N-(2,4-Dichloro­phen­yl)-1,3-thia­zol-2-amine

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

doi:10.1107/S1600536812035301

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2704

doi:10.1107/S1600536812035301

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N-(2,4-Dichlorophenyl)-1,3-thiazol-2-amine

Ayesha Babar,^a Munawar Ali Munawar,^a M. Nawaz Tahir,^b ^* Fateh Ullah ^c and Muhammad Ilyas Tariq ^d

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

(Received 1 August 2012; accepted 9 August 2012; online 15 August 2012)

In the title molecule, C₉H₆Cl₂N₂S, the mean planes of the benzene and thiazole rings make a dihedral angle of 54.18 (8)°. In the crystal, molecules are joined into dimers with an R₂²(8) ring motif by pairs of N—H⋯N hydrogen bonds. These dimers are linked by C—H⋯Cl interactions into layers parallel to (011). The thiazole rings form columns along the c-axis direction, with a centroid–centroid separation of 3.8581 (9) Å, indicating π–π interactions. An intramolecular C—H⋯S contact also occurs.

Related literature

For the synthesis and crystal structure of a related compound, see: Babar et al. (2012 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₆Cl₂N₂S
M_r = 245.12
Monoclinic, P 2₁ /c
a = 13.0270 (9) Å
b = 10.1183 (6) Å
c = 7.7159 (5) Å
β = 91.974 (3)°
V = 1016.44 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 296 K
0.33 × 0.28 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.778, T_max = 0.844
8039 measured reflections
2245 independent reflections
1957 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.080
S = 1.04
2245 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.30 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	2.07	2.9302 (19)	174
C3—H3⋯Cl2ⁱⁱ	0.93	2.82	3.7483 (17)	173
C6—H6⋯S1	0.93	2.87	3.2056 (19)	103
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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: 10.1107/S1600536812035301/yk2069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035301/yk2069Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812035301/yk2069Isup3.cml

checkCIF report

Comment top

The title compound has been prepared in continuation to our ongoing project of synthesizing various derivatives of N-phenyl-1,3-thiazol-2-amine. We have recently published the synthesis and crystal structure of N-(2,4,6-trimethylphenyl)-1,3-thiazol-2-amine (Babar et al., 2012) which is related to the title compound.

In the title compound (Fig. 1), the 1,3-dichlorobenzene group A (C1–C6/CL1/CL2) and 1,3-thiazol-2-amine group B (N1/C7/S1/C8/C9/N2) are planar with r.m.s. deviations of 0.009 Å and 0.030 Å, respectively. The dihedral angle between the planes of A and B is 53.28 (4)°. The molecules are joined into dimers by pairs of N—H···N hydrogen bonds (Table 1, Fig. 2), forming R₂²(8) ring motif (Bernstein et al., 1995). The dimers are further linked by C—H···Cl hydrogen bonds into layers parallel to (0 1 1). Thiazole rings form stacks along the c axis direction with intercentroid separation Cg···Cgⁱ [i = x, 3/2 - y, ±1/2 + z] of 3.8581 (9) Å, indicating π–π interactions.

Related literature top

For the synthesis and crystal structure of a related compound, see: Babar et al. (2012). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A mixture of N-(2,4-dichlorophenyl)thiourea (1.00 g, 4.52 mmol) and 2-chloro-1,1-dimethoxyethane(0.93 g, 6.12 mmol) was dissolved in water- methanol mixture (1:2) (100 mL). A few drops of concentrated HCl were added and the reaction mixture was refluxed for 4 h. Water (100 ml) was added, and the mixture was neutralized with aqueous NaOH to pH=8. The resulting precipitate was filtered and washed with ice cold water. The crude product was recrystallized from chloroform - hexane mixture (1:2) to obtain white prisms.

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. Molecular structure of the title compound showing the atom labelling scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing showing molecular dimer linked to the anothers by C—H···Cl interactions.

