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The title compound, C10H12N2O2S, adopts a cis-trans configuration, where the phenyl group and the ethoxy­carbonyl moiety lie, respectively, cis and trans relative to the S atom across the thio­urea C-N bonds. Both N-H atoms participate in intermolecular hydrogen bonds and one also forms an intramolecular hydrogen bond. The mol­ecules in the crystal pack in alternating orientations to form ribbons.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011607/tk6108sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011607/tk6108Isup2.hkl
Contains datablock I

CCDC reference: 217434

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.036
  • wR factor = 0.096
  • Data-to-parameter ratio = 16.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Thiourea compounds are excellent bioactive agents. A number of biological activities are associated with substituted thiourea derivatives (Schroeder, 1955; Antholine & Taketa, 1982), and some N-substituted-N'-alkoxycarbonylthiourea compounds have been used as antifungal agents. N-Substituted-N'-alkoxycarbonylthiourea compounds have also attracted considerable attention in recent years because of its coordination ability with transition metal ions such as CuI, ZnII and CdII (Shen et al., 1997). As a part of our work in researching the coordination behaviour, synthesis and biological activities of N-substituted-N'-alkoxycarbonylthioureas (Zhang et al., 2000, 2001), the crystal structure of the title compound, (I), was determined.

In the molecular structure of (I), the carbonyl and thiocarbonyl moieties point in approximately opposite directions. The compound adopts a cis–trans conformation, where the phenyl group and the ethoxycarbonyl moiety lie respectively cis and trans relative to the S atom across the thiourea C—N bonds. Both N—H atoms participate in the formation of hydrogen bonds. An intramolecular hydrogen bond exists between atoms N1 and O1 (Table 1).

The molecules are connected via N—H···O and N—H···S hydrogen bonds (Fig. 1 and Table 1) and pack in alternating orientations in a ribbon-like fashion approximately parallel to the b direction.

The molecular structure of (I) is analogous to that observed in the crystal structure of N-(o-nitrophenyl)-N'-methoxycarbonylthiourea (Shen, Shi, Kang, Liu et al., 1998) and N-(p-nitrophenyl)-N'-ethoxycarbonylthiourea (Shen, Shi, Kang, Tong et al., 1998). The existence of intramolecular hydrogen bonds in thiourea molecules has significant implications on their coordination properties (Bourne & Kock, 1993). In the coordination compound reported by Bourne & Koch (1993), namely cis-bis(N-benzoyl-N'-propylthiourea)dichloroplatinum(II), the two ligand molecules bind to PtII via the S atoms only, the carbonyl O atom being locked into position by hydrogen bonds similar to that in the free ligands.

Experimental top

Ethyl chloroformate was treated with potassium thiocyanate in ethyl acetate under the condition of solid-liquid phase transfer catalysis using 3% polyethylene glycol-400 as the catalyst to give the corresponding ethoxycarbonyl isothiocyanate, which was reacted with aniline to give the title compound. The solid was separated from the liquid phase by filtration, washed with ethyl acetate and then dried in air. The single crystals was obtained by the slow evaporation of its ethanol solution after two weeks.

Refinement top

The H atoms were included in the riding-model approximation.

