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Acta Cryst. (2007). E63, o3676    [ doi:10.1107/S160053680703680X ]

2-[3-(2-Methylbenzoyl)thioureido]-3-phenylpropionic acid

M. S. M. Yusof, Z. A. Aziz, M. A. Kadir and B. M. Yamin

Abstract top

In the title compound, C18H18N2O3S, the central thiourea and 2-methylphenyl fragments make a dihedral angle of 55.40 (7)°. In the crystal structure, molecules are stabilized by intermolecular O-H...S, N-H...O and C-H...O hydrogen bonds, forming a one-dimensional chain along the a axis.

Comment top

The title compound, (I), is an amino acids derivative of thiourea and analoguos with 2-[3-(4-methoxybenzoyl)thioureido-3-phenylpropionic acid methanol solvate, (II), (Ngah et al., 2005), except that the position of methyl group at the phenyl ring (Fig.1). The molecule maintains its trans-cis configuration with respect to the positions of 2-methylbenzoyl and 3-phenylpropionic acid relative to the S1 atom across the C8—N1 and C8—N2 bonds, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and are comparable to those in (II). The central thiourea (S1/N1/N2/C8), 2-methylphenyl (C1–C6/C20) and phenyl ring (C11–C16) fragments are essentially planar with a maximum deviation of 0.041 (2) Å for atom C7 from the least square planes. The dihedral angles between the central thiourea and 2-methylphenyl fragments is 55.40 (7)°.

There are three intramolecular N—H···O, C—H···S and C—H···O hydrogen bonds, (Table 2), and as a result, a pseudo-five- (S1···H9—C9—N2—C8—S1) and two pseudo-six membered rings (O1···H2—N2—C8—N1—C7—O1), (O1···H20—C20—C5—C6—C7—O1) are formed. In the crystal structure the molecules are stabilized by intermolecular O—H···S, N—H···O and C—H···O hydrogen bonds, (Table 2), forming a one-dimensional chain along to a axis (Fig.2).

Related literature top

For structures analogous to the title compound, see: Ngah et al. (2005). For details of the normal bond lengths and angles found in the title compound, see: Allen et al. (1987).

Experimental top

A solution of L-phenylalanine in acetone was added dropwise to a two-necked round-bottomed flask containing an equimolar solution of 2-methylbenzoyl isothiocyanate in distilled acetone. The mixture was refluxed for about 5 h to complete the reaction. The resulting solution was poured into a beaker containing some ice cubes. The white precipitate obtained was filtered and washed with distilled water and cold ethanol before dried under vacuum. Good quality crystals of (I) were obtained by recrystallization from methanol (yield 81%, m.p. 385.2–386.4 K).

