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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1162.
Published online 2010 April 24. doi:  10.1107/S1600536810013863
PMCID: PMC2979166

1-(4-Chloro­phen­yl)-3-(2-thienylcarbon­yl)thio­urea

Abstract

The title compound, C12H9ClN2OS2, exists in the thio­amide form with an intra­molecular N—H(...)O hydrogen bond across the thio­urea and the carbonyl group. The dihedral angle between the rings is 10.36 (11)°. In the crystal structure, mol­ecules are linked into chains by weak inter­molecular C—H(...)Cl hydrogen-bonding inter­actions.

Related literature

For general background to the biological activity of thio­urea derivatives, see: Xu et al. (2004 [triangle]); Gu et al. (2007 [triangle]). For related structures, see: Saeed et al. (2008 [triangle], 2009 [triangle]). For the cytotoxicity of anti­cancer drugs to normal cells in cancer therapy, see: Saeed et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1162-scheme1.jpg

Experimental

Crystal data

  • C12H9ClN2OS2
  • M r = 296.78
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1162-efi7.jpg
  • a = 4.6552 (7) Å
  • b = 11.660 (2) Å
  • c = 23.630 (4) Å
  • β = 95.626 (2)°
  • V = 1276.4 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.61 mm−1
  • T = 300 K
  • 0.42 × 0.19 × 0.08 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.783, T max = 0.953
  • 8549 measured reflections
  • 3102 independent reflections
  • 2578 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.107
  • S = 1.07
  • 3102 reflections
  • 172 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT and CrystalStructure (Rigaku/MSC and Rigaku, 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 DIAMOND (Brandenburg, 1998 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013863/lx2142sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013863/lx2142Isup2.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 Hong Kong Polytechnic University for providing laboratory and analytical facilities.

supplementary crystallographic information

Comment

Thiourea and its derivatives are an important class of organic compounds in which sulfur is the major ligand atom which plays an important role in coordination chemistry with transition metals. Thiourea and its derivatives have found extensive applications in the fields of medicine, agriculture and analytical chemistry. Thioureas are also known to exhibit a wide range of biological activities including anticancer (Saeed et al., 2010), antifungal (Saeed et al., 2008), antiviral, antibacterial, anti-tubercular, anti-thyroidal, herbicidal and insecticidal activities, organocatalyst (Gu et al., 2007) and as agrochemicals (Xu et al., 2004).

The 4-chlorophenyl ring is slightly twisted {15.04 (8)°} from the thiourea plane. The thioureido group is also slightly twisted {5.0 (1)°} from the thiophene ring plane of S2/C9/C10/C11/C12. The molecular packing (Fig. 2) exhibits the thioamide form with an intramolecular N–H···O hydrogen bond across the thiourea system, with a N1–H1N···O1 (Table 1). The crystal packing (Fig. 2) is stabilized by weak intermolecular C–H···Cl hydrogen bonds between the thiophene H atom and the chlorine of an adjacent molecule, with a C12–H12···Cl1i (Table 1).

Experimental

A solution of 2-thiophenecarbonyl chloride (0.01 mol) in anhydrous acetone (80 ml) was added dropwise to a suspension of ammonium thiocyanate (0.01 mol) in anhydrous acetone (50 ml) and the reaction mixture was refluxed for 50 minutes. After cooling to room temperature, a solution of 4-chloroaniline (0.01 mol) in dry acetone (25 ml) was added and the resulting mixture refluxed for 2 h. The reaction mixture was poured into five times its volume of cold water, upon which the thiourea precipitated. The product was recrystallized from ethanol as white block crystals.

Refinement

The H atoms bound C atoms were located from difference Fourier map and refined freely. All H atoms of C atoms were positioned geometrically and refined using a riding model, with C–H = 0.93 Å for aryl and thiophenyl H atoms. Uiso(H) = 1.2Ueq(C) for aryl thiophenyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
Fig. 2.
N–H···O and C–H···Cl interactions (dotted lines) in the crystal structure of the title compound. [Symmetry codes: (i) x - 5/2, - y + 1/2, z - 1/2 (ii) x + 5/2, - y + 1/2, z + 1/2.]

