N-Ethoxy­carbonyl-N'-phenyl­thio­urea

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.

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

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S1. Comment

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 Cu^I, Zn^II and Cd^II (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 Pt^II via the S atoms only, the carbonyl O atom being locked into position by hydrogen bonds similar to that in the free ligands.

S2. Experimental

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.

S3. Refinement

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

Computing details

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

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

Crystal data

C10H12N2O2S	Z = 2
Mr = 224.28	F(000) = 236
Triclinic, P1	Dx = 1.305 Mg m^−3
a = 5.787 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.218 (2) Å	Cell parameters from 31 reflections
c = 10.501 (2) Å	θ = 3.5–13.8°
α = 109.39 (2)°	µ = 0.27 mm^−1
β = 94.41 (2)°	T = 296 K
γ = 100.04 (1)°	Block, colorless
V = 570.6 (2) Å^3	0.58 × 0.44 × 0.30 mm

Data collection

Siemens P4 diffractometer	1823 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.009
Graphite monochromator	θmax = 26.5°, θmin = 2.1°
ω scans	h = 0→7
Absorption correction: empirical (using intensity measurements) (XSCANS; Siemens, 1994)	k = −11→11
Tmin = 0.858, Tmax = 0.923	l = −13→13
2611 measured reflections	3 standard reflections every 97 reflections
2277 independent reflections	intensity decay: 2.4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 0.1635P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2277 reflections	Δρmax = 0.19 e Å^−3
138 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.099 (7)

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.40194 (10)	0.18086 (5)	0.64239 (5)	0.0579 (2)
O1	1.0080 (2)	0.33985 (12)	0.43949 (13)	0.0518 (3)
O2	0.9551 (2)	0.10527 (12)	0.32376 (13)	0.0537 (4)
N1	0.7186 (3)	0.39717 (14)	0.63107 (15)	0.0475 (4)
H1N	0.8285	0.4293	0.5918	0.057*
N2	0.7293 (3)	0.17541 (14)	0.48088 (15)	0.0489 (4)
H2N	0.6721	0.0855	0.4531	0.059*
C1	0.7706 (4)	0.53877 (19)	0.87137 (19)	0.0511 (5)
H1A	0.9024	0.5016	0.8846	0.061*
C2	0.7032 (4)	0.6370 (2)	0.9801 (2)	0.0608 (6)
H2A	0.7892	0.6654	1.0668	0.073*
C3	0.5104 (4)	0.6926 (2)	0.9607 (2)	0.0629 (6)
H3	0.4660	0.7594	1.0338	0.075*
C4	0.3834 (4)	0.6496 (2)	0.8332 (2)	0.0636 (6)
H4	0.2520	0.6873	0.8203	0.076*
C5	0.4477 (3)	0.5507 (2)	0.7231 (2)	0.0547 (5)
H5	0.3606	0.5216	0.6367	0.066*
C6	0.6423 (3)	0.49612 (17)	0.74365 (17)	0.0414 (4)
C7	0.6282 (3)	0.25850 (17)	0.58446 (17)	0.0432 (4)
C8	0.9098 (3)	0.21843 (18)	0.41685 (18)	0.0430 (4)
C9	1.1520 (4)	0.1313 (2)	0.2521 (2)	0.0586 (5)
H9A	1.2942	0.1830	0.3166	0.070*
H9B	1.1172	0.1874	0.1973	0.070*
C10	1.1873 (5)	−0.0080 (3)	0.1639 (3)	0.0867 (8)
H10A	1.2217	−0.0624	0.2192	0.104*
H10B	1.3173	0.0058	0.1149	0.104*
H10C	1.0457	−0.0579	0.1003	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0716 (4)	0.0352 (3)	0.0637 (3)	0.0025 (2)	0.0349 (3)	0.0120 (2)
O1	0.0580 (8)	0.0324 (7)	0.0609 (8)	0.0034 (6)	0.0231 (6)	0.0110 (6)
O2	0.0634 (8)	0.0340 (6)	0.0587 (8)	0.0060 (6)	0.0289 (7)	0.0075 (6)
N1	0.0563 (9)	0.0312 (7)	0.0499 (8)	0.0022 (6)	0.0230 (7)	0.0078 (6)
N2	0.0609 (9)	0.0280 (7)	0.0520 (9)	0.0022 (6)	0.0238 (7)	0.0068 (6)
C1	0.0596 (12)	0.0423 (10)	0.0521 (11)	0.0141 (9)	0.0121 (9)	0.0149 (8)
C2	0.0825 (15)	0.0494 (11)	0.0444 (11)	0.0105 (11)	0.0119 (10)	0.0097 (9)
C3	0.0837 (16)	0.0437 (11)	0.0639 (13)	0.0194 (10)	0.0377 (12)	0.0135 (9)
C4	0.0573 (12)	0.0577 (13)	0.0830 (16)	0.0232 (10)	0.0295 (12)	0.0242 (11)
C5	0.0478 (11)	0.0536 (11)	0.0580 (12)	0.0062 (9)	0.0096 (9)	0.0155 (9)
C6	0.0451 (10)	0.0296 (8)	0.0453 (9)	0.0014 (7)	0.0156 (8)	0.0091 (7)
C7	0.0525 (10)	0.0331 (9)	0.0419 (9)	0.0060 (7)	0.0129 (8)	0.0107 (7)
C8	0.0487 (10)	0.0340 (9)	0.0437 (9)	0.0067 (7)	0.0120 (8)	0.0102 (7)
C9	0.0596 (12)	0.0519 (11)	0.0656 (13)	0.0135 (9)	0.0309 (10)	0.0164 (9)
C10	0.108 (2)	0.0644 (15)	0.1007 (19)	0.0385 (14)	0.0571 (17)	0.0267 (13)