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the hydrogen-bonded molecules showing the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level.
N-Ethoxycarbonyl-N'-phenylthiourea top
Crystal data top
C10H12N2O2SZ = 2
Mr = 224.28F(000) = 236
Triclinic, P1Dx = 1.305 Mg m3
a = 5.787 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.218 (2) ÅCell parameters from 31 reflections
c = 10.501 (2) Åθ = 3.5–13.8°
α = 109.39 (2)°µ = 0.27 mm1
β = 94.41 (2)°T = 296 K
γ = 100.04 (1)°Block, colorless
V = 570.6 (2) Å30.58 × 0.44 × 0.30 mm
Data collection top
Siemens P4
diffractometer
1823 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.009
Graphite monochromatorθmax = 26.5°, θmin = 2.1°
ω scansh = 07
Absorption correction: empirical (using intensity measurements)
(XSCANS; Siemens, 1994)
k = 1111
Tmin = 0.858, Tmax = 0.923l = 1313
2611 measured reflections3 standard reflections every 97 reflections
2277 independent reflections intensity decay: 2.4%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0408P)2 + 0.1635P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2277 reflectionsΔρmax = 0.19 e Å3
138 parametersΔρmin = 0.28 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.099 (7)
Crystal data top
C10H12N2O2Sγ = 100.04 (1)°
Mr = 224.28V = 570.6 (2) Å3
Triclinic, P1Z = 2
a = 5.787 (1) ÅMo Kα radiation
b = 10.218 (2) ŵ = 0.27 mm1
c = 10.501 (2) ÅT = 296 K
α = 109.39 (2)°0.58 × 0.44 × 0.30 mm
β = 94.41 (2)°
Data collection top
Siemens P4
diffractometer
1823 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements)
(XSCANS; Siemens, 1994)
Rint = 0.009
Tmin = 0.858, Tmax = 0.9233 standard reflections every 97 reflections
2611 measured reflections intensity decay: 2.4%
2277 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.096H-atom parameters constrained
S = 1.06Δρmax = 0.19 e Å3
2277 reflectionsΔρmin = 0.28 e Å3
138 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
xyzUiso*/Ueq
S10.40194 (10)0.18086 (5)0.64239 (5)0.0579 (2)
O11.0080 (2)0.33985 (12)0.43949 (13)0.0518 (3)
O20.9551 (2)0.10527 (12)0.32376 (13)0.0537 (4)
N10.7186 (3)0.39717 (14)0.63107 (15)0.0475 (4)
H1N0.82850.42930.59180.057*
N20.7293 (3)0.17541 (14)0.48088 (15)0.0489 (4)
H2N0.67210.08550.45310.059*
C10.7706 (4)0.53877 (19)0.87137 (19)0.0511 (5)
H1A0.90240.50160.88460.061*
C20.7032 (4)0.6370 (2)0.9801 (2)0.0608 (6)
H2A0.78920.66541.06680.073*
C30.5104 (4)0.6926 (2)0.9607 (2)0.0629 (6)
H30.46600.75941.03380.075*
C40.3834 (4)0.6496 (2)0.8332 (2)0.0636 (6)
H40.25200.68730.82030.076*
C50.4477 (3)0.5507 (2)0.7231 (2)0.0547 (5)
H50.36060.52160.63670.066*
C60.6423 (3)0.49612 (17)0.74365 (17)0.0414 (4)
C70.6282 (3)0.25850 (17)0.58446 (17)0.0432 (4)
C80.9098 (3)0.21843 (18)0.41685 (18)0.0430 (4)
C91.1520 (4)0.1313 (2)0.2521 (2)0.0586 (5)
H9A1.29420.18300.31660.070*
H9B1.11720.18740.19730.070*
C101.1873 (5)0.0080 (3)0.1639 (3)0.0867 (8)
H10A1.22170.06240.21920.104*
H10B1.31730.00580.11490.104*
H10C1.04570.05790.10030.104*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0716 (4)0.0352 (3)0.0637 (3)0.0025 (2)0.0349 (3)0.0120 (2)
O10.0580 (8)0.0324 (7)0.0609 (8)0.0034 (6)0.0231 (6)0.0110 (6)
O20.0634 (8)0.0340 (6)0.0587 (8)0.0060 (6)0.0289 (7)0.0075 (6)
N10.0563 (9)0.0312 (7)0.0499 (8)0.0022 (6)0.0230 (7)0.0078 (6)
N20.0609 (9)0.0280 (7)0.0520 (9)0.0022 (6)0.0238 (7)0.0068 (6)
