Ethyl 2-(3-benzoyl­thio­ureido)acetate

The title compound, C₁₂H₁₄N₂O₃S, adopts a cis–trans geometry of the thio­urea group and is stabilized by intra­molecular hydrogen bonds between the carbonyl O atoms and the H atom of the thio­amide group and by a C—H...S interaction. Mol­ecules are linked by two inter­molecular hydrogen bonds (C—H...O and N—H...O), forming a one-dimensional chain parallel to the c axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.042
• wR factor = 0.107
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

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S1. Comment

Some thiourea derivatives of amino acids, such as 2-[3-(4-methoxbenzoyl) thioureido]-3-methylbutyric acid (Ngah et al., 2005), 3-[3-(4-methoxybenzoyl) thioureido]propanoic acid and (Ngah et al., 2005) and 2-(3-benzoylthioureido) ethanoic dimethyl sulfoxide solvate (II) (Ngah et al., 2005) have been synthesized and their structures have been reported. We are interested to synthesize a series of esters containing thiourea moiety by catalytic transesterification. The title compound, (I), is an ester of (II).

The molecule maintains the cis-trans geometry of the thiourea moiety (Fig. 1). The phenyl ring (C1—C6) and (S1/N1/N2/O1/C6/C7/C8/C9) fragments are each planar with maximum deviation of 0.031 (2)Å for C6 atom from the least square plane of the later. The dihedral angle between the two planes is 26.53 (8)°. The bond lengths and angles are in normal ranges (Allen et al., 1987). There are three intramolecular hydrogen bonds, N2—H2···O1, N2—H2···O2 and C9—H9B···S1. As a result, one pseudo-six-membered ring (N2/H2/O1/C7/N1/C8) and two pseudo-five-member ring (N2/H2/O2/C10/C9) and (C9/H9B/S1/C8/N2) are formed, respectively. In the crystal structure, the molecules are linked by N1—H1···O2 and C9—H9B···S1 intermolecular hydrogen bonds to form one dimensional chain along the c axis (Fig. 2).

Related literature

For related literature, see: Allen et al. (1987); Ngah et al. (2005); Yamin & Hassan (2004); Yamin & Yusof (2003).

S2. Experimental

2-(3-Benzoylthioureido)ethanoic acid was prepared as reported (Ngah et al., 2005). 2.38 g (10 mmol) of 2-(3-benzoylthioureido)ethanoic acid and 2.45 g (10 mmol) of lanthanum chloride were refluxed in methanol for 17 h. The resulting solution was left for one day at room temperature. Recrystallization of the resulting solid from dichloromethane gave colourless crystals of (I) [yield: 70%]).

S3. Refinement

All H-atoms attached to C were positioned geometrically and refined using a riding model U_iso=1.2U_eq (C) for aromatic 0.93 Å, U_iso = 1.2U_eq (C) for CH₂ 0.97 Å and U_iso = 1.5U_eq (C) for CH₃ 0.97 Å. Hydrogen atoms attached to N were also positioned geometrically and allowed to ride on their parent atoms and with U_iso(H) = 1.2U_eq(N) for N–H 0.86 Å.

Computing details

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, 2003).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsods drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I) viewed down the a axis. Hydrogen bonds are shown by dashed lines.

Ethyl 2-(3-benzoylthioureido)acetate

Crystal data

C12H14N2O3S	F(000) = 560
Mr = 266.31	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2409 reflections
a = 11.908 (4) Å	θ = 1.7–26.0°
b = 7.795 (3) Å	µ = 0.25 mm^−1
c = 14.024 (5) Å	T = 298 K
β = 95.600 (5)°	Block, colourless
V = 1295.5 (8) Å^3	0.46 × 0.36 × 0.22 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2537 independent reflections
Radiation source: fine-focus sealed tube	1967 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→13
Tmin = 0.893, Tmax = 0.947	k = −9→9
6762 measured reflections	l = −16→17

