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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3078.
Published online 2010 November 6. doi:  10.1107/S1600536810044193
PMCID: PMC3011524

2,4-Dichloro-N-(1,3-thia­zol-2-yl)benzamide

Abstract

In the mol­ecular structure of the title compound, C10H6Cl2N2OS, the dihedral angle between the benzene plane and the plane defined by the amide functionality is 8.6 (1)°, while the thia­zole ring plane is twisted with respect to the amide plane by 68.71 (5)°. In the crystal, pairs of inter­molecular N—H(...)N hydrogen-bond inter­actions connect the mol­ecules into inversion dimers. π–π inter­actions are also observed between neighbouring thia­zole and phen­yl rings [centroid–centroid distance = 3.5905 (13) Å] and a weak C—H(...)π interaction also occurs.

Related literature

For the synthesis of related thia­zole derivatives and their application, see: Raman et al. (2000 [triangle]); Yunus et al. (2007 [triangle], 2008 [triangle]). For microwave-assisted synthesis of amides, see Wang et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3078-scheme1.jpg

Experimental

Crystal data

  • C10H6Cl2N2OS
  • M r = 273.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3078-efi1.jpg
  • a = 14.054 (3) Å
  • b = 13.063 (3) Å
  • c = 6.2880 (14) Å
  • β = 101.578 (3)°
  • V = 1130.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.74 mm−1
  • T = 304 K
  • 0.38 × 0.27 × 0.07 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.768, T max = 0.950
  • 5906 measured reflections
  • 1993 independent reflections
  • 1820 reflections with I > 2σ(I)
  • R int = 0.014

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.080
  • S = 1.06
  • 1993 reflections
  • 149 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT and CrystalStructure (Rigaku/MSC, 2006 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]) and Mercury (Macrae et al., 2008 [triangle]); software used to prepare material for publication: SHELX97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044193/im2236sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044193/im2236Isup2.hkl

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

Acknowledgments

The authors are grateful to the Department of Chemistry, Research Complex, Allama Iqbal Open University, Islamabad and the University of Hong Kong, Pokfulam, Hong Kong SAR, People’s Republic of China for providing the laboratory and analytical facilities.

supplementary crystallographic information

Comment

Substituted and unsubstituted thiazole derivatives are of great importance in biological systems due to their vast range of biological activities such as anti-inflammatory, analgestic and antipyretic (Raman et al., 2000; Yunus et al., 2007, 2008). On the other hand, amide compounds have extensive applications in pharmaceutical industry (Wang et al., 2008).

The title compound, 2,4-dichloro-N-thiazol-2-yl-benzamide, C10H6Cl2N2OS, crystallizes in the monoclinic space group P21/c (#14). The molecule is not planar showing a dihedral angle of 8.6 (1)° of the amide group, C3—C5/N2/O1 with respect to the phenyl ring plane, C5—C10/Cl1/Cl2. The thiazolyl ring, C1—C3/N1/S1, is twisted (68.71 (5)°) relative to the amide group. In additon, the phenyl ring plane makes a dihedral angle of 74.89 (5)° with the thiazole ring plane.

There are pair-wise inter-molecular N2—H2N···N1 H-bond interactions linking the molecules into dimeric arrangements. There are also π–π interactions between neighbouring thiazole, S1/N1/C1—C3 (Cg1), and phenyl rings, C5—C10 (Cg2), in the crystal lattice. The distance between ring centroids Cg1 and Cg2 is 3.5905 Å, and dihedral angle between them is determined to 0°.

There is no residual solvent accessible void volume in the unit cell.

Experimental

A mixture of 2,4-dichlorobenzoyl chloride (0.01 mol) and 2-aminothiazole (0.01 mol) was refluxed in acetone (50 ml) for 1.5 h. After cooling to room temperature, the mixture was poured into acidified cold water. The resulting solid was filtered and washed with cold acetone (yield: 72%). Single crystals of the title compound suitable for single-crystal X-ray analysis were obtained by recrystallization of the light yellow solid from ethyl acetate.