Crystal data

C12H9ClN2OS2F(000) = 608
Mr = 296.78Dx = 1.544 Mg m3
Monoclinic, P21/nMelting point: 412 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 4.6552 (7) ÅCell parameters from 8801 reflections
b = 11.660 (2) Åθ = 1.7–28.3°
c = 23.630 (4) ŵ = 0.61 mm1
β = 95.626 (2)°T = 300 K
V = 1276.4 (4) Å3Prism, yellow
Z = 40.42 × 0.19 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer3102 independent reflections
Radiation source: fine-focus sealed tube2578 reflections with I > 2σ(I)
graphiteRint = 0.019
ω scanθmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −6→6
Tmin = 0.783, Tmax = 0.953k = −9→15
8549 measured reflectionsl = −30→31

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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0546P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3
3102 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

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.
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 > 2sigma(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
Cl11.37357 (11)0.14501 (5)0.54454 (2)0.06174 (17)
S10.42417 (13)0.54355 (4)0.38816 (3)0.06558 (19)
S2−0.38487 (12)0.23708 (4)0.20193 (2)0.05870 (17)
O10.0745 (3)0.22204 (11)0.29637 (6)0.0549 (3)
N10.4375 (3)0.31315 (13)0.37757 (6)0.0426 (3)
H1N0.357 (5)0.2572 (18)0.3578 (9)0.053 (6)*
N20.0880 (3)0.41119 (13)0.32158 (7)0.0446 (3)
H2N0.001 (5)0.475 (2)0.3134 (10)0.063 (7)*
C11.1034 (4)0.19841 (16)0.49542 (8)0.0448 (4)
C20.9940 (4)0.12913 (16)0.45099 (8)0.0470 (4)
H21.06550.05540.44700.056*
C30.7761 (4)0.17123 (15)0.41242 (7)0.0446 (4)
H30.70100.12540.38230.053*
C40.6685 (4)0.28161 (15)0.41829 (7)0.0395 (3)
C50.7819 (4)0.34955 (16)0.46329 (8)0.0486 (4)
H50.71110.42330.46770.058*
C61.0007 (4)0.30746 (17)0.50170 (8)0.0506 (4)
H61.07770.35310.53170.061*
C70.3216 (4)0.41540 (14)0.36378 (7)0.0409 (4)
C8−0.0182 (4)0.32019 (15)0.28912 (7)0.0408 (4)
C9−0.2510 (4)0.34711 (15)0.24497 (7)0.0413 (4)
C10−0.3865 (4)0.44880 (17)0.22982 (8)0.0499 (4)
H10−0.34390.51830.24810.060*
C11−0.5988 (5)0.43535 (18)0.18316 (9)0.0574 (5)
H11−0.71090.49520.16710.069*
C12−0.6202 (5)0.32616 (19)0.16464 (9)0.0586 (5)
H12−0.75030.30220.13460.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0533 (3)0.0688 (3)0.0585 (3)−0.0017 (2)−0.0177 (2)0.0113 (2)
S10.0745 (4)0.0364 (2)0.0783 (4)−0.0039 (2)−0.0311 (3)−0.0049 (2)
S20.0706 (3)0.0434 (3)0.0563 (3)0.0030 (2)−0.0228 (2)−0.0074 (2)
O10.0672 (9)0.0381 (6)0.0547 (8)0.0023 (6)−0.0187 (6)−0.0028 (6)
N10.0463 (8)0.0358 (7)0.0429 (8)−0.0042 (6)−0.0088 (6)−0.0016 (6)
N20.0469 (8)0.0372 (7)0.0466 (8)0.0002 (6)−0.0105 (6)−0.0020 (6)
C10.0384 (8)0.0518 (10)0.0427 (9)−0.0060 (7)−0.0035 (7)0.0076 (7)
C20.0494 (10)0.0429 (9)0.0473 (9)0.0012 (8)−0.0023 (7)0.0025 (7)
C30.0491 (9)0.0403 (9)0.0423 (9)−0.0046 (7)−0.0060 (7)−0.0026 (7)
C40.0387 (8)0.0392 (8)0.0394 (8)−0.0047 (6)−0.0026 (6)0.0029 (7)
C50.0552 (10)0.0416 (9)0.0465 (9)−0.0005 (8)−0.0075 (8)−0.0035 (7)
C60.0526 (10)0.0501 (10)0.0460 (9)−0.0084 (8)−0.0113 (8)−0.0045 (8)
C70.0418 (8)0.0395 (8)0.0401 (8)−0.0048 (7)−0.0030 (6)−0.0010 (7)
C80.0428 (8)0.0395 (8)0.0388 (8)−0.0031 (7)−0.0020 (6)0.0002 (7)
C90.0436 (8)0.0394 (9)0.0392 (8)−0.0041 (7)−0.0042 (6)0.0001 (7)
C100.0528 (10)0.0419 (10)0.0519 (10)0.0004 (8)−0.0098 (8)0.0005 (8)
C110.0578 (11)0.0509 (11)0.0595 (12)0.0041 (9)−0.0146 (9)0.0077 (9)
C120.0620 (12)0.0570 (12)0.0514 (10)−0.0013 (9)−0.0214 (9)0.0007 (9)

