N-(2,4,6-Trimethyl­phen­yl)-1,3-thia­zol-2-amine

Babar, A.; Munawar, M.A.; Tahir, M.N.; Khan, A.F.; Tariq, M.I.

doi:10.1107/S1600536812031315

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2441

https://doi.org/10.1107/S1600536812031315

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N-(2,4,6-Trimethylphenyl)-1,3-thiazol-2-amine

Ayesha Babar,^a Munawar Ali Munawar,^a M. Nawaz Tahir,^b ^* Ather Farooq Khan ^c and Muhammad Ilyas Tariq ^d

^aInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, ^cInterdisciplinary Research Centre in Biomedical Materials, COMSATS Institute of Information Technology, Defence Road, Off Raiwind Road, Lahore, Pakistan, and ^dDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 9 July 2012; accepted 10 July 2012; online 14 July 2012)

In the title compound, C₁₂H₁₄N₂S, the dihedral angle between the 1,3,5-trimethylbenzene and 1,3-thiazol-2-amine groups is 73.15 (4)°. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds generate R₂²(8) loops.

Related literature

For background to the biological activities of thiazoles, see: Wilson et al. (2001 ). For a related crystal structure, see: Caranoni & Capella (1982 ).

Experimental

Crystal data

C₁₂H₁₄N₂S
M_r = 218.31
Monoclinic, P 2₁ /c
a = 14.2766 (6) Å
b = 7.0676 (2) Å
c = 13.8598 (6) Å
β = 118.736 (2)°
V = 1226.24 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.32 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.929, T_max = 0.959
10086 measured reflections
2717 independent reflections
2196 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.116
S = 1.05
2717 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.30 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—H1⋯N2ⁱ	0.86	2.16	2.944 (2)	151
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031315/hb6896sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031315/hb6896Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031315/hb6896Isup3.cml

checkCIF report

Comment top

Thiazole and its derivatives exhibit a large number of biological properties, for example antifungal and antibacterial (Wilson et al., 2001) activities. As part of our studies in this area, the title compound (I, Fig. 1) has been synthesized and its crystal structure is now reported.

The crystal structures of 1,3-thiazol-2-amine (Caranoni & Capella, 1982) has been published which is related to (I), (Fig. 1).

In (I), the 1,3,5-trimethylbenzene moiety A (C1–C9) and 1,3-thiazol-2-amine group B (N1/C10/S1/C11/C12/N2) are planar with r.m.s. deviation of 0.0345 Å and 0.0031 Å, respectively. The dihedral angle between A/B is 73.15 (4)°. The molecules are linked into dimers due to H-bondings of N—H···N type with R₂²(8) (Table 1, Fig. 2) ring motif.

Related literature top

For background to the biological activities of thiazoles, see: Wilson et al. (2001). For a related crystal structure, see: Caranoni & Capella (1982).

Experimental top

A mixture of N-mesitylthiourea (1 equiv, 1.00 g, 4.58 mmol), 2-chloro-1,1-dimethoxyethane (1.5 equiv, 1.04 g, 6.8 mmol) and few drops of concentrated HCl were dissolved in water and methanol mixture (1:1) (100 ml). The reaction mixture was refluxed for 6 h. The reaction mixture was diluted with water (100 ml) and basified to pH 8 with aqeous NaOH. The resulting precipitate was filtered, washed with cold water and recrystallized from chloroform and hexane (3:1) solution as yellow prisms.

Structure description top

The crystal structures of 1,3-thiazol-2-amine (Caranoni & Capella, 1982) has been published which is related to (I), (Fig. 1).

For background to the biological activities of thiazoles, see: Wilson et al. (2001). For a related crystal structure, see: Caranoni & Capella (1982).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form dimers with R₂²(8) loops.

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

Crystal data top

C₁₂H₁₄N₂S	F(000) = 464
M_r = 218.31	D_x = 1.183 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2196 reflections
a = 14.2766 (6) Å	θ = 1.6–27.3°
b = 7.0676 (2) Å	µ = 0.23 mm⁻¹
c = 13.8598 (6) Å	T = 296 K
β = 118.736 (2)°	Prism, yellow
V = 1226.24 (9) Å³	0.32 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2717 independent reflections
Radiation source: fine-focus sealed tube	2196 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 7.80 pixels mm^-1	θ_max = 27.3°, θ_min = 1.6°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→9
T_min = 0.929, T_max = 0.959	l = −17→17
10086 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.116	w = 1/[σ²(F_o²) + (0.0574P)² + 0.3377P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2717 reflections	Δρ_max = 0.30 e Å⁻³
140 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (4)