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

Crystal data top

C₉H₆Cl₂N₂S	F(000) = 496
M_r = 245.12	D_x = 1.602 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 912 reflections
a = 13.0270 (9) Å	θ = 1.6–27.2°
b = 10.1183 (6) Å	µ = 0.80 mm⁻¹
c = 7.7159 (5) Å	T = 296 K
β = 91.974 (3)°	Prism, yellow
V = 1016.44 (11) Å³	0.33 × 0.28 × 0.22 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2245 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 7.80 pixels mm^-1	θ_max = 27.2°, θ_min = 1.6°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −12→12
T_min = 0.778, T_max = 0.844	l = −9→9
8039 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0406P)² + 0.2925P] where P = (F_o² + 2F_c²)/3
2245 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₉H₆Cl₂N₂S	V = 1016.44 (11) Å³
M_r = 245.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0270 (9) Å	µ = 0.80 mm⁻¹
b = 10.1183 (6) Å	T = 296 K
c = 7.7159 (5) Å	0.33 × 0.28 × 0.22 mm
β = 91.974 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2245 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1957 reflections with I > 2σ(I)
T_min = 0.778, T_max = 0.844	R_int = 0.020
8039 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
2245 reflections	Δρ_min = −0.30 e Å⁻³
127 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
Cl1	0.24571 (4)	0.37457 (5)	0.29544 (6)	0.0545 (2)
Cl2	−0.05984 (3)	0.34681 (6)	0.74042 (8)	0.0662 (2)
S1	0.33053 (3)	0.77775 (4)	0.66934 (5)	0.0405 (1)
N1	0.35990 (10)	0.51946 (12)	0.57795 (18)	0.0403 (4)
N2	0.49723 (10)	0.66580 (13)	0.57830 (18)	0.0400 (4)
C1	0.26014 (11)	0.48156 (14)	0.6171 (2)	0.0353 (4)
C2	0.19932 (12)	0.41107 (15)	0.4977 (2)	0.0369 (4)
C3	0.10147 (12)	0.36979 (16)	0.5348 (2)	0.0434 (5)
C4	0.06296 (12)	0.40070 (17)	0.6935 (2)	0.0451 (5)
C5	0.12029 (14)	0.47052 (18)	0.8147 (2)	0.0505 (6)
C6	0.21843 (14)	0.50928 (18)	0.7763 (2)	0.0463 (5)
C7	0.40145 (11)	0.64084 (14)	0.60680 (18)	0.0326 (4)
C8	0.43848 (14)	0.87355 (15)	0.6496 (2)	0.0455 (5)
C9	0.51714 (14)	0.79861 (16)	0.6017 (2)	0.0462 (5)
H1	0.39818	0.46092	0.53165	0.0483*
H3	0.06225	0.32185	0.45384	0.0520*
H5	0.09331	0.49142	0.92130	0.0606*
H6	0.25772	0.55521	0.85926	0.0556*
H8	0.44170	0.96415	0.66933	0.0545*
H9	0.58188	0.83417	0.58503	0.0554*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0514 (3)	0.0636 (3)	0.0487 (3)	−0.0090 (2)	0.0058 (2)	−0.0158 (2)
Cl2	0.0351 (2)	0.0737 (3)	0.0905 (4)	−0.0031 (2)	0.0114 (2)	0.0243 (3)
S1	0.0421 (2)	0.0346 (2)	0.0453 (2)	0.0064 (2)	0.0081 (2)	−0.0047 (2)
N1	0.0325 (7)	0.0334 (6)	0.0554 (8)	−0.0019 (5)	0.0082 (6)	−0.0134 (6)
N2	0.0350 (7)	0.0333 (6)	0.0519 (8)	−0.0022 (5)	0.0059 (6)	−0.0070 (6)
C1	0.0319 (7)	0.0302 (7)	0.0438 (8)	0.0008 (6)	0.0034 (6)	−0.0011 (6)
C2	0.0365 (8)	0.0338 (7)	0.0405 (8)	0.0009 (6)	0.0019 (6)	−0.0005 (6)
C3	0.0351 (8)	0.0396 (8)	0.0550 (10)	−0.0030 (6)	−0.0047 (7)	0.0039 (7)
C4	0.0319 (8)	0.0420 (9)	0.0619 (11)	0.0019 (7)	0.0075 (7)	0.0141 (8)
C5	0.0470 (10)	0.0526 (10)	0.0530 (10)	0.0006 (8)	0.0170 (8)	−0.0013 (8)
C6	0.0454 (9)	0.0480 (9)	0.0458 (9)	−0.0049 (7)	0.0059 (7)	−0.0078 (7)
C7	0.0342 (8)	0.0313 (7)	0.0325 (7)	0.0025 (6)	0.0021 (6)	−0.0045 (5)
C8	0.0567 (10)	0.0289 (7)	0.0511 (9)	−0.0023 (7)	0.0071 (8)	−0.0040 (7)
C9	0.0449 (9)	0.0357 (8)	0.0583 (10)	−0.0084 (7)	0.0080 (8)	−0.0052 (7)