C10.0596 (12)0.0423 (10)0.0521 (11)0.0141 (9)0.0121 (9)0.0149 (8)
C20.0825 (15)0.0494 (11)0.0444 (11)0.0105 (11)0.0119 (10)0.0097 (9)
C30.0837 (16)0.0437 (11)0.0639 (13)0.0194 (10)0.0377 (12)0.0135 (9)
C40.0573 (12)0.0577 (13)0.0830 (16)0.0232 (10)0.0295 (12)0.0242 (11)
C50.0478 (11)0.0536 (11)0.0580 (12)0.0062 (9)0.0096 (9)0.0155 (9)
C60.0451 (10)0.0296 (8)0.0453 (9)0.0014 (7)0.0156 (8)0.0091 (7)
C70.0525 (10)0.0331 (9)0.0419 (9)0.0060 (7)0.0129 (8)0.0107 (7)
C80.0487 (10)0.0340 (9)0.0437 (9)0.0067 (7)0.0120 (8)0.0102 (7)
C90.0596 (12)0.0519 (11)0.0656 (13)0.0135 (9)0.0309 (10)0.0164 (9)
C100.108 (2)0.0644 (15)0.1007 (19)0.0385 (14)0.0571 (17)0.0267 (13)
Geometric parameters (Å, º) top
S1—C71.6716 (18)C2—H2A0.9300
O1—C81.207 (2)C3—C41.368 (3)
O2—C81.325 (2)C3—H30.9300
O2—C91.447 (2)C4—C51.385 (3)
N1—C71.328 (2)C4—H40.9300
N1—C61.434 (2)C5—C61.373 (3)
N1—H1N0.8600C5—H50.9300
N2—C81.371 (2)C9—C101.477 (3)
N2—C71.380 (2)C9—H9A0.9700
N2—H2N0.8600C9—H9B0.9700
C1—C61.373 (3)C10—H10A0.9600
C1—C21.381 (3)C10—H10B0.9600
C1—H1A0.9300C10—H10C0.9600
C2—C31.368 (3)
C8—O2—C9116.07 (14)C1—C6—C5120.50 (16)
C7—N1—C6123.30 (14)C1—C6—N1119.11 (16)
C7—N1—H1N118.3C5—C6—N1120.37 (17)
C6—N1—H1N118.3N1—C7—N2116.75 (15)
C8—N2—C7128.04 (14)N1—C7—S1124.23 (13)
C8—N2—H2N116.0N2—C7—S1119.02 (12)
C7—N2—H2N116.0O1—C8—O2125.48 (16)
C6—C1—C2119.79 (19)O1—C8—N2125.56 (15)
C6—C1—H1A120.1O2—C8—N2108.95 (14)
C2—C1—H1A120.1O2—C9—C10107.51 (17)
C3—C2—C1120.2 (2)O2—C9—H9A110.2
C3—C2—H2A119.9C10—C9—H9A110.2
C1—C2—H2A119.9O2—C9—H9B110.2
C4—C3—C2119.70 (19)C10—C9—H9B110.2
C4—C3—H3120.1H9A—C9—H9B108.5
C2—C3—H3120.1C9—C10—H10A109.5
C3—C4—C5120.9 (2)C9—C10—H10B109.5
C3—C4—H4119.6H10A—C10—H10B109.5
C5—C4—H4119.6C9—C10—H10C109.5
C6—C5—C4118.94 (19)H10A—C10—H10C109.5
C6—C5—H5120.5H10B—C10—H10C109.5
C4—C5—H5120.5
C6—C1—C2—C30.5 (3)C6—N1—C7—N2176.13 (17)
C1—C2—C3—C40.5 (3)C6—N1—C7—S14.3 (3)
C2—C3—C4—C50.2 (3)C8—N2—C7—N11.7 (3)
C3—C4—C5—C60.1 (3)C8—N2—C7—S1177.86 (15)
C2—C1—C6—C50.1 (3)C9—O2—C8—O15.1 (3)
C2—C1—C6—N1178.19 (16)C9—O2—C8—N2176.35 (16)
C4—C5—C6—C10.2 (3)C7—N2—C8—O11.9 (3)
C4—C5—C6—N1177.87 (16)C7—N2—C8—O2179.57 (17)
C7—N1—C6—C197.3 (2)C8—O2—C9—C10174.56 (19)
C7—N1—C6—C584.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.513.3556 (16)167
N1—H1N···O1ii0.862.523.2082 (19)138
N1—H1N···O10.862.022.697 (2)135
Symmetry codes: (i) x+1, y, z+1; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC10H12N2O2S
Mr224.28
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)5.787 (1), 10.218 (2), 10.501 (2)
α, β, γ (°)109.39 (2), 94.41 (2), 100.04 (1)
V3)570.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.58 × 0.44 × 0.30
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(XSCANS; Siemens, 1994)
Tmin, Tmax0.858, 0.923
No. of measured, independent and
observed [I > 2σ(I)] reflections
2611, 2277, 1823
Rint0.009
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.096, 1.06
No. of reflections2277
No. of parameters138
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.28

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXTL (Siemens, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···S1i0.862.513.3556 (16)167
N1—H1N···O1ii0.862.523.2082 (19)138
N1—H1N···O10.862.022.697 (2)135
Symmetry codes: (i) x+1, y, z+1; (ii) x+2, y+1, z+1.
 

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