Refinement top

After their location in the difference map, all H-atoms were fixed geometrically at ideal positions and allowed to ride on the parent C, N or O atoms with C—H = 0.93–0.97 Å, N—H = 0.86Å and O—H = 0.80 Å, with Uiso(H)= 1.2Ueq(C, N) and 1.5Ueq (Cmethyl, Ohydroxyl).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound (I), with the 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bonds.
[Figure 2] Fig. 2. Packing diagram of compound (I), viewed down the b axis. The dashed lines denote the intermolecular N—H···O, O—H···S and C—H···O hydrogen bonds.
2-[3-(2-Methylbenzoyl)thioureido]-3-phenylpropionic acid top
Crystal data top
C18H18N2O3SF000 = 720
Mr = 342.40Dx = 1.327 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 947 reflections
a = 7.4377 (16) Åθ = 1.6–25.9º
b = 24.554 (5) ŵ = 0.21 mm−1
c = 9.385 (2) ÅT = 293 (2) K
V = 1713.9 (6) Å3Block, colourless
Z = 40.50 × 0.38 × 0.29 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3339 independent reflections
Radiation source: fine-focus sealed tube3111 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
Detector resolution: 83.66 pixels mm-1θmax = 25.9º
T = 293(2) Kθmin = 1.6º
ω scansh = −8→9
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		k = −30→23
Tmin = 0.904, Tmax = 0.942l = −11→11
9565 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0631P)2 + 0.1974P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.096(Δ/σ)max < 0.001
S = 0.98Δρmax = 0.20 e Å−3
3339 reflectionsΔρmin = −0.14 e Å−3
217 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1396 Freidel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.08 (7)
Crystal data top
C18H18N2O3SV = 1713.9 (6) Å3
Mr = 342.40Z = 4
Orthorhombic, P212121Mo Kα
a = 7.4377 (16) ŵ = 0.21 mm−1
b = 24.554 (5) ÅT = 293 (2) K
c = 9.385 (2) Å0.50 × 0.38 × 0.29 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3339 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		3111 reflections with I > 2σ(I)
Tmin = 0.904, Tmax = 0.942Rint = 0.018
9565 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.096Δρmax = 0.20 e Å−3
S = 0.98Δρmin = −0.14 e Å−3
3339 reflectionsAbsolute structure: Flack (1983), 1396 Freidel pairs
217 parametersFlack parameter: 0.08 (7)
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 > 2sigma(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
xyzUiso*/Ueq
S1−0.13853 (7)1.026957 (19)1.05397 (6)0.05106 (16)
N1−0.18460 (19)0.93256 (6)0.92189 (17)0.0384 (3)
H1A−0.28620.94680.89910.046*
O1−0.00976 (19)0.85763 (6)0.89046 (16)0.0540 (4)
C8−0.0772 (2)0.96311 (7)1.01294 (19)0.0381 (4)
O20.4010 (2)0.96999 (6)0.96043 (15)0.0516 (3)
N20.0706 (2)0.93940 (6)1.06088 (19)0.0452 (4)
H2A0.09350.90691.03170.054*
C170.3630 (3)0.98307 (7)1.0794 (2)0.0423 (4)
C7−0.1486 (3)0.88225 (7)0.86356 (19)0.0387 (4)
C5−0.2457 (3)0.83614 (8)0.6372 (2)0.0422 (4)
O30.4643 (2)1.01424 (7)1.16113 (17)0.0622 (4)
C1−0.4677 (3)0.85934 (8)0.8167 (2)0.0456 (4)
H1B−0.49590.87540.90360.055*
C6−0.2909 (3)0.85943 (7)0.76887 (19)0.0373 (4)
C90.1965 (3)0.96422 (8)1.1589 (2)0.0448 (5)
H9A0.13880.99611.20210.054*
C110.3542 (4)0.87540 (8)1.2309 (2)0.0520 (5)
C4−0.3840 (3)0.81296 (9)0.5593 (2)0.0531 (5)
H4A−0.35790.79740.47140.064*
C100.2496 (3)0.92471 (9)1.2782 (2)0.0526 (5)