Geometric parameters (Å, º) top

Cl1—C2	1.7327 (16)	C2—C3	1.381 (2)
Cl2—C4	1.7399 (16)	C3—C4	1.375 (2)
S1—C7	1.7425 (15)	C4—C5	1.372 (2)
S1—C8	1.7191 (18)	C5—C6	1.379 (3)
N1—C1	1.3979 (19)	C8—C9	1.337 (2)
N1—C7	1.3574 (19)	C3—H3	0.9300
N2—C7	1.2992 (19)	C5—H5	0.9300
N2—C9	1.379 (2)	C6—H6	0.9300
N1—H1	0.8600	C8—H8	0.9300
C1—C6	1.389 (2)	C9—H9	0.9300
C1—C2	1.391 (2)

C7—S1—C8	88.89 (7)	C1—C6—C5	121.76 (15)
C1—N1—C7	125.53 (13)	S1—C7—N2	114.44 (11)
C7—N2—C9	110.16 (13)	S1—C7—N1	123.54 (11)
C7—N1—H1	117.00	N1—C7—N2	121.87 (13)
C1—N1—H1	117.00	S1—C8—C9	109.99 (12)
N1—C1—C6	122.05 (14)	N2—C9—C8	116.50 (16)
N1—C1—C2	120.67 (14)	C2—C3—H3	121.00
C2—C1—C6	117.26 (14)	C4—C3—H3	121.00
C1—C2—C3	121.78 (14)	C4—C5—H5	120.00
Cl1—C2—C3	118.39 (12)	C6—C5—H5	120.00
Cl1—C2—C1	119.83 (12)	C1—C6—H6	119.00
C2—C3—C4	118.92 (15)	C5—C6—H6	119.00
C3—C4—C5	121.14 (15)	S1—C8—H8	125.00
Cl2—C4—C3	118.70 (12)	C9—C8—H8	125.00
Cl2—C4—C5	120.15 (13)	N2—C9—H9	122.00
C4—C5—C6	119.13 (15)	C8—C9—H9	122.00

C8—S1—C7—N1	−174.25 (13)	C6—C1—C2—Cl1	179.25 (12)
C8—S1—C7—N2	1.39 (12)	C6—C1—C2—C3	−0.1 (2)
C7—S1—C8—C9	−0.80 (12)	N1—C1—C6—C5	−179.38 (15)
C7—N1—C1—C2	134.53 (16)	C2—C1—C6—C5	−0.9 (2)
C7—N1—C1—C6	−47.0 (2)	Cl1—C2—C3—C4	−178.59 (13)
C1—N1—C7—S1	−9.7 (2)	C1—C2—C3—C4	0.8 (2)
C1—N1—C7—N2	174.96 (14)	C2—C3—C4—Cl2	−179.29 (12)
C9—N2—C7—S1	−1.53 (17)	C2—C3—C4—C5	−0.5 (3)
C9—N2—C7—N1	174.19 (14)	Cl2—C4—C5—C6	178.34 (14)
C7—N2—C9—C8	0.9 (2)	C3—C4—C5—C6	−0.5 (3)
N1—C1—C2—Cl1	−2.2 (2)	C4—C5—C6—C1	1.2 (3)
N1—C1—C2—C3	178.44 (14)	S1—C8—C9—N2	0.13 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.86	2.07	2.9302 (19)	174
C3—H3···Cl2ⁱⁱ	0.93	2.82	3.7483 (17)	173
C6—H6···S1	0.93	2.87	3.2056 (19)	103

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

Experimental details

Crystal data
Chemical formula	C₉H₆Cl₂N₂S
M_r	245.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.0270 (9), 10.1183 (6), 7.7159 (5)
β (°)	91.974 (3)
V (Å³)	1016.44 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.80
Crystal size (mm)	0.33 × 0.28 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.778, 0.844
No. of measured, independent and observed [I > 2σ(I)] reflections	8039, 2245, 1957
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.04
No. of reflections	2245
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.30

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	2.07	2.9302 (19)	174
C3—H3···Cl2ⁱⁱ	0.93	2.82	3.7483 (17)	173
C6—H6···S1	0.93	2.87	3.2056 (19)	103

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. They are also thankful to the Higher Education Commission (HEC), Pakistan, for financial assistance.

References

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