organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N-(3-Chloro­propion­yl)-N′-phenyl­thio­urea

aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia
*Correspondence e-mail: bohari@ukm.my

(Received 27 January 2010; accepted 9 February 2010; online 13 February 2010)

The title compound, C10H11ClN2OS, adopts a cis-trans configuration with respect to the position of the phenyl and 3-chloro­propionyl groups relative to the thiono group across the C—N bonds. The benzene ring is perpendicular to the propionyl thio­urea fragment with a dihedral angle of 82.62 (10)°. An intra­molecular N—H⋯O inter­action occurs. The crystal structure is stabilized by inter­molecular N—H⋯S hydrogen bonds, which link pairs of mol­ecules, building up R22(8) ring motifs, and C—H.. π inter­actions.

Related literature

For related structures, see: Ismail et al. (2007[Ismail, N. L., Othman, E. & Yamin, B. M. (2007). Acta Cryst. E63, o2442-o2443.]); Ismail & Yamin (2009[Ismail, N. & Yamin, B. M. (2009). X-ray Struct. Anal. Online, 25, 39-40]). For hydrogen-bond motifs, see: Etter et al.(1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]); Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For reference bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C10H11ClN2OS

  • Mr = 242.72

  • Triclinic, [P \overline 1]

  • a = 5.8088 (12) Å

  • b = 10.467 (2) Å

  • c = 10.660 (2) Å

  • α = 112.811 (3)°

  • β = 101.855 (3)°

  • γ = 95.483 (3)°

  • V = 573.6 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.49 mm−1

  • T = 298 K

  • 0.49 × 0.45 × 0.27 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.795, Tmax = 0.879

  • 5617 measured reflections

  • 2103 independent reflections

  • 1798 reflections with I > 2σ(I)

  • Rint = 0.016

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.113

  • S = 1.04

  • 2103 reflections

  • 136 parameters

  • H-atom parameters constrained

  • Δρmax = 0.54 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O1 0.86 2.01 2.677 (3) 134
N1—H1A⋯S1i 0.86 2.53 3.3709 (19) 165
C1—H1CCg1ii 0.97 2.84 3.466 123
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+2, -y+1, -z.

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995[Nardelli, M. (1995). J. Appl. Cryst. 28, 659.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

The presence of both alpha and ipso chlorine atoms in 2-chloropropionyl chloride could lead to a complicated reaction when reacted with a nucleophile such as thiocyanate depending on the solvent used. For example, the reaction of 2-chloropropionyl chloride with ammonium thiocyanate and succeedingly with aniline in acetone was found to give 4,5,6-trimethyl-1- phenyl-3,4-dihydropyrimidine-2(1H)-thione (Ismail et al., 2007) instead of the expected N-phenyl-N'-(2-chloropropionyl) thiourea. However, in the present study, the same reaction but with 3-chloropropionyl chloride, the expected N-phenyl-N'-(3-chloropropionyl)thiourea (I) was indeed obtained.

The whole molecule is not planar (Fig.1). The benzene (C5—C10) ring and propionylthiourea fragment, S1/N1/N2/(C1—C4) are each planar with maximum deviation of 0.062 (2)Å for C3 atom from the least square plane. The benzene ring is roughly perpendicular to the propionylthiourea fragment with dihedral angle between the two planes of 82.62 (10)°. A smaller dihedral angle of 12.68 (7)° was observed in an analogous compound of N-(3-chloropropionyl)-N'(4-fluorophenyl) thiourea (II) (Ismail & Yamin, 2009).The trans-cis configuration of the propionyl and phenyl groups relative to the thiono group respectively, across their C—N bonds, is maintained. The bond lengths and angles are in normal range (Allen et al.,1987) and comparable to those in (II).

