N-Benzoyl-N'-(2-hydroxy­ethyl)­thio­urea

In the title compound, C₁₀H₁₂N₂O₂S, the carbonyl and thio­carbonyl moieties are pointing in approximately opposite directions, and the six atoms in the hydrogen-bonded ring structure are almost coplanar.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.138
• Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level A:



PLAT_725  Alert A D-H     Calc     0.82086, Rep     0.90000, Dev.      0.08 Ang.
                     N1   -H1A     1.555   1.555

PLAT_726  Alert A H...A   Calc     2.28131, Rep     2.22000, Dev.      0.06 Ang.
                     H1A  -O2      1.555   4.576

PLAT_728  Alert A D-H..A  Calc      166.02, Rep      159.00, Dev.      7.02 Deg.
                     N1   -H1A  -O2      1.555   1.555   4.576


 Alert Level C:



PLAT_707  Alert C D...A   Calc    3.084(2), Rep    3.081(3), Dev.      1.50 Sigma
                     N1   -O2      1.555   4.576


 3 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

Thiourea compounds are excellent agents of bioactive substances. A number of biological activities are associated with substituted thiourea derivatives (Schroeder, 1955). A survey of literature reveals that some work has been reported on benzoylthiourea, which has found plenty of applications as a facile and simple ligand in determination of traces of transition metal, and as an available starting material in preparation of a wide variety of metal complexes (Koch, 2001). As a part of our work in studying the coordination behaviour of benzoylthiourea and its bioactivity, and in continuation of previous work on benzoylthiourea (Wei & Zhang, 1998), the crystal structure of the title compound, (I), is reported. To date, the coordination compound synthesis of N-benzoyl-N'-(2-hydroxyethyl)thiourea with Os, (VIII) (Bhowol, 1975), and Pt, (II) (Koch et al., 1995), have been reported, and its cyclization reaction with H₂SO₄ also has been investigated (Klayman & Woods, 1975). In a ¹³C NMR study (Imrich et al., 1994), the differences between the benzoyl (CO) chemical shift values of N-monosubstituted and N,N-disubstituted thioureas indicated the existence of an intramolecular hydrogen bond, namely between the benzoyl CO and the NH groups. The indication also was supported by ¹H NMR spectrum (Koch et al., 1995).

Fig. 1 shows the molecular crystal structure of (I), indicating that the carbonyl and thiocarbonyl moieties point in approximate opposite directions. The six atoms in the hydrogen-bonded ring structure are almost coplanar. The N2—H proton pendant arm extends to the carbonyl oxygen atom and forms an intramolecular hydrogen bond between them, and the other intra- or intermolecular hydrogen bonds are also formed (Table 1). The structure is analogous to that observed in the crystal structure of N-propyl-N'-benzoylthiourea (Dago et al., 1989), N-benzoyl-N'-(2,6-dimethylphenyl)thiourea (Usman et al., 2002), N-benzoyl-N'-phenylthiourea (Yamin & Yusof, 2003a) and N-benzoyl-N'-p-bromophenylthiourea (Yamin & Yusof, 2003b). The existence of hydrogen bonding in a benzoyl-thiourea molecular six-membered ring structure has significant implications on coordination properties (Bourne & Kock, 1993), suggest the possibility of intramolecular hydrogen-bond-controlled coordination behaviour of these ligands. In the coordination compound reported by Bourne & Kock, viz. 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 hydrogen bond similar to that in the free ligands.

S2. Experimental

Reagents and organic solvents are analytical reagents grade and commercially available. Benzoyl chloride was treated with ammonium thiocyanate in CH₂Cl₂ under solid-liquid phase transfer catalysis conditions using 3% polyethylene glycol-600 as the catalyst to give the corresponding benzoyl isothiocyanate, which was reacted with ethanolamine to give the title compound. The solid was separated from the liquid phase by filtration, washed with CH₂Cl₂ and then dried in air. The single crystals was obtained by the slow evaporation of its ethanol solution after 2 weeks, one of them was selected optically for the diffraction study and glued to a glass fibre.

S3. Refinement

The structure was solved by direct methods (Sheldrick, 1990) and successive difference Fourier syntheses. The positions of all H atoms were fixed geometrically and distances to H atoms were set by the program.

Computing details

Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 SDP/VAX (Enraf-Nonius, 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b).

Figures

Fig. 1. View of the molecule showing the labelling of the non-H atoms. Displacement ellipsoids are plotted at the 50% probability level.

