N-Propionylthio­urea

Yamin, B.M.; Othman, E.A.

doi:10.1107/S160053680706031X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o313

https://doi.org/10.1107/S160053680706031X

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N-Propionylthiourea

Bohari M. Yamin ^a and Eliyanti A. Othman ^a ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: eliyanti84@yahoo.com.my

(Received 10 November 2007; accepted 18 November 2007; online 21 December 2007)

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 (10 $[\overline{1}]$ ) 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 ); Rosli et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₄H₈N₂OS
M_r = 132.19
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.119
S = 1.02
1291 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1	0.86	2.00	2.658 (3)	133
N1—H1D⋯O1ⁱ	0.86	2.11	2.935 (3)	160
N2—H2D⋯S1ⁱⁱ	0.86	2.57	3.409 (3)	166
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -z+1.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706031X/ci2516Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Structure description top

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

Computing details top

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

Figures top

	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.

N-Propionylthiourea top

Crystal data top

C₄H₈N₂OS	F(000) = 280
M_r = 132.19	D_x = 1.333 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1291 reflections
a = 5.0790 (15) Å	θ = 2.6–26.0°
b = 14.342 (4) Å	µ = 0.40 mm⁻¹
c = 9.273 (3) Å	T = 298 K
β = 102.744 (6)°	Block, yellow
V = 658.8 (3) Å³	0.48 × 0.19 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1291 independent reflections
Radiation source: fine-focus sealed tube	910 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 83.66 pixels mm^-1	θ_max = 26.0°, θ_min = 2.6°
ω scan	h = −6→5
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −16→17
T_min = 0.832, T_max = 0.946	l = −9→11
3622 measured reflections

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0492P)² + 0.293P] where P = (F_o² + 2F_c²)/3
1291 reflections	(Δ/σ)_max = 0.001
73 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₄H₈N₂OS	V = 658.8 (3) Å³
M_r = 132.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.0790 (15) Å	µ = 0.40 mm⁻¹
b = 14.342 (4) Å	T = 298 K
c = 9.273 (3) Å	0.48 × 0.19 × 0.14 mm
β = 102.744 (6)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1291 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	910 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.946	R_int = 0.029
3622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
1291 reflections	Δρ_min = −0.16 e Å⁻³
73 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	0.01989 (18)	0.06361 (6)	0.28118 (8)	0.0646 (3)
O1	0.7005 (4)	0.22101 (13)	0.58191 (18)	0.0537 (5)
N1	0.4084 (4)	0.18551 (14)	0.3657 (2)	0.0428 (6)
H1D	0.3630	0.2009	0.2739	0.051*
C4	0.2638 (5)	0.11286 (17)	0.4084 (3)	0.0413 (6)
N2	0.3300 (5)	0.08712 (15)	0.5470 (2)	0.0514 (6)
H2C	0.4587	0.1151	0.6072	0.062*
H2D	0.2448	0.0422	0.5779	0.062*
C3	0.6154 (5)	0.23647 (18)	0.4506 (3)	0.0431 (6)
C2	0.7271 (7)	0.3102 (2)	0.3675 (3)	0.0635 (9)
H2A	0.7959	0.2807	0.2892	0.076*
H2B	0.5808	0.3512	0.3212	0.076*
C1	0.9454 (7)	0.3677 (2)	0.4578 (3)	0.0706 (9)
H1A	1.0051	0.4130	0.3958	0.106*
H1B	1.0940	0.3282	0.5022	0.106*
H1C	0.8785	0.3990	0.5340	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0696 (6)	0.0701 (6)	0.0465 (5)	−0.0255 (4)	−0.0038 (4)	0.0050 (4)
O1	0.0653 (13)	0.0566 (12)	0.0324 (10)	−0.0098 (10)	−0.0040 (8)	0.0002 (8)
N1	0.0498 (14)	0.0479 (13)	0.0273 (10)	−0.0060 (11)	0.0013 (9)	0.0028 (9)
C4	0.0445 (15)	0.0408 (15)	0.0385 (14)	0.0040 (12)	0.0089 (11)	−0.0008 (11)
N2	0.0633 (16)	0.0523 (14)	0.0357 (12)	−0.0122 (12)	0.0045 (10)	0.0034 (10)
C3	0.0473 (17)	0.0420 (15)	0.0373 (14)	0.0028 (12)	0.0032 (11)	−0.0015 (11)
C2	0.073 (2)	0.063 (2)	0.0484 (17)	−0.0223 (17)	−0.0002 (15)	0.0073 (14)
C1	0.076 (2)	0.069 (2)	0.064 (2)	−0.0238 (18)	0.0095 (17)	−0.0026 (16)

Geometric parameters (Å, º) top

S1—C4	1.668 (3)	C3—C2	1.492 (4)
O1—C3	1.219 (3)	C2—C1	1.483 (4)
N1—C3	1.377 (3)	C2—H2A	0.97
N1—C4	1.382 (3)	C2—H2B	0.97
N1—H1D	0.86	C1—H1A	0.96
C4—N2	1.308 (3)	C1—H1B	0.96
N2—H2C	0.86	C1—H1C	0.96
N2—H2D	0.86

C3—N1—C4	128.6 (2)	C1—C2—C3	115.1 (2)
C3—N1—H1D	115.7	C1—C2—H2A	108.5
C4—N1—H1D	115.7	C3—C2—H2A	108.5
N2—C4—N1	117.2 (2)	C1—C2—H2B	108.5
N2—C4—S1	124.4 (2)	C3—C2—H2B	108.5
N1—C4—S1	118.37 (18)	H2A—C2—H2B	107.5
C4—N2—H2C	120.0	C2—C1—H1A	109.5
C4—N2—H2D	120.0	C2—C1—H1B	109.5
H2C—N2—H2D	120.0	H1A—C1—H1B	109.5
O1—C3—N1	122.2 (2)	C2—C1—H1C	109.5
O1—C3—C2	123.6 (2)	H1A—C1—H1C	109.5
N1—C3—C2	114.2 (2)	H1B—C1—H1C	109.5

C3—N1—C4—N2	−0.7 (4)	C4—N1—C3—C2	179.8 (3)
C3—N1—C4—S1	179.7 (2)	O1—C3—C2—C1	−2.5 (5)
C4—N1—C3—O1	0.7 (4)	N1—C3—C2—C1	178.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1	0.86	2.00	2.658 (3)	133
N1—H1D···O1ⁱ	0.86	2.11	2.935 (3)	160
N2—H2D···S1ⁱⁱ	0.86	2.57	3.409 (3)	166

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

Experimental details

Crystal data
Chemical formula	C₄H₈N₂OS
M_r	132.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.0790 (15), 14.342 (4), 9.273 (3)
β (°)	102.744 (6)
V (Å³)	658.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.48 × 0.19 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.832, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	3622, 1291, 910
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.119, 1.02
No. of reflections	1291
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1	0.86	2.00	2.658 (3)	133
N1—H1D···O1ⁱ	0.86	2.11	2.935 (3)	160
N2—H2D···S1ⁱⁱ	0.86	2.57	3.409 (3)	166

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

Acknowledgements

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

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. CSD CrossRef Web of Science Google Scholar
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