Methyl 2-(3-benzoyl­thio­ureido)acetate

Hassan, I.N.; Yamin, B.M.; Kassim, M.B.

doi:10.1107/S1600536809046169

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3078

doi:10.1107/S1600536809046169

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Methyl 2-(3-benzoylthioureido)acetate

Ibrahim N. Hassan,^a Bohari M. Yamin ^a and Mohammad B. Kassim ^a ^*

^aSchool of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 22 October 2009; accepted 3 November 2009; online 14 November 2009)

In the title compound, C₁₁H₁₂N₂O₃S, the methyl acetate and benzoyl groups adopt a cis-trans configuration with respect to the thiono S atom across the C—N bonds. An intramolecular N—H⋯O hydrogen bond is observed. In the crystal packing, molecules are linked by intermolecular N—H⋯S and C—H⋯O hydrogen bonds to form a two-dimensional network lying parallel to (101).

Related literature

For bond-length data, see: Allen et al. (1987 ). For related structures, see: Hassan et al. (2008a ,b ,c ); Yamin & Hassan (2004 ). For the preparation, see: Hassan et al. (2008a).

Experimental

Crystal data

C₁₁H₁₂N₂O₃S
M_r = 252.29
Monoclinic, P 2₁ /n
a = 14.5804 (15) Å
b = 4.9740 (5) Å
c = 16.9133 (16) Å
β = 96.210 (2)°
V = 1219.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.48 × 0.14 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.884, T_max = 0.984
6881 measured reflections
2264 independent reflections
1600 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.089
wR(F²) = 0.172
S = 1.24
2264 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.02	2.676 (4)	132
N1—H1A⋯S1ⁱ	0.86	2.77	3.547 (3)	151
C9—H9A⋯O2ⁱⁱ	0.97	2.54	3.358 (6)	142
C9—H9A⋯O2ⁱⁱⁱ	0.97	2.58	3.211 (5)	123
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y+1, z; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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, PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046169/ci2952sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046169/ci2952Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is a methyl ester derivative of glycine thiourea analogous to our previously reported ethyl-2-(3-benzoylthioureido)acetate (II) (Hassan et al., 2008a), propyl-2-(3-benzoylthioureido)acetate (III) (Hassan et al., 2008b) and butyl-2-(3-benzoylthioureido)acetate (IV) (Hassan et al., 2008c). The methyl acetate fragment and the benzoyl group adopt a cis-trans configuration, respectively, with respect to the thiono S atom across the C—N bonds (Fig 1). The dihedral angle between the phenyl ring (C1–C6) and the central fragment (S1/N1/N2/C8/C9) is 20.12 (19)°. The bond lengths (Allen et al., 1987) and angles in the molecule are in normal ranges and comparable to those of (II), (III) and (IV). The methyl acetate group (O2/O3/C9/C10/C11) is planar, with a maximum deviation of 0.023 (3) Å for atom O3. The dihedral angle between the phenyl ring and the methyl acetate group is 73.4 (2)°. An intramolecular N2—H2A···O1 hydrogen bond (Table 1) forms a pseudo-five-membered N2/H2A/O1/C7/N1/C8 ring.

Intermolecular N1—H1A···S1 and C9—H9A···O2 hydrogen bonds (Table 1) link the molecules into a two-dimensional network parallel to the (101) (Fig 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For related structures, see: Hassan et al. (2008a,b,c); Yamin & Hassan (2004). For the preparation, see: Hassan et al. (2008a).

Experimental top

The title compound was synthesized according to a previously reported method (Hassan et al., 2008a). Yellowish crystals, suitable for X-ray analysis, were obtained by slow evaporation of a CH₂Cl₂ solution at room temperature (yield 73%).

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

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates a hydrogen bond.
	Fig. 2. Crystal packing of the title compound, viewed normal to the (101). Hydrogen bonds are shown as dashed lines.

