4-(2,4,6-Trimethyl­benz­yl)-1,3-thia­zol-2-amine

Maharramov, A.M.; Khalilov, A.N.; Gurbanov, A.V.; Allahverdiyev, M.A.; Ng, S.W.

doi:10.1107/S1600536811006386

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o721

doi:10.1107/S1600536811006386

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4-(2,4,6-Trimethylbenzyl)-1,3-thiazol-2-amine

Abel M. Maharramov,^a Ali N. Khalilov,^a Atash V. Gurbanov,^a Mirze A. Allahverdiyev ^a and Seik Weng Ng ^b ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 16 February 2011; accepted 19 February 2011; online 26 February 2011)

The methylene C atom in the title compound, C₁₃H₁₆N₂S, is connected to a five-membered thiazole ring and a mesityl substituent. The rings are aligned at 75.4 (1)°. The amino substitutent interacts with the ring N atom of an adjacent molecule by an intermolecular N—H⋯N hydrogen bond, generating a helical chain running along the b axis.

Related literature

For background to the synthetic procedure,: see: Yadigarov et al. (2010 ).

Experimental

Crystal data

C₁₃H₁₆N₂S
M_r = 232.34
Monoclinic, P 2₁ /n
a = 5.5028 (5) Å
b = 30.832 (3) Å
c = 7.8355 (7) Å
β = 110.016 (1)°
V = 1249.08 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.933, T_max = 0.955
7129 measured reflections
2749 independent reflections
2486 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.120
S = 1.06
2749 reflections
156 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯N2ⁱ	0.88 (1)	2.06 (1)	2.907 (2)	163 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006386/im2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006386/im2269Isup2.hkl

checkCIF report

Comment top

A recent study reported the reaction of 1-chloro-3-(2,4,6-trimethylphenyl)-propan-2-one with primary amines. The chlorine atom in the α-chloro ketone is not replaced directly by an amino RNH– group. The intermediate product undergoes a Favorskii rearrangement that furnishes a compound having two methylene groups between the aromatic system and the amido unit (Yadigarov et al., 2010). The present study employs thiourea as the amine. One of its amino –NH₂ groups is involved in the formation of the thiazolyl ring in the resulting product (Scheme I, Fig. 1). The methylene carbon is connected to the five-membered thiazolyl ring and the six-membered mesityl group. The rings are aligned at 75.4 (1) °. The amino –NH₂ substitutent interacts with the ring N atom of an adjacent molecule by an N–H···N hydrogen bond generating a helical chain that runs along the b-axis of the monoclinic unit cell.

Related literature top

For background to the synthetic procedure,: see: Yadigarov et al. (2010).

Experimental top

1-Chloro-3-(2,4,6-trimethylphenyl)-propan-2-one (10 mmol) and thiourea (10 mmol) were stirred in water (100 ml) for an hour. A precipitate formed and this was collected and redissolved in hot ethanol. Slow evaporation of the solvent gave colorless crystals in 50% yield; m.p. 380–381 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₃H₁₆N₂S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-(2,4,6-Trimethylbenzyl)-1,3-thiazol-2-amine top

Crystal data top

C₁₃H₁₆N₂S	F(000) = 496
M_r = 232.34	D_x = 1.235 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3598 reflections
a = 5.5028 (5) Å	θ = 2.6–29.1°
b = 30.832 (3) Å	µ = 0.23 mm⁻¹
c = 7.8355 (7) Å	T = 100 K
β = 110.016 (1)°	Prism, colorless
V = 1249.08 (19) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	2749 independent reflections
Radiation source: fine-focus sealed tube	2486 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.933, T_max = 0.955	k = −40→24
7129 measured reflections	l = −9→10

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.060P)² + 0.6878P] where P = (F_o² + 2F_c²)/3
2749 reflections	(Δ/σ)_max = 0.001
156 parameters	Δρ_max = 0.38 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₃H₁₆N₂S	V = 1249.08 (19) Å³
M_r = 232.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.5028 (5) Å	µ = 0.23 mm⁻¹
b = 30.832 (3) Å	T = 100 K
c = 7.8355 (7) Å	0.30 × 0.20 × 0.20 mm
β = 110.016 (1)°

