2-Chloro-N-[4-(4-chloro­phen­yl)-1,3-thia­zol-2-yl]acetamide

Saravanan, K.; Priya, K.; Anand, S.A.A.; Kabilan, S.; Selvanayagam, S.

doi:10.1107/S2414314616009032

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160903

doi:10.1107/S2414314616009032

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2-Chloro-N-[4-(4-chlorophenyl)-1,3-thiazol-2-yl]acetamide

K. Saravanan,^a K. Priya,^a S. Athavan Alias Anand,^a S. Kabilan ^a ^* and S. Selvanayagam ^b ‡

^aDrug Discovery Lab, Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, India, and ^bPG & Research Department of Physics, Government Arts College, Melur 625 106, India
^*Correspondence e-mail: profskabilan@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 2 June 2016; accepted 3 June 2016; online 14 June 2016)

In the title acetamide, C₁₁H₈Cl₂N₂OS, the chlorophenyl ring is oriented at an angle of 7.1 (1)° with respect to the thiazole ring. In the crystal, molecules are linked via C—H⋯O intermolecular interactions, forming C(10) chains propagating in a zigzag manner along the b axis.

Keywords: crystal structure; acetamide derivatives; C—H⋯N and C—H⋯O hydrogen bonds.

CCDC reference: 1483458

Structure description

In a continuation of our work on the crystal structure analysis of acetamide derivatives, we have undertaken a single-crystal X-ray diffraction study for the title compound, and the results are presented here. The molecular structure of the title compound is illustrated in Fig. 1. The geometry of the present structure, apart from atom Cl2. is comparable with that reported for a similar structure, namely 2-chloro-N-(4-phenyl-1,3-thiazol-2-yl)acetamide (II) (Saravanan et al., 2016 ). The superposition of the structures (Fig. 2) using Qmol (Gans & Shalloway, 2001 ), gives r.m.s. deviations of 0.858 and 0.595 Å, respectively, for molecules A and B in (II). The thiazole ring is planar with a maximum deviation of 0.005 (3) Å for atom C7. Chlorine atom Cl2 is deviates by 0.033 (1) Å from the best plane through the chlorophenyl ring. The chlorophenyl ring is oriented at an angle of 7.1 (1)° to the thiazole ring. The molecular structure is influenced by an intramolecular C—H⋯N short contact (Table 1). In the crystal, C—H⋯O interactions link the molecules, forming C(10) chains propagating along the b axis in a zigzag manner (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N1	0.93	2.47	2.827 (4)	103
C5—H5⋯O1ⁱ	0.93	2.58	3.498 (5)	169
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
Superposition of the present structure except Cl2 (cyan) with the similar reported structure (molecule A in green and molecule B in brown; Saravanan et al., 2016

Figure 3
Crystal packing of the title compound, viewed down the c axis. The C—H⋯N and C—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

). For clarity, H atoms not involved in these hydrogen bonds have been omitted.

Synthesis and crystallization

To a solution of the 4-(4-chlorophenyl) thiazol-2-amine (1.5 g, 7.14 mmol) in dry toluene (25 ml), K₂CO₃ (1.97 g, 14.28 mmol) and chloroacetyl chloride (0.57 ml, 7.14 mmol) was added. The reaction mixture was heated to reflux for 3 h. After completion of the reaction (monitored by pre-coated TLC), the reaction mixture was cooled to RT and diluted with DCM (45 ml). The organic layer was washed with saturated NaHCO₃ solution, water (10 ml × 3) and dried over Na₂SO₄. The filtrate was concentrated and the crude product mass was purified by precipitation using petroleum ether and diethyl ether (3:1) to give a colorless solid. This solid was recrystallized in ethyl acetate to yield a colorless crystal of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₈Cl₂N₂OS
M_r	287.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.0940 (12), 14.738 (3), 15.703 (3)
β (°)	96.932 (9)
V (Å³)	1170.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.72
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
No. of measured, independent and observed [I > 2σ(I)] reflections	6510, 2688, 1679
R_int	0.100
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.178, 0.98
No. of reflections	2688
No. of parameters	160
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.41
Computer programs: SMART and SAINT (Bruker, 2002 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1483458

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616009032/bt4014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009032/bt4014Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616009032/bt4014Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

2-Chloro-N-[4-(4-chlorophenyl)-1,3-thiazol-2-yl]acetamide top

Crystal data top

C₁₁H₈Cl₂N₂OS	F(000) = 584
M_r = 287.15	D_x = 1.630 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.0940 (12) Å	Cell parameters from 4320 reflections
b = 14.738 (3) Å	θ = 3.2–26.9°
c = 15.703 (3) Å	µ = 0.72 mm⁻¹
β = 96.932 (9)°	T = 296 K
V = 1170.3 (4) Å³	Block, colourless
Z = 4	0.24 × 0.22 × 0.20 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.100
Radiation source: fine-focus sealed tube	θ_max = 27.6°, θ_min = 3.1°
ω scans	h = −6→6
6510 measured reflections	k = −18→19
2688 independent reflections	l = −20→12
1679 reflections with I > 2σ(I)

