	119.50 (9)	C4—C7—H7A	109.5
C3—C2—N1	113.28 (10)	C4—C7—H7B	109.5
C3—C2—C4	127.71 (10)	H7A—C7—H7B	109.5
N1—C2—C4	118.99 (10)	C4—C7—H7C	109.5
C2—C3—N3	130.61 (11)	H7A—C7—H7C	109.5
C2—C3—S1	112.26 (9)	H7B—C7—H7C	109.5
N3—C3—S1	117.12 (9)	N4—C8—N5	115.32 (11)
C2—C4—C5	109.61 (10)	N4—C8—H8	122.3
C2—C4—C6	109.04 (10)	N5—C8—H8	122.3
C5—C4—C6	109.23 (13)	N5—C9—N3	110.70 (11)
C2—C4—C7	111.65 (11)	N5—C9—H9	124.6
C5—C4—C7	108.55 (12)	N3—C9—H9	124.6
C6—C4—C7	108.73 (11)	C1—N1—C2	111.81 (10)
C4—C5—H5A	109.5	C1—N2—H2A	120.0
C4—C5—H5B	109.5	C1—N2—H2B	120.0
H5A—C5—H5B	109.5	H2A—N2—H2B	120.0
C4—C5—H5C	109.5	C9—N3—N4	109.38 (10)
H5A—C5—H5C	109.5	C9—N3—C3	127.35 (10)
H5B—C5—H5C	109.5	N4—N3—C3	123.03 (10)
C4—C6—H6A	109.5	C8—N4—N3	101.98 (10)
C4—C6—H6B	109.5	C9—N5—C8	102.60 (11)
H6A—C6—H6B	109.5

C3—S1—C1—N1	1.03 (10)	S1—C1—N1—C2	−1.71 (13)
C3—S1—C1—N2	179.99 (11)	C3—C2—N1—C1	1.65 (15)
N1—C2—C3—N3	−179.45 (11)	C4—C2—N1—C1	−179.57 (10)
C4—C2—C3—N3	1.9 (2)	N5—C9—N3—N4	0.78 (15)
N1—C2—C3—S1	−0.87 (13)	N5—C9—N3—C3	175.29 (12)
C4—C2—C3—S1	−179.52 (10)	C2—C3—N3—C9	117.79 (16)
C1—S1—C3—C2	−0.05 (9)	S1—C3—N3—C9	−60.72 (15)
C1—S1—C3—N3	178.73 (10)	C2—C3—N3—N4	−68.38 (18)
C3—C2—C4—C5	−157.79 (14)	S1—C3—N3—N4	113.10 (11)
N1—C2—C4—C5	23.63 (17)	N5—C8—N4—N3	1.00 (15)
C3—C2—C4—C6	82.69 (16)	C9—N3—N4—C8	−1.03 (14)
N1—C2—C4—C6	−95.90 (13)	C3—N3—N4—C8	−175.83 (11)
C3—C2—C4—C7	−37.48 (17)	N3—C9—N5—C8	−0.16 (15)
N1—C2—C4—C7	143.94 (12)	N4—C8—N5—C9	−0.56 (16)
N2—C1—N1—C2	179.41 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N5ⁱ	0.88	2.22	3.0049 (16)	148
N2—H2A···N1ⁱⁱ	0.88	2.17	3.0392 (14)	168

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

Experimental details

Crystal data
Chemical formula	C₉H₁₃N₅S
M_r	223.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.7487 (4), 14.2240 (8), 10.2697 (5)
β (°)	91.452 (1)
V (Å³)	1131.54 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.47 × 0.43 × 0.37

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.887, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	6167, 2463, 2187
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.07
No. of reflections	2463
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.31

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—H2B···N5ⁱ	0.88	2.22	3.0049 (16)	148.3
N2—H2A···N1ⁱⁱ	0.88	2.17	3.0392 (14)	167.7

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

References

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Shao, L., Zhou, X., Jin, Z. & Fang, J. X. (2008). Heteroat. Chem. 19, 2–6. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, X., Shao, L., Jin, Z., Liu, J. B., Dai, H. & Fang, J. X. (2007). Heteroatom Chem. 18, 55–59. Web of Science CrossRef CAS Google Scholar

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o2057

doi:10.1107/S1600536809029912

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