Data collection top

Bruker APEXII diffractometer	2749 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2486 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.955	R_int = 0.024
7129 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.38 e Å⁻³
2749 reflections	Δρ_min = −0.24 e Å⁻³
156 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.65720 (8)	0.220399 (14)	0.75764 (6)	0.02680 (15)
N1	0.2450 (3)	0.26387 (5)	0.7802 (2)	0.0283 (3)
H11	0.351 (3)	0.2757 (6)	0.8795 (19)	0.030 (5)*
H12	0.080 (2)	0.2637 (8)	0.764 (3)	0.038 (6)*
N2	0.1780 (3)	0.20379 (5)	0.58369 (19)	0.0241 (3)
C1	0.3278 (3)	0.23024 (5)	0.7040 (2)	0.0215 (3)
C2	0.5821 (3)	0.17807 (6)	0.6029 (2)	0.0267 (4)
H2	0.7056	0.1604	0.5759	0.032*
C3	0.3239 (3)	0.17382 (5)	0.5263 (2)	0.0244 (3)
C4	0.1797 (4)	0.13975 (6)	0.3931 (3)	0.0338 (4)
H4A	0.0544	0.1542	0.2862	0.041*
H4B	0.0800	0.1217	0.4502	0.041*
C5	0.3520 (3)	0.11046 (6)	0.3288 (2)	0.0282 (4)
C6	0.3814 (4)	0.11748 (6)	0.1605 (2)	0.0301 (4)
C7	0.5436 (4)	0.09018 (7)	0.1069 (3)	0.0344 (4)
H7	0.5633	0.0950	−0.0075	0.041*
C8	0.6772 (4)	0.05629 (6)	0.2137 (3)	0.0344 (4)
C9	0.6454 (4)	0.04995 (6)	0.3799 (3)	0.0365 (4)
H9	0.7352	0.0269	0.4557	0.044*
C10	0.4858 (4)	0.07644 (6)	0.4388 (3)	0.0336 (4)
C11	0.2363 (5)	0.15279 (7)	0.0330 (3)	0.0473 (6)
H11A	0.2694	0.1807	0.0966	0.071*
H11B	0.0505	0.1465	−0.0085	0.071*
H11C	0.2946	0.1541	−0.0719	0.071*
C12	0.8478 (4)	0.02682 (8)	0.1499 (3)	0.0487 (6)
H12A	0.9348	0.0438	0.0820	0.073*
H12B	0.7419	0.0042	0.0711	0.073*
H12C	0.9776	0.0133	0.2552	0.073*
C13	0.4571 (7)	0.06770 (8)	0.6208 (3)	0.0609 (8)
H13A	0.5687	0.0434	0.6802	0.091*
H13B	0.2767	0.0605	0.6029	0.091*
H13C	0.5074	0.0936	0.6974	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0157 (2)	0.0299 (2)	0.0334 (3)	−0.00014 (16)	0.00646 (16)	−0.00426 (18)
N1	0.0173 (7)	0.0329 (8)	0.0320 (8)	0.0012 (6)	0.0049 (6)	−0.0077 (7)
N2	0.0193 (7)	0.0246 (7)	0.0269 (7)	−0.0006 (6)	0.0061 (5)	−0.0005 (6)
C1	0.0171 (7)	0.0248 (8)	0.0214 (7)	0.0014 (6)	0.0051 (6)	0.0038 (6)
C2	0.0229 (8)	0.0246 (8)	0.0342 (9)	0.0014 (7)	0.0118 (7)	−0.0012 (7)
C3	0.0241 (8)	0.0230 (8)	0.0267 (8)	0.0000 (7)	0.0096 (6)	0.0010 (7)
C4	0.0296 (9)	0.0303 (9)	0.0407 (10)	−0.0038 (8)	0.0110 (8)	−0.0094 (8)
C5	0.0298 (9)	0.0229 (8)	0.0295 (9)	−0.0032 (7)	0.0072 (7)	−0.0051 (7)
C6	0.0343 (9)	0.0249 (9)	0.0255 (9)	−0.0034 (7)	0.0031 (7)	−0.0002 (7)
C7	0.0414 (10)	0.0374 (11)	0.0234 (9)	−0.0047 (9)	0.0098 (8)	−0.0049 (8)
C8	0.0328 (10)	0.0319 (10)	0.0339 (10)	−0.0014 (8)	0.0055 (8)	−0.0129 (8)
C9	0.0458 (11)	0.0245 (9)	0.0292 (9)	0.0056 (8)	0.0000 (8)	−0.0014 (8)
C10	0.0489 (11)	0.0239 (9)	0.0260 (9)	−0.0024 (8)	0.0102 (8)	−0.0025 (7)
C11	0.0621 (14)	0.0328 (11)	0.0353 (11)	0.0052 (10)	0.0016 (10)	0.0071 (9)
C12	0.0402 (12)	0.0481 (13)	0.0552 (14)	0.0031 (10)	0.0127 (10)	−0.0213 (11)
C13	0.118 (2)	0.0327 (12)	0.0400 (13)	0.0024 (13)	0.0379 (15)	0.0050 (10)

