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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o313.
Published online 2007 December 21. doi:  10.1107/S160053680706031X
PMCID: PMC2915358

N-Propionylthio­urea

Abstract

The mol­ecule of the title compound, C4H8N2OS, is essentially planar; it adopts a trans configuration with respect to the position of the propionyl group relative to the thiono S atom about the C—N bond. The mol­ecular structure is stabilized by an intra­molecular N—H(...)O hydrogen bond between the propionyl O atom and the amide H atom. Mol­ecules are linked into a two-dimensional network parallel to the (10An external file that holds a picture, illustration, etc.
Object name is e-64-0o313-efi1.jpg) plane by N—H(...)O and N—H(...)S inter­molecular hydrogen bonds.

Related literature

For the crystal structures of thio­urea analogues, see: Yusof et al. (2007 [triangle]); Rosli et al. (2006 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o313-scheme1.jpg

Experimental

Crystal data

  • C4H8N2OS
  • M r = 132.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o313-efi2.jpg
  • a = 5.0790 (15) Å
  • b = 14.342 (4) Å
  • c = 9.273 (3) Å
  • β = 102.744 (6)°
  • V = 658.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.40 mm−1
  • T = 298 (2) K
  • 0.48 × 0.19 × 0.14 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.832, T max = 0.946
  • 3622 measured reflections
  • 1291 independent reflections
  • 910 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.119
  • S = 1.02
  • 1291 reflections
  • 73 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 [triangle]) and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706031X/ci2516sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706031X/ci2516Isup2.hkl

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

Acknowledgments

The authors thank the Ministry of Higher Education of Malaysia and Universiti Kebangsaan Malaysian for the research grant UKM-OUP-BTT-28/2007.

supplementary crystallographic information

Comment

Most carbonoylthiourea of the type, R1HNC(S)NHR2, such as N-butanoyl-N'- (4-nitrophenyl)thiourea (Yusof et al., 2007) can be prepared from the reaction of carbonoylchloride with ammonium thiocyanate which give carbonoyl- isothiocyanate, an intermediate for the formation of thiourea moiety when reacted with the amine compounds. However, the title compound (Fig.1) was unexpectedly obtained when the mixture of propionyl chloride and ammonium thiocyanate was stirred for 30 minutes before adding the amine compound.

The molecule is essentially planar, with a maximum deviation of 0.021 (3) Å for atom C1 from the mean plane. The propionyl group, C1/C2/C3/O1, is trans relative to the thiono C4?S1 group across the C4—N1 bond. The bond lengths and angles are in normal ranges (Allen et al., 1987). The molecular structure is stabilized by an intramolecular hydrogen bond, N2—H2C···O1 (Table 1), which forms a S(6) ring. In the crystal structure, the molecules are linked by N1—H1D···Oi and N2—H2D···S1ii intermolecular hydrogen bonds, forming a two-dimensional network (Fig. 2) parallel to the (1 0 1) plane.

Experimental

A solution of ammonium thiocyanate (0.05 mol, 3.80 g) in acetone (30 ml) was added dropwise to a solution of propionyl chloride (0.05 mol, 4.63 g) in acetone (20 ml). The mixture was stirred for 30 min and the resulting light yellow solution was filtered. Single crystals of the title compound were obtained by slow evaporation of the solution (yield 90%; m.p. 420.2–421.0 K).

Refinement

H atoms were positioned geometrically (C—H = 0.96 Å and N—H= 0.86 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2–1.5(methyl) Ueq(parent atom).