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.178	w = 1/[σ²(F_o²) + (0.0772P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
2688 reflections	Δρ_max = 0.47 e Å⁻³
160 parameters	Δρ_min = −0.41 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1	0.40270 (17)	0.34381 (7)	0.21301 (7)	0.0471 (3)
O1	0.3657 (5)	0.15655 (18)	0.18809 (18)	0.0564 (7)
N1	−0.0350 (5)	0.39261 (18)	0.12588 (19)	0.0394 (7)
N2	0.0005 (6)	0.2354 (2)	0.1381 (2)	0.0438 (7)
Cl1	0.1848 (3)	−0.02066 (7)	0.11890 (9)	0.0789 (5)
Cl2	−0.4015 (2)	0.82462 (7)	0.03508 (7)	0.0614 (4)
C1	−0.2452 (7)	0.5616 (2)	0.0659 (2)	0.0453 (8)
H1	−0.3220	0.5072	0.0460	0.054*
C2	−0.3652 (8)	0.6429 (3)	0.0384 (2)	0.0476 (9)
H2A	−0.5208	0.6435	0.0008	0.057*
C3	−0.2477 (7)	0.7222 (2)	0.0683 (2)	0.0418 (8)
C4	−0.0174 (8)	0.7233 (2)	0.1237 (2)	0.0476 (9)
H4	0.0591	0.7780	0.1429	0.057*
C5	0.0987 (7)	0.6419 (2)	0.1506 (2)	0.0428 (8)
H5	0.2545	0.6419	0.1882	0.051*
C6	−0.0146 (6)	0.5598 (2)	0.1221 (2)	0.0358 (7)
C7	0.1045 (6)	0.4713 (2)	0.1506 (2)	0.0371 (7)
C8	0.3431 (7)	0.4571 (2)	0.1969 (2)	0.0450 (8)
H8	0.4594	0.5030	0.2173	0.054*
C9	0.0985 (6)	0.3231 (2)	0.1550 (2)	0.0376 (8)
C10	0.1383 (7)	0.1575 (2)	0.1540 (2)	0.0417 (8)
C11	−0.0185 (8)	0.0745 (2)	0.1235 (3)	0.0550 (10)
H11A	−0.1120	0.0860	0.0670	0.066*
H11B	−0.1490	0.0622	0.1622	0.066*
H2	−0.158 (4)	0.237 (3)	0.113 (3)	0.097 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0321 (5)	0.0426 (5)	0.0636 (6)	0.0025 (4)	−0.0066 (4)	0.0069 (4)
O1	0.0468 (15)	0.0449 (15)	0.0721 (18)	0.0114 (12)	−0.0144 (13)	−0.0022 (12)
N1	0.0294 (13)	0.0330 (14)	0.0553 (18)	0.0026 (12)	0.0035 (12)	−0.0003 (12)
N2	0.0324 (15)	0.0346 (15)	0.063 (2)	0.0055 (12)	−0.0021 (14)	−0.0005 (13)
Cl1	0.0867 (9)	0.0387 (6)	0.1008 (10)	0.0226 (6)	−0.0312 (7)	−0.0140 (5)
Cl2	0.0659 (7)	0.0399 (5)	0.0780 (8)	0.0161 (5)	0.0067 (5)	0.0094 (4)
C1	0.0434 (19)	0.0308 (17)	0.059 (2)	0.0009 (15)	−0.0051 (16)	−0.0019 (15)
C2	0.046 (2)	0.045 (2)	0.050 (2)	0.0063 (17)	−0.0031 (16)	0.0050 (16)
C3	0.0453 (19)	0.0345 (18)	0.047 (2)	0.0061 (15)	0.0113 (16)	0.0048 (14)
C4	0.051 (2)	0.0354 (19)	0.057 (2)	−0.0032 (17)	0.0087 (17)	−0.0020 (16)
C5	0.0361 (17)	0.0380 (18)	0.053 (2)	−0.0023 (15)	−0.0014 (15)	−0.0026 (15)
C6	0.0310 (16)	0.0369 (17)	0.0398 (18)	−0.0022 (13)	0.0057 (13)	0.0013 (14)
C7	0.0323 (16)	0.0348 (17)	0.0439 (19)	−0.0018 (13)	0.0041 (14)	0.0007 (13)
C8	0.0373 (18)	0.040 (2)	0.055 (2)	−0.0026 (15)	−0.0048 (15)	0.0018 (15)
C9	0.0258 (15)	0.0360 (18)	0.051 (2)	0.0021 (13)	0.0047 (14)	0.0000 (14)
C10	0.0390 (18)	0.0384 (19)	0.047 (2)	0.0102 (15)	0.0011 (15)	0.0005 (14)
C11	0.054 (2)	0.0349 (19)	0.073 (3)	0.0117 (17)	−0.0055 (19)	−0.0040 (18)