Geometric parameters (Å, º) top

S1—C2	1.7323 (18)	C7—C8	1.383 (3)
S1—C1	1.7415 (16)	C7—H7	0.9500
N1—C1	1.351 (2)	C8—C9	1.386 (3)
N1—H11	0.88 (1)	C8—C12	1.509 (3)
N1—H12	0.87 (1)	C9—C10	1.389 (3)
N2—C1	1.304 (2)	C9—H9	0.9500
N2—C3	1.396 (2)	C10—C13	1.512 (3)
C2—C3	1.346 (2)	C11—H11A	0.9800
C2—H2	0.9500	C11—H11B	0.9800
C3—C4	1.502 (2)	C11—H11C	0.9800
C4—C5	1.515 (2)	C12—H12A	0.9800
C4—H4A	0.9900	C12—H12B	0.9800
C4—H4B	0.9900	C12—H12C	0.9800
C5—C10	1.397 (3)	C13—H13A	0.9800
C5—C6	1.399 (3)	C13—H13B	0.9800
C6—C7	1.393 (3)	C13—H13C	0.9800
C6—C11	1.508 (3)

C2—S1—C1	89.03 (8)	C6—C7—H7	118.8
C1—N1—H11	119.3 (14)	C7—C8—C9	117.63 (18)
C1—N1—H12	115.1 (16)	C7—C8—C12	121.1 (2)
H11—N1—H12	118 (2)	C9—C8—C12	121.3 (2)
C1—N2—C3	110.84 (14)	C8—C9—C10	121.79 (18)
N2—C1—N1	125.03 (15)	C8—C9—H9	119.1
N2—C1—S1	114.43 (12)	C10—C9—H9	119.1
N1—C1—S1	120.50 (13)	C9—C10—C5	119.78 (17)
C3—C2—S1	110.36 (13)	C9—C10—C13	119.37 (19)
C3—C2—H2	124.8	C5—C10—C13	120.84 (19)
S1—C2—H2	124.8	C6—C11—H11A	109.5
C2—C3—N2	115.33 (15)	C6—C11—H11B	109.5
C2—C3—C4	127.16 (16)	H11A—C11—H11B	109.5
N2—C3—C4	117.47 (15)	C6—C11—H11C	109.5
C3—C4—C5	113.94 (15)	H11A—C11—H11C	109.5
C3—C4—H4A	108.8	H11B—C11—H11C	109.5
C5—C4—H4A	108.8	C8—C12—H12A	109.5
C3—C4—H4B	108.8	C8—C12—H12B	109.5
C5—C4—H4B	108.8	H12A—C12—H12B	109.5
H4A—C4—H4B	107.7	C8—C12—H12C	109.5
C10—C5—C6	119.39 (17)	H12A—C12—H12C	109.5
C10—C5—C4	120.04 (17)	H12B—C12—H12C	109.5
C6—C5—C4	120.56 (17)	C10—C13—H13A	109.5
C5—C6—C7	118.95 (17)	C10—C13—H13B	109.5
C5—C6—C11	122.00 (18)	H13A—C13—H13B	109.5
C7—C6—C11	119.01 (18)	C10—C13—H13C	109.5
C8—C7—C6	122.45 (18)	H13A—C13—H13C	109.5
C8—C7—H7	118.8	H13B—C13—H13C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···N2ⁱ	0.88 (1)	2.06 (1)	2.907 (2)	163 (2)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N₂S
M_r	232.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	5.5028 (5), 30.832 (3), 7.8355 (7)
β (°)	110.016 (1)
V (Å³)	1249.08 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.933, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	7129, 2749, 2486
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.120, 1.06
No. of reflections	2749
No. of parameters	156
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···N2ⁱ	0.88 (1)	2.06 (1)	2.907 (2)	163 (2)

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

We thank Baku State University and the University of Malaya for supporting this study.

References

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