Methyl 2-(3-benzoylthioureido)acetate top

Crystal data top

C₁₁H₁₂N₂O₃S	F(000) = 528
M_r = 252.29	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 871 reflections
a = 14.5804 (15) Å	θ = 1.8–25.5°
b = 4.9740 (5) Å	µ = 0.26 mm⁻¹
c = 16.9133 (16) Å	T = 298 K
β = 96.210 (2)°	Needle, colourless
V = 1219.4 (2) Å³	0.48 × 0.14 × 0.06 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2264 independent reflections
Radiation source: fine-focus sealed tube	1600 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 25.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −17→17
T_min = 0.884, T_max = 0.984	k = −5→6
6881 measured reflections	l = −17→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.089	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.24	w = 1/[σ²(F_o²) + (0.0474P)² + 0.746P] where P = (F_o² + 2F_c²)/3
2264 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₁H₁₂N₂O₃S	V = 1219.4 (2) Å³
M_r = 252.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.5804 (15) Å	µ = 0.26 mm⁻¹
b = 4.9740 (5) Å	T = 298 K
c = 16.9133 (16) Å	0.48 × 0.14 × 0.06 mm
β = 96.210 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2264 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1600 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.984	R_int = 0.048
6881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.089	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.24	Δρ_max = 0.26 e Å⁻³
2264 reflections	Δρ_min = −0.18 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
S1	0.50901 (8)	0.0880 (3)	0.62465 (7)	0.0818 (5)
O1	0.2035 (2)	0.1002 (7)	0.53998 (17)	0.0725 (10)
N1	0.3541 (2)	−0.0034 (7)	0.53458 (18)	0.0545 (9)
H1A	0.3909	−0.0822	0.5055	0.065*
C9	0.3780 (3)	0.4046 (9)	0.7161 (2)	0.0610 (12)
H9A	0.3380	0.5543	0.7257	0.073*
H9B	0.4388	0.4763	0.7105	0.073*
C6	0.2391 (3)	−0.2034 (9)	0.4391 (2)	0.0494 (10)
N2	0.3429 (2)	0.2733 (8)	0.64340 (18)	0.0576 (10)
H2A	0.2854	0.2906	0.6265	0.069*
O3	0.4423 (2)	0.3093 (7)	0.84511 (17)	0.0740 (10)
C7	0.2621 (3)	−0.0237 (9)	0.5083 (2)	0.0535 (11)
C1	0.2954 (3)	−0.4110 (9)	0.4191 (2)	0.0555 (11)
H1B	0.3509	−0.4435	0.4501	0.067*
O2	0.3394 (2)	0.0172 (7)	0.7891 (2)	0.0812 (10)
C10	0.3840 (3)	0.2182 (10)	0.7862 (2)	0.0553 (11)
C8	0.3961 (3)	0.1265 (9)	0.6015 (2)	0.0542 (11)
C5	0.1559 (3)	−0.1619 (9)	0.3927 (2)	0.0602 (12)
H5A	0.1168	−0.0250	0.4056	0.072*
C4	0.1308 (3)	−0.3236 (10)	0.3269 (3)	0.0654 (13)
H4A	0.0753	−0.2938	0.2956	0.078*
C3	0.1877 (4)	−0.5258 (11)	0.3085 (3)	0.0704 (14)
H3A	0.1707	−0.6352	0.2647	0.084*
C2	0.2700 (3)	−0.5688 (10)	0.3542 (3)	0.0640 (13)
H2B	0.3088	−0.7062	0.3409	0.077*
C11	0.4497 (4)	0.1530 (13)	0.9180 (3)	0.0918 (19)
H11A	0.4937	0.2362	0.9568	0.138*
H11B	0.4698	−0.0259	0.9074	0.138*
H11C	0.3906	0.1454	0.9381	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0492 (7)	0.1335 (14)	0.0612 (8)	0.0052 (8)	−0.0012 (5)	−0.0188 (8)
O1	0.0499 (18)	0.093 (3)	0.075 (2)	0.0001 (17)	0.0082 (15)	−0.0248 (19)
N1	0.0436 (19)	0.070 (3)	0.049 (2)	0.0069 (17)	0.0017 (15)	−0.0076 (18)
C9	0.065 (3)	0.059 (3)	0.058 (3)	−0.006 (2)	0.006 (2)	−0.009 (2)
C6	0.049 (2)	0.055 (3)	0.045 (2)	−0.014 (2)	0.0068 (19)	0.003 (2)
N2	0.052 (2)	0.066 (3)	0.054 (2)	0.0030 (19)	−0.0007 (17)	−0.0090 (19)
O3	0.073 (2)	0.095 (3)	0.0531 (18)	−0.0153 (19)	0.0021 (15)	−0.0035 (18)
C7	0.048 (2)	0.058 (3)	0.055 (3)	−0.002 (2)	0.008 (2)	0.002 (2)
C1	0.062 (3)	0.051 (3)	0.054 (3)	−0.004 (2)	0.005 (2)	0.001 (2)
O2	0.092 (2)	0.065 (2)	0.086 (2)	−0.017 (2)	0.0060 (18)	0.0004 (19)
C10	0.051 (3)	0.056 (3)	0.060 (3)	0.001 (2)	0.014 (2)	−0.009 (2)
C8	0.054 (3)	0.062 (3)	0.045 (2)	−0.001 (2)	0.0012 (19)	0.001 (2)
C5	0.058 (3)	0.060 (3)	0.063 (3)	−0.007 (2)	0.008 (2)	−0.003 (2)
C4	0.059 (3)	0.075 (4)	0.059 (3)	−0.016 (3)	−0.006 (2)	0.006 (3)
C3	0.093 (4)	0.063 (3)	0.054 (3)	−0.018 (3)	0.005 (3)	−0.004 (3)
C2	0.080 (3)	0.051 (3)	0.062 (3)	0.000 (2)	0.011 (2)	−0.005 (2)
C11	0.098 (4)	0.123 (5)	0.055 (3)	0.017 (4)	0.008 (3)	0.011 (3)