Geometric parameters (Å, º)

S1—C7	1.6716 (18)	C2—H2A	0.9300
O1—C8	1.207 (2)	C3—C4	1.368 (3)
O2—C8	1.325 (2)	C3—H3	0.9300
O2—C9	1.447 (2)	C4—C5	1.385 (3)
N1—C7	1.328 (2)	C4—H4	0.9300
N1—C6	1.434 (2)	C5—C6	1.373 (3)
N1—H1N	0.8600	C5—H5	0.9300
N2—C8	1.371 (2)	C9—C10	1.477 (3)
N2—C7	1.380 (2)	C9—H9A	0.9700
N2—H2N	0.8600	C9—H9B	0.9700
C1—C6	1.373 (3)	C10—H10A	0.9600
C1—C2	1.381 (3)	C10—H10B	0.9600
C1—H1A	0.9300	C10—H10C	0.9600
C2—C3	1.368 (3)
C8—O2—C9	116.07 (14)	C1—C6—C5	120.50 (16)
C7—N1—C6	123.30 (14)	C1—C6—N1	119.11 (16)
C7—N1—H1N	118.3	C5—C6—N1	120.37 (17)
C6—N1—H1N	118.3	N1—C7—N2	116.75 (15)
C8—N2—C7	128.04 (14)	N1—C7—S1	124.23 (13)
C8—N2—H2N	116.0	N2—C7—S1	119.02 (12)
C7—N2—H2N	116.0	O1—C8—O2	125.48 (16)
C6—C1—C2	119.79 (19)	O1—C8—N2	125.56 (15)
C6—C1—H1A	120.1	O2—C8—N2	108.95 (14)
C2—C1—H1A	120.1	O2—C9—C10	107.51 (17)
C3—C2—C1	120.2 (2)	O2—C9—H9A	110.2
C3—C2—H2A	119.9	C10—C9—H9A	110.2
C1—C2—H2A	119.9	O2—C9—H9B	110.2
C4—C3—C2	119.70 (19)	C10—C9—H9B	110.2
C4—C3—H3	120.1	H9A—C9—H9B	108.5
C2—C3—H3	120.1	C9—C10—H10A	109.5
C3—C4—C5	120.9 (2)	C9—C10—H10B	109.5
C3—C4—H4	119.6	H10A—C10—H10B	109.5
C5—C4—H4	119.6	C9—C10—H10C	109.5
C6—C5—C4	118.94 (19)	H10A—C10—H10C	109.5
C6—C5—H5	120.5	H10B—C10—H10C	109.5
C4—C5—H5	120.5
C6—C1—C2—C3	−0.5 (3)	C6—N1—C7—N2	−176.13 (17)
C1—C2—C3—C4	0.5 (3)	C6—N1—C7—S1	4.3 (3)
C2—C3—C4—C5	−0.2 (3)	C8—N2—C7—N1	−1.7 (3)
C3—C4—C5—C6	−0.1 (3)	C8—N2—C7—S1	177.86 (15)
C2—C1—C6—C5	0.1 (3)	C9—O2—C8—O1	5.1 (3)
C2—C1—C6—N1	178.19 (16)	C9—O2—C8—N2	−176.35 (16)
C4—C5—C6—C1	0.2 (3)	C7—N2—C8—O1	−1.9 (3)
C4—C5—C6—N1	−177.87 (16)	C7—N2—C8—O2	179.57 (17)
C7—N1—C6—C1	97.3 (2)	C8—O2—C9—C10	174.56 (19)
C7—N1—C6—C5	−84.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1^i	0.86	2.51	3.3556 (16)	167
N1—H1N···O1^ii	0.86	2.52	3.2082 (19)	138
N1—H1N···O1	0.86	2.02	2.697 (2)	135

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