H10A0.32090.94441.34770.063*
H10B0.14100.91251.32560.063*
C2−0.6009 (3)0.83567 (10)0.7367 (3)0.0588 (6)
H2B−0.71880.83550.76950.071*
C3−0.5594 (3)0.81220 (10)0.6076 (3)0.0625 (6)
H3A−0.64900.79590.55320.075*
C20−0.0583 (3)0.83576 (10)0.5790 (2)0.0613 (6)
H20A−0.05760.81790.48790.092*
H20B0.01940.81660.64340.092*
H20C−0.01660.87250.56820.092*
C160.5398 (4)0.87715 (10)1.2231 (2)0.0615 (6)
H16A0.60000.90901.24770.074*
C120.2681 (5)0.82709 (10)1.1949 (3)0.0745 (8)
H12A0.14350.82491.20020.089*
C130.3668 (7)0.78194 (11)1.1511 (3)0.1000 (12)
H13A0.30810.74991.12620.120*
C140.5507 (7)0.78483 (14)1.1446 (3)0.1008 (13)
H14A0.61650.75451.11660.121*
C150.6375 (5)0.83178 (13)1.1789 (3)0.0850 (9)
H15B0.76220.83361.17280.102*
H30.56431.01781.13100.128*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0447 (3)0.0341 (2)0.0744 (3)−0.0009 (2)−0.0013 (2)−0.0124 (2)
N10.0348 (8)0.0341 (7)0.0461 (8)−0.0001 (6)−0.0029 (6)−0.0047 (6)
O10.0457 (8)0.0498 (8)0.0665 (9)0.0125 (7)−0.0129 (7)−0.0214 (7)
C80.0340 (9)0.0383 (9)0.0420 (9)−0.0040 (7)0.0056 (7)−0.0040 (7)
O20.0557 (9)0.0550 (8)0.0440 (7)−0.0029 (7)−0.0019 (6)−0.0021 (6)
N20.0394 (8)0.0415 (8)0.0546 (9)0.0034 (6)−0.0058 (8)−0.0165 (7)
C170.0452 (10)0.0340 (9)0.0478 (10)0.0043 (8)−0.0074 (9)−0.0035 (8)
C70.0391 (10)0.0390 (9)0.0380 (8)0.0006 (8)0.0030 (8)−0.0044 (7)
C50.0486 (11)0.0396 (9)0.0382 (9)0.0017 (8)−0.0021 (8)0.0010 (8)
O30.0520 (9)0.0669 (10)0.0677 (9)−0.0151 (7)−0.0005 (8)−0.0245 (8)
C10.0429 (11)0.0488 (11)0.0452 (10)−0.0003 (8)0.0022 (8)−0.0066 (8)
C60.0429 (10)0.0309 (8)0.0381 (9)0.0005 (7)−0.0031 (7)−0.0012 (7)
C90.0405 (10)0.0455 (11)0.0485 (10)0.0016 (8)−0.0031 (8)−0.0161 (8)
C110.0739 (15)0.0472 (10)0.0349 (9)−0.0004 (10)−0.0011 (10)0.0051 (8)
C40.0633 (14)0.0558 (11)0.0401 (10)−0.0019 (10)−0.0063 (10)−0.0105 (9)
C100.0519 (12)0.0644 (13)0.0414 (10)−0.0060 (10)0.0045 (9)−0.0080 (9)
C20.0372 (12)0.0717 (14)0.0677 (13)−0.0046 (10)−0.0002 (10)−0.0099 (12)
C30.0528 (13)0.0717 (15)0.0631 (14)−0.0060 (11)−0.0179 (11)−0.0163 (11)
C200.0571 (13)0.0737 (14)0.0530 (12)−0.0055 (11)0.0107 (11)−0.0135 (11)
C160.0757 (17)0.0606 (14)0.0482 (11)0.0121 (12)−0.0019 (11)0.0065 (10)
C120.109 (2)0.0534 (15)0.0612 (15)−0.0117 (14)−0.0116 (15)0.0098 (12)
C130.186 (4)0.0415 (14)0.0725 (18)−0.001 (2)−0.017 (3)0.0040 (12)
C140.179 (4)0.0629 (19)0.0608 (16)0.046 (2)0.006 (2)0.0088 (14)
C150.106 (2)0.089 (2)0.0592 (15)0.041 (2)0.0097 (16)0.0165 (15)
Geometric parameters (Å, °) top
S1—C81.6775 (18)C11—C121.389 (3)
N1—C71.377 (2)C11—C101.506 (3)
N1—C81.390 (2)C4—C31.381 (3)
N1—H1A0.8600C4—H4A0.9300
O1—C71.223 (2)C10—H10A0.9700
C8—N21.323 (3)C10—H10B0.9700
O2—C171.196 (2)C2—C31.377 (3)
N2—C91.447 (2)C2—H2B0.9300
N2—H2A0.8600C3—H3A0.9300
C17—O31.320 (2)C20—H20A0.9600
O3—H30.8000C20—H20B0.9600
C17—C91.518 (3)C20—H20C0.9600
C7—C61.491 (3)C16—C151.393 (4)
C5—C41.385 (3)C16—H16A0.9300
C5—C61.402 (3)C12—C131.392 (5)
C5—C201.497 (3)C12—H12A0.9300
C1—C21.372 (3)C13—C141.370 (5)
C1—C61.389 (3)C13—H13A0.9300
C1—H1B0.9300C14—C151.360 (5)
C9—C101.533 (3)C14—H14A0.9300
C9—H9A0.9800C15—H15B0.9300
C11—C161.383 (4)
C17—O3—H3113.00C5—C4—H4A118.9
C7—N1—C8128.09 (16)C11—C10—C9115.26 (16)
C7—N1—H1A116.0C11—C10—H10A108.5
C8—N1—H1A116.0C9—C10—H10A108.5