Geometric parameters (Å, º) top

S1—C8	1.661 (4)	O3—C11	1.452 (5)
O1—C7	1.223 (5)	C1—C2	1.368 (6)
N1—C7	1.371 (5)	C1—H1B	0.93
N1—C8	1.387 (5)	O2—C10	1.197 (5)
N1—H1A	0.86	C5—C4	1.389 (6)
C9—N2	1.437 (5)	C5—H5A	0.93
C9—C10	1.499 (6)	C4—C3	1.361 (6)
C9—H9A	0.97	C4—H4A	0.93
C9—H9B	0.97	C3—C2	1.372 (6)
C6—C1	1.384 (6)	C3—H3A	0.93
C6—C5	1.386 (5)	C2—H2B	0.93
C6—C7	1.482 (6)	C11—H11A	0.96
N2—C8	1.326 (5)	C11—H11B	0.96
N2—H2A	0.86	C11—H11C	0.96
O3—C10	1.318 (5)

C7—N1—C8	129.0 (3)	O2—C10—C9	124.3 (4)
C7—N1—H1A	115.5	O3—C10—C9	111.3 (4)
C8—N1—H1A	115.5	N2—C8—N1	117.4 (4)
N2—C9—C10	112.4 (4)	N2—C8—S1	124.0 (3)
N2—C9—H9A	109.1	N1—C8—S1	118.6 (3)
C10—C9—H9A	109.1	C6—C5—C4	120.4 (4)
N2—C9—H9B	109.1	C6—C5—H5A	119.8
C10—C9—H9B	109.1	C4—C5—H5A	119.8
H9A—C9—H9B	107.9	C3—C4—C5	119.8 (4)
C1—C6—C5	118.6 (4)	C3—C4—H4A	120.1
C1—C6—C7	123.6 (4)	C5—C4—H4A	120.1
C5—C6—C7	117.9 (4)	C4—C3—C2	120.2 (5)
C8—N2—C9	122.3 (4)	C4—C3—H3A	119.9
C8—N2—H2A	118.9	C2—C3—H3A	119.9
C9—N2—H2A	118.9	C1—C2—C3	120.5 (5)
C10—O3—C11	116.2 (4)	C1—C2—H2B	119.8
O1—C7—N1	121.8 (4)	C3—C2—H2B	119.8
O1—C7—C6	122.7 (4)	O3—C11—H11A	109.5
N1—C7—C6	115.5 (4)	O3—C11—H11B	109.5
C2—C1—C6	120.5 (4)	H11A—C11—H11B	109.5
C2—C1—H1B	119.7	O3—C11—H11C	109.5
C6—C1—H1B	119.7	H11A—C11—H11C	109.5
O2—C10—O3	124.4 (4)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.02	2.676 (4)	132
C9—H9B···S1	0.97	2.68	3.027 (4)	101
N1—H1A···S1ⁱ	0.86	2.77	3.547 (3)	151
C9—H9A···O2ⁱⁱ	0.97	2.54	3.358 (6)	142
C9—H9A···O2ⁱⁱⁱ	0.97	2.58	3.211 (5)	123

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₃S
M_r	252.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	14.5804 (15), 4.9740 (5), 16.9133 (16)
β (°)	96.210 (2)
V (Å³)	1219.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.48 × 0.14 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.884, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	6881, 2264, 1600
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.089, 0.172, 1.24
No. of reflections	2264
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.18

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.02	2.676 (4)	132
N1—H1A···S1ⁱ	0.86	2.77	3.547 (3)	151
C9—H9A···O2ⁱⁱ	0.97	2.54	3.358 (6)	142
C9—H9A···O2ⁱⁱⁱ	0.97	2.58	3.211 (5)	123

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for providing the facilities and the Ministry of Science, Technology and Innovation for the research fund (Nos. UKM-ST-01FRGS0016–2006, UKM-GUP-BTT-07-30-190 and UKM-OUP-TK-16-73/2009).

References

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