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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.096
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.70 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C8      ..       6.10 su
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C20

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.90
           From the CIF: _reflns_number_total               3339
           Count of symmetry unique reflns         1943
           Completeness (_total/calc)            171.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1396
           Fraction of Friedel pairs measured     0.718
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C9     = .          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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 = 0.86 Å and O—H = 0.80 Å, with U_iso(H)= 1.2Ueq(C, N) and 1.5Ueq (C_methyl, O_hydroxyl).

Computing details

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

	Fig. 1. Molecular structure of the title compound (I), with the 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bonds.
	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

Crystal data

C18H18N2O3S	F(000) = 720
Mr = 342.40	Dx = 1.327 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 947 reflections
a = 7.4377 (16) Å	θ = 1.6–25.9°
b = 24.554 (5) Å	µ = 0.21 mm^−1
c = 9.385 (2) Å	T = 293 K
V = 1713.9 (6) Å^3	Block, colourless
Z = 4	0.50 × 0.38 × 0.29 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3339 independent reflections
Radiation source: fine-focus sealed tube	3111 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 83.66 pixels mm^-1	θmax = 25.9°, θmin = 1.6°
ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −30→23
Tmin = 0.904, Tmax = 0.942	l = −11→11
9565 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0631P)^2 + 0.1974P] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3339 reflections	Δρmax = 0.20 e Å^−3
217 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1396 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (7)

