Methyl 2-(3-benzoyl­thio­ureido)acetate

Abstract

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,

• a = 14.5804 (15) Å

• b = 4.9740 (5) Å

• c = 16.9133 (16) Å

• β = 96.210 (2)°

• V = 1219.4 (2) ų

• 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[F ² > 2σ(F ²)] = 0.089

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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%).

Refinement

H atoms were positioned geometrically [N-H = 0.86 Å and C-H = 0.93-0.97 Å] and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq (C,N) and 1.5U_eq(C_methyl).

Figures

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.

Crystal data

C11H12N2O3S	F(000) = 528
Mr = 252.29	Dx = 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

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

Refinement

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(Fo2) + (0.0474P)2 + 0.746P] where P = (Fo2 + 2Fc2)/3
2264 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.18 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	0.50901 (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 (Ų)

	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, °)

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, °)

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.