N-benzoyl-N'-(2-hydroxyethyl)-Thiourea

Crystal data

C10H12N2O2S	F(000) = 472
Mr = 224.28	Dx = 1.375 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.083 (3) Å	Cell parameters from 25 reflections
b = 4.549 (1) Å	θ = 10–20°
c = 14.279 (3) Å	µ = 0.28 mm^−1
β = 102.44 (3)°	T = 293 K
V = 1083.6 (4) Å^3	Block, colorless
Z = 4	0.4 × 0.3 × 0.2 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.091
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.2°
Graphite monochromator	h = −20→19
ω/2θ scans	k = −5→5
3712 measured reflections	l = 0→16
1908 independent reflections	3 standard reflections every 60 min
1564 reflections with I > 2σ(I)	intensity decay: 0.2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.062P)^2 + 0.3405P] where P = (Fo^2 + 2Fc^2)/3
1908 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

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	0.08551 (3)	0.45894 (16)	0.95174 (4)	0.0592 (3)
N1	0.21786 (9)	0.7725 (4)	0.97426 (12)	0.0454 (4)
H1A	0.2015	0.8143	1.0226	0.050*
N2	0.18859 (10)	0.4902 (4)	0.83755 (12)	0.0469 (5)
H2A	0.2362	0.5520	0.8277	0.080*
O1	0.31531 (10)	0.8284 (5)	0.89041 (12)	0.0657 (5)
O2	0.13441 (10)	0.6596 (4)	0.64428 (11)	0.0625 (5)
H2B	0.1046	0.7612	0.6008	0.080*
C1	0.40592 (16)	1.1841 (8)	1.0294 (2)	0.0750 (8)
H1B	0.4265	1.1317	0.9742	0.080*
C2	0.45035 (19)	1.3645 (9)	1.0993 (3)	0.0909 (11)
H2C	0.5019	1.4339	1.0925	0.080*
C3	0.42197 (18)	1.4399 (7)	1.1765 (3)	0.0836 (10)
H3A	0.4531	1.5631	1.2253	0.080*
C4	0.3497 (2)	1.3431 (10)	1.1847 (3)	0.1034 (13)
H4A	0.3288	1.4008	1.2391	0.080*
C5	0.30506 (16)	1.1622 (9)	1.1165 (2)	0.0890 (11)
H5A	0.2540	1.0911	1.1246	0.080*
C6	0.33226 (12)	1.0822 (5)	1.03780 (16)	0.0498 (5)
C7	0.28909 (12)	0.8850 (5)	0.96115 (15)	0.0473 (5)
C8	0.16700 (12)	0.5742 (5)	0.91664 (14)	0.0423 (5)
C9	0.14017 (13)	0.3015 (5)	0.76514 (16)	0.0524 (6)
H9A	0.1087	0.1731	0.7956	0.080*
H9B	0.1745	0.1819	0.7359	0.080*
C10	0.08607 (15)	0.4766 (6)	0.68919 (17)	0.0584 (6)
H10A	0.0544	0.3474	0.6429	0.080*
H10B	0.0506	0.5943	0.7173	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0512 (4)	0.0748 (5)	0.0566 (4)	−0.0166 (3)	0.0227 (3)	−0.0127 (3)
N1	0.0428 (8)	0.0551 (11)	0.0403 (9)	−0.0020 (8)	0.0137 (7)	−0.0035 (8)
N2	0.0482 (9)	0.0519 (11)	0.0429 (10)	−0.0024 (8)	0.0153 (7)	−0.0031 (8)
O1	0.0589 (9)	0.0844 (13)	0.0607 (10)	−0.0164 (9)	0.0282 (8)	−0.0106 (10)
O2	0.0696 (10)	0.0715 (12)	0.0477 (9)	0.0072 (9)	0.0154 (7)	0.0058 (8)
C1	0.0632 (14)	0.094 (2)	0.0660 (16)	−0.0273 (15)	0.0104 (12)	0.0060 (16)
C2	0.0765 (18)	0.099 (2)	0.088 (2)	−0.0425 (19)	−0.0017 (16)	0.009 (2)
C3	0.0782 (19)	0.069 (2)	0.087 (2)	−0.0107 (15)	−0.0191 (17)	−0.0104 (17)
C4	0.0780 (19)	0.134 (3)	0.099 (2)	−0.020 (2)	0.0203 (17)	−0.061 (3)
C5	0.0563 (14)	0.124 (3)	0.090 (2)	−0.0232 (17)	0.0237 (14)	−0.051 (2)
C6	0.0430 (10)	0.0473 (13)	0.0560 (13)	0.0012 (9)	0.0037 (9)	0.0053 (10)
C7	0.0436 (10)	0.0492 (12)	0.0496 (12)	0.0016 (10)	0.0108 (9)	0.0051 (10)
C8	0.0420 (10)	0.0451 (11)	0.0397 (10)	0.0044 (9)	0.0087 (8)	0.0032 (9)
C9	0.0607 (12)	0.0494 (13)	0.0498 (12)	−0.0055 (10)	0.0183 (10)	−0.0094 (10)
C10	0.0574 (13)	0.0689 (16)	0.0484 (12)	−0.0060 (11)	0.0101 (10)	−0.0110 (11)