Refinement

The structure was solved by direct methods (SHELXS97) and expanded using Fourier techniques. All non-H atoms were refined anisotropically. C-bound H atoms are all placed geometrically C—H = 0.93 Å for phenyl H-atoms. They were refined using a riding model with Uiso(H) = 1.2 Ueq (Carrier). N-bound H atoms were located from difference Fourier map and are refined isotropically.

Highest peak is 0.25 at (0.9753, 0.3236, 0.26385) [0.97Å from Cl2] Deepest hole is -0.24 at (0.2315, 0.6265, 0.1208) [0.79Å from Cl1]

Figures

Fig. 1.
ORTEP plot of the compound with thermal ellipsoids at the 50% probability level and showing the atom numbering scheme.
Fig. 2.
Packing diagram.

Crystal data

C10H6Cl2N2OSF(000) = 552
Mr = 273.13Dx = 1.604 Mg m3
Monoclinic, P21/cMelting point: 487 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 14.054 (3) ÅCell parameters from 6065 reflections
b = 13.063 (3) Åθ = 2.2–25.0°
c = 6.2880 (14) ŵ = 0.74 mm1
β = 101.578 (3)°T = 304 K
V = 1130.8 (4) Å3Block, colourless
Z = 40.38 × 0.27 × 0.07 mm

Data collection

Bruker SMART 1000 CCD diffractometer1993 independent reflections
Radiation source: fine-focus sealed tube1820 reflections with I > 2σ(I)
graphiteRint = 0.014
ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −16→15
Tmin = 0.768, Tmax = 0.950k = −15→13
5906 measured reflectionsl = −6→7

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.0375P)2 + 0.4293P] where P = (Fo2 + 2Fc2)/3
1993 reflections(Δ/σ)max < 0.001
149 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

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

xyzUiso*/Ueq
Cl10.24941 (4)0.64173 (4)0.24448 (11)0.0739 (2)
Cl20.02120 (5)0.61769 (6)0.82771 (11)0.0849 (2)
S10.41434 (3)0.32850 (4)0.00755 (7)0.04892 (15)
O10.25039 (10)0.34891 (11)0.1798 (2)0.0592 (4)
N10.53725 (10)0.42950 (11)0.2878 (2)0.0452 (3)
N20.38052 (10)0.43647 (12)0.3593 (3)0.0441 (3)
C10.53294 (15)0.33469 (15)−0.0224 (3)0.0536 (5)
H10.55680.3037−0.13430.064*
C20.58651 (14)0.39011 (15)0.1371 (3)0.0500 (4)
H20.65250.40130.14570.060*
C30.44612 (12)0.40332 (12)0.2379 (3)0.0399 (4)
C40.28500 (12)0.41126 (13)0.3182 (3)0.0436 (4)
C50.22451 (12)0.46497 (13)0.4549 (3)0.0435 (4)
C60.20114 (12)0.56805 (14)0.4270 (3)0.0471 (4)
C70.13838 (13)0.61528 (15)0.5405 (3)0.0549 (5)
H70.12200.68390.51750.066*
C80.10102 (13)0.55811 (18)0.6880 (3)0.0571 (5)
C90.12440 (15)0.45612 (18)0.7240 (4)0.0637 (5)
H90.09970.41910.82710.076*
C100.18494 (14)0.40987 (16)0.6047 (3)0.0561 (5)
H100.19940.34070.62520.067*
H2N0.4017 (14)0.4739 (16)0.456 (3)0.048 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0751 (4)0.0560 (3)0.1005 (5)0.0071 (3)0.0411 (3)0.0226 (3)
Cl20.0658 (4)0.1064 (5)0.0910 (5)0.0030 (3)0.0361 (3)−0.0242 (4)
S10.0525 (3)0.0473 (3)0.0460 (3)−0.00460 (19)0.0078 (2)−0.01145 (19)
O10.0506 (8)0.0593 (8)0.0655 (9)−0.0091 (6)0.0061 (6)−0.0187 (7)
N10.0420 (8)0.0449 (8)0.0487 (8)−0.0020 (6)0.0095 (6)−0.0084 (6)
N20.0398 (8)0.0430 (8)0.0485 (8)−0.0022 (6)0.0064 (6)−0.0130 (7)
C10.0596 (11)0.0544 (11)0.0499 (10)−0.0013 (9)0.0186 (9)−0.0099 (8)
C20.0471 (10)0.0517 (11)0.0540 (10)−0.0015 (8)0.0168 (8)−0.0067 (8)
C30.0446 (9)0.0331 (8)0.0411 (9)0.0008 (7)0.0065 (7)−0.0029 (7)
C40.0424 (9)0.0385 (9)0.0479 (9)−0.0003 (7)0.0042 (7)−0.0012 (7)
C50.0344 (8)0.0457 (9)0.0482 (9)−0.0023 (7)0.0035 (7)−0.0020 (7)
C60.0399 (9)0.0460 (10)0.0555 (10)−0.0028 (7)0.0098 (8)−0.0009 (8)
C70.0451 (10)0.0489 (11)0.0705 (13)0.0011 (8)0.0108 (9)−0.0080 (9)
C80.0402 (9)0.0740 (14)0.0580 (11)−0.0009 (9)0.0123 (8)−0.0108 (10)
C90.0597 (12)0.0747 (15)0.0614 (12)−0.0019 (11)0.0234 (10)0.0083 (11)
C100.0534 (11)0.0518 (11)0.0635 (12)0.0001 (9)0.0123 (9)0.0086 (9)