Geometric parameters (Å, º) top

S1—C8	1.710 (4)	C2—C3	1.369 (5)
S1—C9	1.727 (3)	C2—H2A	0.9300
O1—C10	1.216 (4)	C3—C4	1.374 (5)
N1—C9	1.283 (4)	C4—C5	1.381 (5)
N1—C7	1.390 (4)	C4—H4	0.9300
N2—C10	1.352 (4)	C5—C6	1.391 (5)
N2—C9	1.401 (4)	C5—H5	0.9300
N2—H2	0.856 (10)	C6—C7	1.485 (5)
Cl1—C11	1.750 (4)	C7—C8	1.355 (5)
Cl2—C3	1.751 (3)	C8—H8	0.9300
C1—C6	1.382 (5)	C10—C11	1.507 (5)
C1—C2	1.390 (5)	C11—H11A	0.9700
C1—H1	0.9300	C11—H11B	0.9700

C8—S1—C9	87.85 (16)	C1—C6—C7	119.7 (3)
C9—N1—C7	109.6 (3)	C5—C6—C7	121.9 (3)
C10—N2—C9	125.7 (3)	C8—C7—N1	114.6 (3)
C10—N2—H2	123 (3)	C8—C7—C6	127.2 (3)
C9—N2—H2	111 (3)	N1—C7—C6	118.1 (3)
C6—C1—C2	121.5 (3)	C7—C8—S1	111.2 (3)
C6—C1—H1	119.2	C7—C8—H8	124.4
C2—C1—H1	119.2	S1—C8—H8	124.4
C3—C2—C1	118.1 (3)	N1—C9—N2	120.5 (3)
C3—C2—H2A	120.9	N1—C9—S1	116.8 (3)
C1—C2—H2A	120.9	N2—C9—S1	122.7 (2)
C2—C3—C4	122.1 (3)	O1—C10—N2	122.5 (3)
C2—C3—Cl2	118.2 (3)	O1—C10—C11	124.8 (3)
C4—C3—Cl2	119.7 (3)	N2—C10—C11	112.8 (3)
C3—C4—C5	119.0 (3)	C10—C11—Cl1	111.7 (3)
C3—C4—H4	120.5	C10—C11—H11A	109.3
C5—C4—H4	120.5	Cl1—C11—H11A	109.3
C4—C5—C6	120.7 (3)	C10—C11—H11B	109.3
C4—C5—H5	119.6	Cl1—C11—H11B	109.3
C6—C5—H5	119.6	H11A—C11—H11B	107.9
C1—C6—C5	118.4 (3)

C6—C1—C2—C3	0.3 (6)	C5—C6—C7—N1	173.7 (3)
C1—C2—C3—C4	0.2 (6)	N1—C7—C8—S1	−0.8 (4)
C1—C2—C3—Cl2	−179.0 (3)	C6—C7—C8—S1	−178.5 (3)
C2—C3—C4—C5	−0.4 (6)	C9—S1—C8—C7	0.3 (3)
Cl2—C3—C4—C5	178.8 (3)	C7—N1—C9—N2	−179.5 (3)
C3—C4—C5—C6	0.1 (5)	C7—N1—C9—S1	−0.9 (4)
C2—C1—C6—C5	−0.5 (5)	C10—N2—C9—N1	169.4 (3)
C2—C1—C6—C7	179.1 (3)	C10—N2—C9—S1	−9.1 (5)
C4—C5—C6—C1	0.3 (5)	C8—S1—C9—N1	0.4 (3)
C4—C5—C6—C7	−179.3 (3)	C8—S1—C9—N2	178.9 (3)
C9—N1—C7—C8	1.1 (4)	C9—N2—C10—O1	2.4 (6)
C9—N1—C7—C6	179.0 (3)	C9—N2—C10—C11	−176.6 (3)
C1—C6—C7—C8	171.7 (4)	O1—C10—C11—Cl1	−14.5 (5)
C5—C6—C7—C8	−8.6 (6)	N2—C10—C11—Cl1	164.5 (3)
C1—C6—C7—N1	−6.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N1	0.93	2.47	2.827 (4)	103
C5—H5···O1ⁱ	0.93	2.58	3.498 (5)	169

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

Footnotes

‡Additional correspondence author, e-mail: s_selvanayagam@rediffmail.com.

Acknowledgements

The authors are thankful for the funding support from the Department of Biotechnology North East Collaboration (DBT NEC) Research Project, Grant No. BT/252/NE/TBP/2011, New Delhi, India.

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