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.3616P] where P = (Fo^2 + 2Fc^2)/3
2537 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.23 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	0.36516 (4)	0.11910 (9)	0.60927 (4)	0.0632 (2)
O1	0.01958 (11)	0.1765 (2)	0.44591 (9)	0.0615 (4)
O2	0.21706 (12)	0.0629 (2)	0.25554 (10)	0.0657 (4)
O3	0.37578 (11)	−0.0928 (2)	0.25994 (9)	0.0626 (4)
N1	0.15088 (12)	0.2028 (2)	0.57452 (10)	0.0454 (4)
H1	0.1613	0.2428	0.6319	0.055*
N2	0.22969 (13)	0.0690 (2)	0.45050 (11)	0.0506 (4)
H2	0.1650	0.0821	0.4183	0.061*
C1	−0.03537 (15)	0.2974 (3)	0.68490 (13)	0.0482 (5)
H1A	0.0242	0.2412	0.7196	0.058*
C2	−0.11815 (16)	0.3747 (3)	0.73213 (14)	0.0540 (5)
H2A	−0.1145	0.3696	0.7986	0.065*
C3	−0.20575 (16)	0.4590 (3)	0.68161 (15)	0.0545 (5)
H3	−0.2610	0.5118	0.7139	0.065*
C4	−0.21224 (16)	0.4658 (3)	0.58254 (15)	0.0564 (5)
H4	−0.2714	0.5237	0.5483	0.068*
C5	−0.13077 (15)	0.3864 (3)	0.53472 (14)	0.0506 (5)
H5	−0.1361	0.3887	0.4681	0.061*
C6	−0.04087 (14)	0.3032 (2)	0.58545 (12)	0.0417 (4)
C7	0.04366 (15)	0.2218 (3)	0.52873 (13)	0.0455 (4)
C8	0.24393 (15)	0.1270 (2)	0.53931 (13)	0.0438 (4)
C9	0.31818 (16)	−0.0154 (3)	0.40544 (13)	0.0530 (5)
H9A	0.3234	−0.1342	0.4260	0.064*
H9B	0.3898	0.0398	0.4250	0.064*
C10	0.29539 (15)	−0.0079 (3)	0.29841 (13)	0.0477 (5)
C11	0.36926 (19)	−0.1060 (4)	0.15628 (15)	0.0689 (6)
H11A	0.3349	−0.0035	0.1270	0.083*
H11B	0.3236	−0.2041	0.1345	0.083*
C12	0.4835 (2)	−0.1258 (5)	0.1294 (2)	0.1037 (11)
H12A	0.5247	−0.0212	0.1424	0.155*
H12B	0.4808	−0.1518	0.0623	0.155*
H12C	0.5205	−0.2176	0.1658	0.155*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0420 (3)	0.0982 (5)	0.0482 (3)	0.0141 (3)	−0.0011 (2)	−0.0037 (3)
O1	0.0460 (8)	0.0913 (11)	0.0454 (8)	0.0093 (7)	−0.0038 (6)	−0.0176 (7)
O2	0.0519 (8)	0.0904 (12)	0.0549 (8)	0.0172 (8)	0.0059 (7)	0.0103 (8)
O3	0.0517 (8)	0.0912 (11)	0.0451 (8)	0.0174 (8)	0.0064 (6)	−0.0090 (7)
N1	0.0373 (8)	0.0613 (11)	0.0374 (8)	0.0036 (7)	0.0020 (6)	−0.0044 (7)
N2	0.0394 (8)	0.0679 (11)	0.0440 (9)	0.0061 (8)	0.0027 (7)	−0.0091 (8)
C1	0.0392 (9)	0.0605 (13)	0.0441 (10)	0.0027 (9)	−0.0004 (8)	0.0007 (9)
C2	0.0479 (11)	0.0718 (14)	0.0423 (10)	−0.0006 (10)	0.0049 (8)	−0.0038 (10)
C3	0.0431 (10)	0.0649 (14)	0.0567 (12)	0.0026 (10)	0.0109 (9)	−0.0082 (10)
C4	0.0413 (10)	0.0695 (14)	0.0582 (12)	0.0115 (10)	0.0030 (9)	0.0066 (10)
C5	0.0427 (10)	0.0663 (14)	0.0420 (10)	0.0027 (10)	0.0005 (8)	0.0031 (9)
C6	0.0340 (9)	0.0472 (11)	0.0437 (9)	−0.0023 (8)	0.0020 (7)	−0.0009 (8)
C7	0.0403 (9)	0.0530 (12)	0.0425 (10)	−0.0013 (8)	0.0000 (8)	−0.0003 (8)
C8	0.0403 (9)	0.0491 (11)	0.0426 (10)	0.0020 (8)	0.0069 (8)	0.0048 (8)
C9	0.0486 (11)	0.0632 (14)	0.0479 (11)	0.0103 (10)	0.0078 (9)	−0.0017 (10)
C10	0.0407 (10)	0.0548 (12)	0.0480 (10)	−0.0036 (9)	0.0075 (8)	−0.0022 (9)
C11	0.0648 (13)	0.0956 (18)	0.0464 (12)	0.0088 (13)	0.0057 (10)	−0.0100 (12)
C12	0.0712 (17)	0.176 (3)	0.0673 (16)	0.0198 (19)	0.0224 (13)	−0.0087 (19)

Geometric parameters (Å, º)