Geometric parameters (Å, °)

Cl1—C11.7408 (18)C2—H20.9300
S1—C71.6548 (17)C3—C41.393 (2)
S2—C121.693 (2)C3—H30.9300
S2—C91.7158 (17)C4—C51.388 (2)
O1—C81.229 (2)C5—C61.386 (3)
N1—C71.336 (2)C5—H50.9300
N1—C41.419 (2)C6—H60.9300
N1—H1N0.87 (2)C8—C91.463 (2)
N2—C81.373 (2)C9—C101.374 (2)
N2—C71.402 (2)C10—C111.415 (3)
N2—H2N0.86 (2)C10—H100.9300
C1—C61.372 (3)C11—C121.347 (3)
C1—C21.382 (3)C11—H110.9300
C2—C31.385 (2)C12—H120.9300
C12—S2—C991.64 (10)C1—C6—C5119.94 (17)
C7—N1—C4131.12 (15)C1—C6—H6120.0
C7—N1—H1N113.5 (14)C5—C6—H6120.0
C4—N1—H1N115.4 (14)N1—C7—N2114.12 (15)
C8—N2—C7129.51 (16)N1—C7—S1128.69 (13)
C8—N2—H2N113.9 (16)N2—C7—S1117.15 (13)
C7—N2—H2N116.5 (16)O1—C8—N2122.64 (16)
C6—C1—C2121.18 (16)O1—C8—C9121.65 (16)
C6—C1—Cl1119.75 (14)N2—C8—C9115.71 (15)
C2—C1—Cl1119.06 (15)C10—C9—C8131.32 (16)
C1—C2—C3118.96 (17)C10—C9—S2111.10 (13)
C1—C2—H2120.5C8—C9—S2117.57 (13)
C3—C2—H2120.5C9—C10—C11112.03 (17)
C2—C3—C4120.61 (16)C9—C10—H10124.0
C2—C3—H3119.7C11—C10—H10124.0
C4—C3—H3119.7C12—C11—C10112.44 (18)
C5—C4—C3119.35 (16)C12—C11—H11123.8
C5—C4—N1125.26 (16)C10—C11—H11123.8
C3—C4—N1115.33 (15)C11—C12—S2112.79 (15)
C6—C5—C4119.96 (18)C11—C12—H12123.6
C6—C5—H5120.0S2—C12—H12123.6
C4—C5—H5120.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.87 (2)1.91 (2)2.651 (2)143 (2)
C12—H12···Cl1i0.932.693.523 (2)149

Symmetry codes: (i) x−5/2, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2142).

References

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