There is one intrahydrogen bond, N2—H2A···O1 forming the pseudo-six membered ring, N2/C4/N1/C3/O1···H2A. In the crystal structure, the molecules are linked by N1—H1A···S1 intermolecular hydrogen bond forming dimers through a R22(8) ring (Etter et al., 1990 ; Bernstein et al., 1995) extending along the c-axis (Table 1, Fig.2). In addition, there is also a C1—H1C.,.π bond with the benzene (C5—C10) ring (Table 1).

Related literature top

For related structures, see: Ismail et al. (2007); Ismail & Yamin (2009). For hydrogen-bond motifs, see: Etter et al.(1990); Bernstein et al. (1995). For reference bond lengths, see: Allen et al. (1987).

Experimental top

30 ml acetone solution of aniline was added into 30 ml acetone containing 3-chloropropionyl isothiocyanate (1.49, 0.01 mol). The mixture was refluxed for 2 hours. The solution was filtered and left to evaporate at room temperature. The white precipitate obtained after a few days, was washed with water and cold ethanol. The colorless crsytals were obtained by recrystallization from ethanol. Yield 90%; m.p 389.7-391.2 K; 1H NMR (400 MHz, CDCl3-d6):δ (ppm)= 12.32 (s,1H), 9.99 (s,1H), 7.63 (m,4H, HAr), 7.41 (s,1H, HAr), 3.8 (d,2H,Cl—CH2), 2.9 (d,2H,CH2). 13C NMR (400 MHz, CDCl3-d6):δ (ppm)= 38.32, 39.76, 124.70, 127.35, 127.35, 129.08, 129.08, 137.30, 171.22, 178.49.

Refinement top

After locating the hydrogen atoms from a different-Fourier map, they were positioned geonmetrically with C—H=0.93-0.97Å and N—H=0.86Å respectively, and constrained to all their parent atoms with Uiso(H)=1.2Ueq(parent atom). There is a highest peak and deepest hole of 0.97 and 0.81 Å respectively from S1 atom.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I),with displacement ellipsods drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram of (I) viewed down the a axis. Hydrogen bonds are shown by dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) -x+2, -y+2, -z+1]
N-(3-chloropropionyl)-N'-phenylthiourea top
Crystal data top
C10H11ClN2OSZ = 2
Mr = 242.72F(000) = 252
Triclinic, P1Dx = 1.405 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8088 (12) ÅCell parameters from 3405 reflections
b = 10.467 (2) Åθ = 2.1–25.5°
c = 10.660 (2) ŵ = 0.49 mm1
α = 112.811 (3)°T = 298 K
β = 101.855 (3)°Block, colourless
γ = 95.483 (3)°0.49 × 0.45 × 0.27 mm
V = 573.6 (2) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2103 independent reflections
Radiation source: fine-focus sealed tube1798 reflections with I > 2σ(I)
Detector resolution: 83.66 pixels mm-1Rint = 0.016
ω scanθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 77
Tmin = 0.795, Tmax = 0.879k = 1212
5617 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0559P)2 + 0.2663P]
where P = (Fo2 + 2Fc2)/3
2103 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C10H11ClN2OSγ = 95.483 (3)°
Mr = 242.72V = 573.6 (2) Å3
Triclinic, P1Z = 2
a = 5.8088 (12) ÅMo Kα radiation
b = 10.467 (2) ŵ = 0.49 mm1
c = 10.660 (2) ÅT = 298 K
α = 112.811 (3)°0.49 × 0.45 × 0.27 mm
β = 101.855 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2103 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1798 reflections with I > 2σ(I)
Tmin = 0.795, Tmax = 0.879Rint = 0.016
5617 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.04Δρmax = 0.54 e Å3
2103 reflectionsΔρmin = 0.43 e Å3
136 parameters
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.