Geometric parameters (Å, °)

Cl1—C61.7370 (19)C2—H20.9300
Cl2—C81.741 (2)C4—C51.499 (2)
S1—C11.716 (2)C5—C101.387 (3)
S1—C31.7299 (16)C5—C61.389 (3)
O1—C41.219 (2)C6—C71.386 (3)
N1—C31.302 (2)C7—C81.374 (3)
N1—C21.381 (2)C7—H70.9300
N2—C41.356 (2)C8—C91.380 (3)
N2—C31.379 (2)C9—C101.381 (3)
N2—H2N0.79 (2)C9—H90.9300
C1—C21.339 (3)C10—H100.9300
C1—H10.9300
C1—S1—C388.40 (9)C10—C5—C4119.82 (16)
C3—N1—C2109.94 (15)C6—C5—C4121.89 (16)
C4—N2—C3124.36 (15)C7—C6—C5121.70 (17)
C4—N2—H2N120.1 (14)C7—C6—Cl1117.84 (15)
C3—N2—H2N115.5 (14)C5—C6—Cl1120.46 (14)
C2—C1—S1110.84 (14)C8—C7—C6118.32 (19)
C2—C1—H1124.6C8—C7—H7120.8
S1—C1—H1124.6C6—C7—H7120.8
C1—C2—N1115.56 (17)C7—C8—C9121.65 (19)
C1—C2—H2122.2C7—C8—Cl2118.02 (17)
N1—C2—H2122.2C9—C8—Cl2120.32 (17)
N1—C3—N2121.23 (15)C8—C9—C10119.04 (19)
N1—C3—S1115.25 (13)C8—C9—H9120.5
N2—C3—S1123.49 (13)C10—C9—H9120.5
O1—C4—N2122.43 (17)C9—C10—C5121.08 (19)
O1—C4—C5122.07 (15)C9—C10—H10119.5
N2—C4—C5115.51 (15)C5—C10—H10119.5
C10—C5—C6118.16 (17)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the thiazole ring.
D—H···AD—HH···AD···AD—H···A
N2—H2N···N1i0.79 (2)2.09 (2)2.880 (2)178 (2)
C1—H1···Cg1ii0.932.813.501 (2)132

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2236).

References

  • Bruker (1998). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2006). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
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  • Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst.41, 466–470.
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