Crystal data top

C₁₂H₁₄N₂S	V = 1226.24 (9) Å³
M_r = 218.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.2766 (6) Å	µ = 0.23 mm⁻¹
b = 7.0676 (2) Å	T = 296 K
c = 13.8598 (6) Å	0.32 × 0.22 × 0.18 mm
β = 118.736 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2717 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2196 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.959	R_int = 0.027
10086 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	Δρ_max = 0.30 e Å⁻³
2717 reflections	Δρ_min = −0.24 e Å⁻³
140 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.28549 (3)	0.60626 (7)	0.20694 (3)	0.0510 (2)
N1	0.37642 (11)	0.6678 (2)	0.42680 (11)	0.0489 (4)
N2	0.46689 (11)	0.4830 (2)	0.35713 (11)	0.0457 (4)
C1	0.28129 (12)	0.7598 (2)	0.41025 (12)	0.0417 (5)
C2	0.25718 (15)	0.9401 (3)	0.36248 (14)	0.0503 (5)
C3	0.16150 (17)	1.0218 (3)	0.34372 (15)	0.0619 (7)
C4	0.09327 (16)	0.9380 (3)	0.37534 (15)	0.0640 (7)
C5	0.12224 (14)	0.7638 (3)	0.42681 (14)	0.0579 (6)
C6	0.21467 (13)	0.6720 (2)	0.44421 (12)	0.0464 (5)
C7	0.24324 (19)	0.4809 (3)	0.49949 (19)	0.0689 (8)
C8	0.3330 (2)	1.0470 (3)	0.3358 (2)	0.0774 (9)
C9	−0.0095 (2)	1.0332 (5)	0.3547 (2)	0.1073 (13)
C10	0.38520 (12)	0.5850 (2)	0.34340 (12)	0.0385 (4)
C11	0.36100 (15)	0.4680 (3)	0.16835 (14)	0.0522 (6)
C12	0.45154 (15)	0.4168 (3)	0.25688 (14)	0.0499 (6)
H1	0.43021	0.66451	0.49200	0.0586*
H3	0.14255	1.13832	0.30825	0.0742*
H5	0.07821	0.70656	0.45048	0.0694*
H7A	0.18460	0.43399	0.50812	0.1034*
H7B	0.30533	0.49271	0.57044	0.1034*
H7C	0.25797	0.39442	0.45505	0.1034*
H8A	0.31727	1.17980	0.33141	0.1162*
H8B	0.32495	1.00412	0.26651	0.1162*
H8C	0.40502	1.02536	0.39246	0.1162*
H9A	−0.05817	1.03567	0.27711	0.1608*
H9B	0.00533	1.16026	0.38250	0.1608*
H9C	−0.04105	0.96399	0.39150	0.1608*
H11	0.34159	0.43378	0.09636	0.0626*
H12	0.50176	0.34047	0.25128	0.0599*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0449 (3)	0.0634 (3)	0.0357 (2)	0.0060 (2)	0.0122 (2)	0.0011 (2)
N1	0.0442 (7)	0.0644 (9)	0.0332 (6)	0.0155 (7)	0.0148 (5)	0.0007 (6)
N2	0.0449 (7)	0.0542 (8)	0.0398 (7)	0.0100 (6)	0.0217 (6)	0.0047 (6)
C1	0.0410 (8)	0.0480 (9)	0.0323 (7)	0.0071 (7)	0.0147 (6)	−0.0023 (6)
C2	0.0594 (10)	0.0491 (9)	0.0441 (9)	0.0067 (8)	0.0263 (8)	0.0009 (7)
C3	0.0747 (13)	0.0597 (11)	0.0479 (10)	0.0267 (10)	0.0268 (9)	0.0082 (8)
C4	0.0539 (10)	0.0921 (15)	0.0403 (9)	0.0287 (10)	0.0182 (8)	0.0018 (9)
C5	0.0448 (9)	0.0857 (14)	0.0432 (9)	0.0020 (9)	0.0212 (7)	−0.0026 (9)
C6	0.0481 (9)	0.0532 (9)	0.0347 (7)	0.0004 (7)	0.0174 (7)	−0.0039 (7)
C7	0.0830 (14)	0.0585 (12)	0.0719 (13)	−0.0024 (10)	0.0425 (12)	0.0080 (10)
C8	0.0980 (17)	0.0590 (12)	0.0915 (17)	−0.0005 (12)	0.0585 (15)	0.0086 (11)
C9	0.0779 (16)	0.166 (3)	0.0768 (16)	0.0672 (19)	0.0362 (13)	0.0210 (17)
C10	0.0377 (7)	0.0420 (8)	0.0340 (7)	0.0021 (6)	0.0158 (6)	0.0044 (6)
C11	0.0656 (11)	0.0535 (10)	0.0407 (8)	−0.0042 (8)	0.0282 (8)	−0.0051 (7)
C12	0.0594 (10)	0.0505 (10)	0.0500 (9)	0.0078 (8)	0.0344 (8)	0.0015 (7)