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
xyzUiso*/Ueq
Cl10.23811 (13)1.37819 (8)0.50799 (7)0.0777 (3)
S11.10045 (13)0.86771 (7)0.31949 (6)0.0653 (2)
O10.5152 (3)1.07380 (16)0.16725 (14)0.0539 (4)
N10.7823 (3)1.03263 (18)0.32922 (17)0.0497 (4)
H1A0.84131.06140.41860.060*
N20.7847 (3)0.87565 (18)0.10659 (17)0.0484 (4)
H2A0.67810.91540.07530.058*
C10.3405 (4)1.2689 (3)0.3640 (2)0.0594 (6)
H1B0.20911.19350.29670.071*
H1C0.39311.32440.31670.071*
C20.5422 (4)1.2067 (2)0.4124 (2)0.0539 (5)
H2B0.49681.16230.47070.065*
H2C0.68091.28150.46960.065*
C30.6079 (4)1.0991 (2)0.2902 (2)0.0434 (5)
C40.8769 (4)0.9252 (2)0.2443 (2)0.0452 (5)
C50.8541 (4)0.7586 (2)0.00691 (19)0.0435 (5)
C61.0500 (4)0.7804 (2)0.0412 (2)0.0543 (5)
H6A1.14040.87070.00870.065*
C71.1101 (5)0.6653 (3)0.1391 (3)0.0618 (6)
H7A1.24210.67870.17250.074*
C80.9790 (5)0.5329 (3)0.1872 (2)0.0635 (7)
H8A1.02210.45650.25240.076*
C90.7837 (5)0.5125 (2)0.1393 (3)0.0646 (7)
H9A0.69340.42210.17240.078*
C100.7203 (4)0.6258 (2)0.0418 (2)0.0541 (5)
H10A0.58720.61200.00940.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0802 (5)0.0871 (5)0.0664 (4)0.0432 (4)0.0358 (4)0.0181 (4)
S10.0877 (5)0.0664 (4)0.0387 (3)0.0470 (3)0.0082 (3)0.0157 (3)
O10.0636 (9)0.0576 (9)0.0367 (8)0.0276 (7)0.0084 (7)0.0145 (7)
N10.0632 (11)0.0471 (10)0.0316 (8)0.0248 (8)0.0058 (7)0.0090 (7)
N20.0596 (11)0.0462 (10)0.0345 (9)0.0255 (8)0.0069 (7)0.0110 (7)
C10.0641 (14)0.0675 (15)0.0476 (12)0.0343 (12)0.0188 (11)0.0180 (11)
C20.0604 (13)0.0556 (13)0.0400 (11)0.0260 (11)0.0097 (10)0.0126 (10)
C30.0480 (11)0.0397 (10)0.0384 (11)0.0137 (9)0.0082 (8)0.0125 (8)
C40.0560 (12)0.0387 (10)0.0384 (10)0.0162 (9)0.0102 (9)0.0130 (8)
C50.0524 (11)0.0440 (11)0.0313 (9)0.0205 (9)0.0066 (8)0.0126 (8)
C60.0513 (12)0.0552 (13)0.0508 (12)0.0123 (10)0.0090 (10)0.0182 (10)
C70.0600 (14)0.0798 (18)0.0559 (14)0.0321 (13)0.0245 (11)0.0301 (13)
C80.0891 (18)0.0620 (15)0.0459 (13)0.0419 (14)0.0251 (12)0.0194 (11)
C90.0920 (19)0.0416 (12)0.0555 (14)0.0182 (12)0.0218 (13)0.0130 (10)
C100.0650 (14)0.0484 (12)0.0517 (12)0.0169 (10)0.0219 (11)0.0192 (10)
Geometric parameters (Å, º) top
Cl1—C11.778 (2)C2—H2B0.9700
S1—C41.669 (2)C2—H2C0.9700
O1—C31.221 (2)C5—C101.369 (3)
N1—C31.367 (3)C5—C61.375 (3)
N1—C41.386 (3)C6—C71.385 (3)
N1—H1A0.8600C6—H6A0.9300
N2—C41.320 (3)C7—C81.361 (4)
N2—C51.433 (2)C7—H7A0.9300
N2—H2A0.8600C8—C91.367 (4)
C1—C21.490 (3)C8—H8A0.9300
C1—H1B0.9700C9—C101.381 (3)
C1—H1C0.9700C9—H9A0.9300
C2—C31.503 (3)C10—H10A0.9300
C3—N1—C4128.77 (17)N2—C4—N1117.03 (18)
C3—N1—H1A115.6N2—C4—S1123.88 (16)
C4—N1—H1A115.6N1—C4—S1119.09 (15)
C4—N2—C5122.97 (17)C10—C5—C6120.60 (19)
C4—N2—H2A118.5C10—C5—N2119.22 (19)