S1—C8	1.6656 (19)	C3—C4	1.385 (3)
O1—C7	1.221 (2)	C3—H3	0.9300
O2—C10	1.194 (2)	C4—C5	1.379 (3)
O3—C10	1.322 (2)	C4—H4	0.9300
O3—C11	1.452 (2)	C5—C6	1.387 (3)
N1—C7	1.380 (2)	C5—H5	0.9300
N1—C8	1.388 (2)	C6—C7	1.485 (3)
N1—H1	0.8600	C9—C10	1.500 (3)
N2—C8	1.320 (2)	C9—H9A	0.9700
N2—C9	1.439 (2)	C9—H9B	0.9700
N2—H2	0.8600	C11—C12	1.455 (3)
C1—C2	1.379 (3)	C11—H11A	0.9700
C1—C6	1.390 (2)	C11—H11B	0.9700
C1—H1A	0.9300	C12—H12A	0.9600
C2—C3	1.370 (3)	C12—H12B	0.9600
C2—H2A	0.9300	C12—H12C	0.9600
C10—O3—C11	118.29 (16)	O1—C7—C6	121.65 (16)
C7—N1—C8	127.91 (15)	N1—C7—C6	116.19 (15)
C7—N1—H1	116.0	N2—C8—N1	116.61 (15)
C8—N1—H1	116.0	N2—C8—S1	124.54 (14)
C8—N2—C9	122.58 (15)	N1—C8—S1	118.83 (14)
C8—N2—H2	118.7	N2—C9—C10	110.66 (16)
C9—N2—H2	118.7	N2—C9—H9A	109.5
C2—C1—C6	120.11 (17)	C10—C9—H9A	109.5
C2—C1—H1A	119.9	N2—C9—H9B	109.5
C6—C1—H1A	119.9	C10—C9—H9B	109.5
C3—C2—C1	120.33 (18)	H9A—C9—H9B	108.1
C3—C2—H2A	119.8	O2—C10—O3	125.96 (18)
C1—C2—H2A	119.8	O2—C10—C9	125.28 (18)
C2—C3—C4	120.14 (18)	O3—C10—C9	108.75 (16)
C2—C3—H3	119.9	O3—C11—C12	107.9 (2)
C4—C3—H3	119.9	O3—C11—H11A	110.1
C5—C4—C3	119.86 (18)	C12—C11—H11A	110.1
C5—C4—H4	120.1	O3—C11—H11B	110.1
C3—C4—H4	120.1	C12—C11—H11B	110.1
C4—C5—C6	120.32 (18)	H11A—C11—H11B	108.4
C4—C5—H5	119.8	C11—C12—H12A	109.5
C6—C5—H5	119.8	C11—C12—H12B	109.5
C5—C6—C1	119.22 (17)	H12A—C12—H12B	109.5
C5—C6—C7	117.04 (16)	C11—C12—H12C	109.5
C1—C6—C7	123.72 (16)	H12A—C12—H12C	109.5
O1—C7—N1	122.16 (17)	H12B—C12—H12C	109.5
C6—C1—C2—C3	−0.6 (3)	C5—C6—C7—N1	154.41 (18)
C1—C2—C3—C4	0.6 (3)	C1—C6—C7—N1	−26.8 (3)
C2—C3—C4—C5	0.5 (3)	C9—N2—C8—N1	−178.79 (17)
C3—C4—C5—C6	−1.5 (3)	C9—N2—C8—S1	2.7 (3)
C4—C5—C6—C1	1.5 (3)	C7—N1—C8—N2	1.6 (3)
C4—C5—C6—C7	−179.66 (19)	C7—N1—C8—S1	−179.77 (16)
C2—C1—C6—C5	−0.5 (3)	C8—N2—C9—C10	−158.69 (18)
C2—C1—C6—C7	−179.21 (19)	C11—O3—C10—O2	−1.2 (3)
C8—N1—C7—O1	−3.0 (3)	C11—O3—C10—C9	178.55 (19)
C8—N1—C7—C6	177.93 (17)	N2—C9—C10—O2	2.4 (3)
C5—C6—C7—O1	−24.7 (3)	N2—C9—C10—O3	−177.34 (17)
C1—C6—C7—O1	154.1 (2)	C10—O3—C11—C12	153.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	1.95	2.633 (2)	135
N2—H2···O2	0.86	2.43	2.724 (2)	101
C9—H9B···S1	0.97	2.70	3.045 (2)	101
N1—H1···O2^i	0.86	2.35	3.164 (2)	158
C2—H2A···O1^i	0.93	2.51	3.298 (3)	143

Symmetry code: (i) x, −y+1/2, z+1/2.