Geometric parameters (Å, º) top

S1—C10	1.7428 (15)	C6—C7	1.509 (3)
S1—C11	1.720 (2)	C11—C12	1.335 (3)
N1—C1	1.421 (2)	C3—H3	0.9300
N1—C10	1.354 (2)	C5—H5	0.9300
N2—C10	1.305 (2)	C7—H7A	0.9600
N2—C12	1.380 (2)	C7—H7B	0.9600
N1—H1	0.8600	C7—H7C	0.9600
C1—C6	1.393 (3)	C8—H8A	0.9600
C1—C2	1.401 (2)	C8—H8B	0.9600
C2—C3	1.388 (3)	C8—H8C	0.9600
C2—C8	1.505 (4)	C9—H9A	0.9600
C3—C4	1.379 (3)	C9—H9B	0.9600
C4—C5	1.383 (3)	C9—H9C	0.9600
C4—C9	1.511 (4)	C11—H11	0.9300
C5—C6	1.384 (3)	C12—H12	0.9300

C10—S1—C11	88.94 (8)	C4—C3—H3	119.00
C1—N1—C10	122.23 (14)	C4—C5—H5	119.00
C10—N2—C12	110.02 (15)	C6—C5—H5	119.00
C1—N1—H1	119.00	C6—C7—H7A	109.00
C10—N1—H1	119.00	C6—C7—H7B	109.00
N1—C1—C2	119.41 (17)	C6—C7—H7C	109.00
N1—C1—C6	119.75 (13)	H7A—C7—H7B	109.00
C2—C1—C6	120.82 (17)	H7A—C7—H7C	109.00
C1—C2—C3	117.6 (2)	H7B—C7—H7C	109.00
C3—C2—C8	120.31 (19)	C2—C8—H8A	109.00
C1—C2—C8	122.1 (2)	C2—C8—H8B	109.00
C2—C3—C4	122.9 (2)	C2—C8—H8C	109.00
C3—C4—C9	121.2 (2)	H8A—C8—H8B	109.00
C3—C4—C5	117.7 (2)	H8A—C8—H8C	109.00
C5—C4—C9	121.1 (2)	H8B—C8—H8C	110.00
C4—C5—C6	122.1 (2)	C4—C9—H9A	110.00
C1—C6—C5	118.75 (15)	C4—C9—H9B	110.00
C5—C6—C7	120.70 (19)	C4—C9—H9C	109.00
C1—C6—C7	120.55 (18)	H9A—C9—H9B	110.00
S1—C10—N2	114.35 (12)	H9A—C9—H9C	109.00
S1—C10—N1	121.78 (13)	H9B—C9—H9C	109.00
N1—C10—N2	123.87 (14)	S1—C11—H11	125.00
S1—C11—C12	110.05 (14)	C12—C11—H11	125.00
N2—C12—C11	116.6 (2)	N2—C12—H12	122.00
C2—C3—H3	119.00	C11—C12—H12	122.00

C11—S1—C10—N1	−179.66 (15)	N1—C1—C6—C5	−179.71 (14)
C11—S1—C10—N2	−0.05 (14)	N1—C1—C6—C7	0.6 (2)
C10—S1—C11—C12	0.38 (17)	C2—C1—C6—C5	2.0 (2)
C10—N1—C1—C2	−76.7 (2)	C2—C1—C6—C7	−177.69 (16)
C10—N1—C1—C6	104.96 (18)	C1—C2—C3—C4	3.6 (3)
C1—N1—C10—S1	6.9 (2)	C8—C2—C3—C4	−174.12 (19)
C1—N1—C10—N2	−172.72 (16)	C2—C3—C4—C5	−0.8 (3)
C12—N2—C10—S1	−0.29 (19)	C2—C3—C4—C9	179.1 (2)
C12—N2—C10—N1	179.31 (17)	C3—C4—C5—C6	−1.7 (3)
C10—N2—C12—C11	0.6 (3)	C9—C4—C5—C6	178.44 (18)
N1—C1—C2—C3	177.48 (15)	C4—C5—C6—C1	1.1 (3)
N1—C1—C2—C8	−4.8 (2)	C4—C5—C6—C7	−179.29 (18)
C6—C1—C2—C3	−4.2 (2)	S1—C11—C12—N2	−0.7 (3)
C6—C1—C2—C8	173.51 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.16	2.944 (2)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₂S
M_r	218.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.2766 (6), 7.0676 (2), 13.8598 (6)
β (°)	118.736 (2)
V (Å³)	1226.24 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.32 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.929, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	10086, 2717, 2196
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.645

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.116, 1.05
No. of reflections	2717
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.16	2.944 (2)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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