C5—N2—H2A118.5C6—C5—N2120.17 (19)
C2—C1—Cl1111.32 (16)C5—C6—C7118.7 (2)
C2—C1—H1B109.4C5—C6—H6A120.7
Cl1—C1—H1B109.4C7—C6—H6A120.7
C2—C1—H1C109.4C8—C7—C6121.0 (2)
Cl1—C1—H1C109.4C8—C7—H7A119.5
H1B—C1—H1C108.0C6—C7—H7A119.5
C1—C2—C3111.71 (17)C7—C8—C9119.9 (2)
C1—C2—H2B109.3C7—C8—H8A120.1
C3—C2—H2B109.3C9—C8—H8A120.1
C1—C2—H2C109.3C8—C9—C10120.1 (2)
C3—C2—H2C109.3C8—C9—H9A119.9
H2B—C2—H2C107.9C10—C9—H9A119.9
O1—C3—N1122.97 (18)C5—C10—C9119.7 (2)
O1—C3—C2123.17 (18)C5—C10—H10A120.1
N1—C3—C2113.86 (17)C9—C10—H10A120.1
Cl1—C1—C2—C3172.29 (17)C4—N2—C5—C686.1 (3)
C4—N1—C3—O13.2 (4)C10—C5—C6—C70.5 (3)
C4—N1—C3—C2177.1 (2)N2—C5—C6—C7179.04 (19)
C1—C2—C3—O14.3 (3)C5—C6—C7—C80.1 (3)
C1—C2—C3—N1176.1 (2)C6—C7—C8—C90.4 (4)
C5—N2—C4—N1175.79 (19)C7—C8—C9—C100.3 (4)
C5—N2—C4—S15.2 (3)C6—C5—C10—C90.6 (3)
C3—N1—C4—N22.1 (3)N2—C5—C10—C9179.2 (2)
C3—N1—C4—S1176.94 (18)C8—C9—C10—C50.2 (4)
C4—N2—C5—C1095.3 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C5–C10 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.862.012.677 (3)134
N1—H1A···S1i0.862.533.3709 (19)165
C1—H1C···Cg1ii0.972.843.466123
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+2, y+1, z.

Experimental details

Crystal data
Chemical formulaC10H11ClN2OS
Mr242.72
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)5.8088 (12), 10.467 (2), 10.660 (2)
α, β, γ (°)112.811 (3), 101.855 (3), 95.483 (3)
V3)573.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.49 × 0.45 × 0.27
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.795, 0.879
No. of measured, independent and
observed [I > 2σ(I)] reflections
5617, 2103, 1798
Rint0.016
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.113, 1.04
No. of reflections2103
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.43

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C5–C10 ring.
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.862.012.677 (3)134
N1—H1A···S1i0.862.533.3709 (19)165
C1—H1C···Cg1ii0.972.843.466123
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+2, y+1, z.
 

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia for the research grant UKM-OUP-NBT-27–144 and Universiti Kebangsaan Malaysia for the research facilities.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef CAS Web of Science IUCr Journals Google Scholar
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First citationIsmail, N. & Yamin, B. M. (2009). X-ray Struct. Anal. Online, 25, 39–40  CSD CrossRef CAS Google Scholar
First citationNardelli, M. (1995). J. Appl. Cryst. 28, 659.  CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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