N2—C8—N1116.69 (16)C11—C10—H10B108.5
N2—C8—S1124.00 (14)C9—C10—H10B108.5
N1—C8—S1119.31 (14)H10A—C10—H10B107.5
C8—N2—C9124.64 (15)C1—C2—C3119.8 (2)
C8—N2—H2A117.7C1—C2—H2B120.1
C9—N2—H2A117.7C3—C2—H2B120.1
O2—C17—O3124.3 (2)C2—C3—C4119.7 (2)
O2—C17—C9124.73 (17)C2—C3—H3A120.2
O3—C17—C9110.95 (16)C4—C3—H3A120.2
O1—C7—N1121.69 (17)C5—C20—H20A109.5
O1—C7—C6122.44 (16)C5—C20—H20B109.5
N1—C7—C6115.85 (16)H20A—C20—H20B109.5
C4—C5—C6117.07 (19)C5—C20—H20C109.5
C4—C5—C20119.74 (18)H20A—C20—H20C109.5
C6—C5—C20123.18 (18)H20B—C20—H20C109.5
C2—C1—C6120.47 (19)C11—C16—C15120.8 (3)
C2—C1—H1B119.8C11—C16—H16A119.6
C6—C1—H1B119.8C15—C16—H16A119.6
C1—C6—C5120.71 (18)C11—C12—C13120.6 (3)
C1—C6—C7118.66 (16)C11—C12—H12A119.7
C5—C6—C7120.56 (17)C13—C12—H12A119.7
N2—C9—C17110.12 (16)C14—C13—C12119.9 (3)
N2—C9—C10111.37 (17)C14—C13—H13A120.1
C17—C9—C10109.96 (16)C12—C13—H13A120.1
N2—C9—H9A108.4C15—C14—C13120.5 (3)
C17—C9—H9A108.4C15—C14—H14A119.8
C10—C9—H9A108.4C13—C14—H14A119.8
C16—C11—C12118.3 (2)C14—C15—C16120.0 (4)
C16—C11—C10120.4 (2)C14—C15—H15B120.0
C12—C11—C10121.3 (3)C16—C15—H15B120.0
C3—C4—C5122.27 (19)C14—C15—H3139.4
C3—C4—H4A118.9H15B—C15—H393.7
C7—N1—C8—N2−6.9 (3)O2—C17—C9—C10109.4 (2)
C7—N1—C8—S1172.36 (15)O3—C17—C9—C10−68.2 (2)
N1—C8—N2—C9−178.50 (18)C6—C5—C4—C3−0.3 (3)
S1—C8—N2—C92.3 (3)C20—C5—C4—C3−179.9 (2)
C8—N1—C7—O11.3 (3)C16—C11—C10—C988.8 (2)
C8—N1—C7—C6179.99 (17)C12—C11—C10—C9−91.7 (2)
C2—C1—C6—C51.0 (3)N2—C9—C10—C1165.7 (2)
C2—C1—C6—C7−175.9 (2)C17—C9—C10—C11−56.7 (2)
C4—C5—C6—C1−0.6 (3)C6—C1—C2—C3−0.5 (3)
C20—C5—C6—C1179.0 (2)C1—C2—C3—C4−0.4 (4)
C4—C5—C6—C7176.29 (17)C5—C4—C3—C20.8 (4)
C20—C5—C6—C7−4.1 (3)C12—C11—C16—C150.7 (3)
O1—C7—C6—C1129.8 (2)C10—C11—C16—C15−179.7 (2)
N1—C7—C6—C1−48.8 (2)C16—C11—C12—C13−0.6 (4)
O1—C7—C6—C5−47.1 (3)C10—C11—C12—C13179.8 (2)
N1—C7—C6—C5134.26 (18)C11—C12—C13—C140.7 (4)
C8—N2—C9—C17−103.6 (2)C12—C13—C14—C15−0.9 (5)
C8—N2—C9—C10134.17 (19)C13—C14—C15—C161.0 (5)
O2—C17—C9—N2−13.7 (3)C11—C16—C15—C14−0.9 (4)
O3—C17—C9—N2168.75 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.952.636 (2)135
C9—H9A···S10.982.603.091 (2)111
C20—H20B···O10.962.542.994 (3)109
C1—H1B···O2i0.932.503.187 (3)130
C2—H2B···O1i0.932.503.409 (3)165
N1—H1A···O2i0.862.463.237 (2)150
O3—H3···S1ii0.802.343.1361 (17)177
C9—H9A···O2iii0.982.583.338 (2)134
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1/2, −y+2, z+1/2.
Selected geometric parameters (Å, °) top
S1—C81.6775 (18)C8—N21.323 (3)
N1—C81.390 (2)C17—O31.320 (2)
N2—C8—N1116.69 (16)N1—C8—S1119.31 (14)
N2—C8—S1124.00 (14)O1—C7—N1121.69 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.861.952.636 (2)135
C9—H9A···S10.982.603.091 (2)111
C20—H20B···O10.962.542.994 (3)109
C1—H1B···O2i0.932.503.187 (3)130
C2—H2B···O1i0.932.503.409 (3)165
N1—H1A···O2i0.862.463.237 (2)150
O3—H3···S1ii0.802.343.1361 (17)177
C9—H9A···O2iii0.982.583.338 (2)134
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1/2, −y+2, z+1/2.
Acknowledgements top

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia and Universiti Malaysia Terengganu for research grants (IRPA Nos. 09–02-02–993) and the Ministry of Higher Education Malaysia for FRGS grants (No. 59005).

references
References top

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