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates a hydrogen bond.
Fig. 2.
The molecular packing of the title compound, viewed approximately down the c axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C4H8N2OSF000 = 280
Mr = 132.19Dx = 1.333 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1291 reflections
a = 5.0790 (15) Åθ = 2.6–26.0º
b = 14.342 (4) ŵ = 0.40 mm1
c = 9.273 (3) ÅT = 298 (2) K
β = 102.744 (6)ºBlock, yellow
V = 658.8 (3) Å30.48 × 0.19 × 0.14 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer1291 independent reflections
Radiation source: fine-focus sealed tube910 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
Detector resolution: 83.66 pixels mm-1θmax = 26.0º
T = 298(2) Kθmin = 2.6º
ω scanh = −6→5
Absorption correction: multi-scan(SADABS; Bruker, 2000)k = −16→17
Tmin = 0.832, Tmax = 0.946l = −9→11
3622 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.119  w = 1/[σ2(Fo2) + (0.0492P)2 + 0.293P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
1291 reflectionsΔρmax = 0.23 e Å3
73 parametersΔρmin = −0.16 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
S10.01989 (18)0.06361 (6)0.28118 (8)0.0646 (3)
O10.7005 (4)0.22101 (13)0.58191 (18)0.0537 (5)
N10.4084 (4)0.18551 (14)0.3657 (2)0.0428 (6)
H1D0.36300.20090.27390.051*
C40.2638 (5)0.11286 (17)0.4084 (3)0.0413 (6)
N20.3300 (5)0.08712 (15)0.5470 (2)0.0514 (6)
H2C0.45870.11510.60720.062*
H2D0.24480.04220.57790.062*
C30.6154 (5)0.23647 (18)0.4506 (3)0.0431 (6)
C20.7271 (7)0.3102 (2)0.3675 (3)0.0635 (9)
H2A0.79590.28070.28920.076*
H2B0.58080.35120.32120.076*
C10.9454 (7)0.3677 (2)0.4578 (3)0.0706 (9)
H1A1.00510.41300.39580.106*
H1B1.09400.32820.50220.106*
H1C0.87850.39900.53400.106*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0696 (6)0.0701 (6)0.0465 (5)−0.0255 (4)−0.0038 (4)0.0050 (4)
O10.0653 (13)0.0566 (12)0.0324 (10)−0.0098 (10)−0.0040 (8)0.0002 (8)
N10.0498 (14)0.0479 (13)0.0273 (10)−0.0060 (11)0.0013 (9)0.0028 (9)
C40.0445 (15)0.0408 (15)0.0385 (14)0.0040 (12)0.0089 (11)−0.0008 (11)
N20.0633 (16)0.0523 (14)0.0357 (12)−0.0122 (12)0.0045 (10)0.0034 (10)
C30.0473 (17)0.0420 (15)0.0373 (14)0.0028 (12)0.0032 (11)−0.0015 (11)
C20.073 (2)0.063 (2)0.0484 (17)−0.0223 (17)−0.0002 (15)0.0073 (14)
C10.076 (2)0.069 (2)0.064 (2)−0.0238 (18)0.0095 (17)−0.0026 (16)

Geometric parameters (Å, °)

S1—C41.668 (3)C3—C21.492 (4)
O1—C31.219 (3)C2—C11.483 (4)
N1—C31.377 (3)C2—H2A0.97
N1—C41.382 (3)C2—H2B0.97
N1—H1D0.86C1—H1A0.96
C4—N21.308 (3)C1—H1B0.96
N2—H2C0.86C1—H1C0.96
N2—H2D0.86
C3—N1—C4128.6 (2)C1—C2—C3115.1 (2)
C3—N1—H1D115.7C1—C2—H2A108.5
C4—N1—H1D115.7C3—C2—H2A108.5
N2—C4—N1117.2 (2)C1—C2—H2B108.5
N2—C4—S1124.4 (2)C3—C2—H2B108.5
N1—C4—S1118.37 (18)H2A—C2—H2B107.5
C4—N2—H2C120.0C2—C1—H1A109.5
C4—N2—H2D120.0C2—C1—H1B109.5
H2C—N2—H2D120.0H1A—C1—H1B109.5
O1—C3—N1122.2 (2)C2—C1—H1C109.5
O1—C3—C2123.6 (2)H1A—C1—H1C109.5
N1—C3—C2114.2 (2)H1B—C1—H1C109.5
C3—N1—C4—N2−0.7 (4)C4—N1—C3—C2179.8 (3)
C3—N1—C4—S1179.7 (2)O1—C3—C2—C1−2.5 (5)
C4—N1—C3—O10.7 (4)N1—C3—C2—C1178.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2C···O10.862.002.658 (3)133
N1—H1D···O1i0.862.112.935 (3)160
N2—H2D···S1ii0.862.573.409 (3)166

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2516).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19.
  • Bruker (2000). SADABS (Version 2.01), SMART (Version 5.630) and SAINT (Version 6.36a). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Nardelli, M. (1995). J. Appl. Cryst.28, 659.
  • Rosli, M. M., Karthikeyan, M. S., Fun, H.-K., Razak, I. A., Patil, P. S., Holla, B. S. & Dharmaprakash, S. M. (2006). Acta Cryst. E62, o5692–o5693.
  • Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97, University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL Version 5.1. Bruker AXS, Inc., Madison, Wisconsin, USA.
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Yusof, M. S. M., Yaakob, W. N. A., Kadir, M. A. & Yamin, B. M. (2007). Acta Cryst. E63, o241–o243.

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