Geometric parameters (Å, º)

S1—C8	1.663 (2)	C2—H2C	0.9599
N1—C7	1.370 (3)	C3—C4	1.339 (5)
N1—C8	1.392 (3)	C3—H3A	0.9601
N1—H1A	0.8206	C4—C5	1.373 (4)
N2—C8	1.318 (3)	C4—H4A	0.9598
N2—C9	1.457 (3)	C5—C6	1.355 (4)
N2—H2A	0.9001	C5—H5A	0.9602
O1—C7	1.217 (3)	C6—C7	1.483 (3)
O2—C10	1.419 (3)	C9—C10	1.494 (4)
O2—H2B	0.8501	C9—H9A	0.9600
C1—C6	1.370 (3)	C9—H9B	0.9597
C1—C2	1.385 (5)	C10—H10A	0.9599
C1—H1B	0.9597	C10—H10B	0.9598
C2—C3	1.341 (5)
C7—N1—C8	128.40 (18)	C5—C6—C1	117.8 (3)
C7—N1—H1A	120.1	C5—C6—C7	124.7 (2)
C8—N1—H1A	111.4	C1—C6—C7	117.4 (2)
C8—N2—C9	123.93 (18)	O1—C7—N1	122.1 (2)
C8—N2—H2A	118.2	O1—C7—C6	121.8 (2)
C9—N2—H2A	117.9	N1—C7—C6	116.13 (19)
C10—O2—H2B	109.5	N2—C8—N1	116.11 (18)
C6—C1—C2	120.5 (3)	N2—C8—S1	125.02 (17)
C6—C1—H1B	119.5	N1—C8—S1	118.87 (15)
C2—C1—H1B	119.9	N2—C9—C10	111.6 (2)
C3—C2—C1	120.3 (3)	N2—C9—H9A	109.0
C3—C2—H2C	120.1	C10—C9—H9A	109.5
C1—C2—H2C	119.6	N2—C9—H9B	109.7
C4—C3—C2	119.4 (3)	C10—C9—H9B	109.1
C4—C3—H3A	120.4	H9A—C9—H9B	107.9
C2—C3—H3A	120.2	O2—C10—C9	108.1 (2)
C3—C4—C5	121.1 (3)	O2—C10—H10A	110.1
C3—C4—H4A	119.5	C9—C10—H10A	110.0
C5—C4—H4A	119.4	O2—C10—H10B	110.1
C6—C5—C4	120.8 (3)	C9—C10—H10B	110.0
C6—C5—H5A	119.5	H10A—C10—H10B	108.5
C4—C5—H5A	119.8
C6—C1—C2—C3	0.5 (5)	C5—C6—C7—O1	177.6 (3)
C1—C2—C3—C4	−1.1 (6)	C1—C6—C7—O1	−4.3 (4)
C2—C3—C4—C5	1.6 (7)	C5—C6—C7—N1	−1.9 (4)
C3—C4—C5—C6	−1.6 (7)	C1—C6—C7—N1	176.2 (2)
C4—C5—C6—C1	1.0 (6)	C9—N2—C8—N1	−175.31 (19)
C4—C5—C6—C7	179.1 (3)	C9—N2—C8—S1	5.4 (3)
C2—C1—C6—C5	−0.4 (5)	C7—N1—C8—N2	−2.4 (3)
C2—C1—C6—C7	−178.7 (3)	C7—N1—C8—S1	177.01 (18)
C8—N1—C7—O1	3.5 (4)	C8—N2—C9—C10	91.3 (3)
C8—N1—C7—C6	−177.0 (2)	N2—C9—C10—O2	60.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.90	1.92	2.631 (2)	134
C1—H1B···O1	0.96	2.44	2.762 (3)	99
N1—H1A···O2^i	0.90	2.22	3.081 (3)	159
C5—H5A···O2	0.96	2.41	3.361 (4)	171
O2—H2B···S1	0.85	2.44	3.206 (2)	150
C9—H9A···S1	0.96	2.68	3.091 (2)	106

Symmetry code: (i) x, −y+3/2, z+1/2.