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

Abstract

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 R ₂ ²(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,

• a = 13.0270 (9) Å

• b = 10.1183 (6) Å

• c = 7.7159 (5) Å

• β = 91.974 (3)°

• V = 1016.44 (11) ų

• 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[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812035301/yk2069Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The hydrogen atoms were positioned geometrically (C—H = 0.93 Å, N—H = 0.86 Å) and refined as riding with U_iso(H) = 1.2U_eq(C, N).

Figures

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.

Crystal data

C9H6Cl2N2S	F(000) = 496
Mr = 245.12	Dx = 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

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

Refinement

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(Fo2) + (0.0406P)2 + 0.2925P] where P = (Fo2 + 2Fc2)/3
2245 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.