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	−0.13853 (7)	1.026957 (19)	1.05397 (6)	0.05106 (16)
N1	−0.18460 (19)	0.93256 (6)	0.92189 (17)	0.0384 (3)
H1A	−0.2862	0.9468	0.8991	0.046*
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)
O2	0.4010 (2)	0.96999 (6)	0.96043 (15)	0.0516 (3)
N2	0.0706 (2)	0.93940 (6)	1.06088 (19)	0.0452 (4)
H2A	0.0935	0.9069	1.0317	0.054*
C17	0.3630 (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)
O3	0.4643 (2)	1.01424 (7)	1.16113 (17)	0.0622 (4)
C1	−0.4677 (3)	0.85934 (8)	0.8167 (2)	0.0456 (4)
H1B	−0.4959	0.8754	0.9036	0.055*
C6	−0.2909 (3)	0.85943 (7)	0.76887 (19)	0.0373 (4)
C9	0.1965 (3)	0.96422 (8)	1.1589 (2)	0.0448 (5)
H9A	0.1388	0.9961	1.2021	0.054*
C11	0.3542 (4)	0.87540 (8)	1.2309 (2)	0.0520 (5)
C4	−0.3840 (3)	0.81296 (9)	0.5593 (2)	0.0531 (5)
H4A	−0.3579	0.7974	0.4714	0.064*
C10	0.2496 (3)	0.92471 (9)	1.2782 (2)	0.0526 (5)
H10A	0.3209	0.9444	1.3477	0.063*
H10B	0.1410	0.9125	1.3256	0.063*
C2	−0.6009 (3)	0.83567 (10)	0.7367 (3)	0.0588 (6)
H2B	−0.7188	0.8355	0.7695	0.071*
C3	−0.5594 (3)	0.81220 (10)	0.6076 (3)	0.0625 (6)
H3A	−0.6490	0.7959	0.5532	0.075*
C20	−0.0583 (3)	0.83576 (10)	0.5790 (2)	0.0613 (6)
H20A	−0.0576	0.8179	0.4879	0.092*
H20B	0.0194	0.8166	0.6434	0.092*
H20C	−0.0166	0.8725	0.5682	0.092*
C16	0.5398 (4)	0.87715 (10)	1.2231 (2)	0.0615 (6)
H16A	0.6000	0.9090	1.2477	0.074*
C12	0.2681 (5)	0.82709 (10)	1.1949 (3)	0.0745 (8)
H12A	0.1435	0.8249	1.2002	0.089*
C13	0.3668 (7)	0.78194 (11)	1.1511 (3)	0.1000 (12)
H13A	0.3081	0.7499	1.1262	0.120*
C14	0.5507 (7)	0.78483 (14)	1.1446 (3)	0.1008 (13)
H14A	0.6165	0.7545	1.1166	0.121*
C15	0.6375 (5)	0.83178 (13)	1.1789 (3)	0.0850 (9)
H15B	0.7622	0.8336	1.1728	0.102*
H3	0.5643	1.0178	1.1310	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0447 (3)	0.0341 (2)	0.0744 (3)	−0.0009 (2)	−0.0013 (2)	−0.0124 (2)
N1	0.0348 (8)	0.0341 (7)	0.0461 (8)	−0.0001 (6)	−0.0029 (6)	−0.0047 (6)
O1	0.0457 (8)	0.0498 (8)	0.0665 (9)	0.0125 (7)	−0.0129 (7)	−0.0214 (7)
C8	0.0340 (9)	0.0383 (9)	0.0420 (9)	−0.0040 (7)	0.0056 (7)	−0.0040 (7)
O2	0.0557 (9)	0.0550 (8)	0.0440 (7)	−0.0029 (7)	−0.0019 (6)	−0.0021 (6)
N2	0.0394 (8)	0.0415 (8)	0.0546 (9)	0.0034 (6)	−0.0058 (8)	−0.0165 (7)
C17	0.0452 (10)	0.0340 (9)	0.0478 (10)	0.0043 (8)	−0.0074 (9)	−0.0035 (8)
C7	0.0391 (10)	0.0390 (9)	0.0380 (8)	0.0006 (8)	0.0030 (8)	−0.0044 (7)
C5	0.0486 (11)	0.0396 (9)	0.0382 (9)	0.0017 (8)	−0.0021 (8)	0.0010 (8)
O3	0.0520 (9)	0.0669 (10)	0.0677 (9)	−0.0151 (7)	−0.0005 (8)	−0.0245 (8)
C1	0.0429 (11)	0.0488 (11)	0.0452 (10)	−0.0003 (8)	0.0022 (8)	−0.0066 (8)
C6	0.0429 (10)	0.0309 (8)	0.0381 (9)	0.0005 (7)	−0.0031 (7)	−0.0012 (7)
C9	0.0405 (10)	0.0455 (11)	0.0485 (10)	0.0016 (8)	−0.0031 (8)	−0.0161 (8)
C11	0.0739 (15)	0.0472 (10)	0.0349 (9)	−0.0004 (10)	−0.0011 (10)	0.0051 (8)
C4	0.0633 (14)	0.0558 (11)	0.0401 (10)	−0.0019 (10)	−0.0063 (10)	−0.0105 (9)
C10	0.0519 (12)	0.0644 (13)	0.0414 (10)	−0.0060 (10)	0.0045 (9)	−0.0080 (9)
C2	0.0372 (12)	0.0717 (14)	0.0677 (13)	−0.0046 (10)	−0.0002 (10)	−0.0099 (12)
C3	0.0528 (13)	0.0717 (15)	0.0631 (14)	−0.0060 (11)	−0.0179 (11)	−0.0163 (11)
C20	0.0571 (13)	0.0737 (14)	0.0530 (12)	−0.0055 (11)	0.0107 (11)	−0.0135 (11)
C16	0.0757 (17)	0.0606 (14)	0.0482 (11)	0.0121 (12)	−0.0019 (11)	0.0065 (10)
C12	0.109 (2)	0.0534 (15)	0.0612 (15)	−0.0117 (14)	−0.0116 (15)	0.0098 (12)
C13	0.186 (4)	0.0415 (14)	0.0725 (18)	−0.001 (2)	−0.017 (3)	0.0040 (12)
C14	0.179 (4)	0.0629 (19)	0.0608 (16)	0.046 (2)	0.006 (2)	0.0088 (14)
C15	0.106 (2)	0.089 (2)	0.0592 (15)	0.041 (2)	0.0097 (16)	0.0165 (15)

Geometric parameters (Å, º)

S1—C8	1.6775 (18)	C11—C12	1.389 (3)
N1—C7	1.377 (2)	C11—C10	1.506 (3)
N1—C8	1.390 (2)	C4—C3	1.381 (3)
N1—H1A	0.8600	C4—H4A	0.9300
O1—C7	1.223 (2)	C10—H10A	0.9700
C8—N2	1.323 (3)	C10—H10B	0.9700
O2—C17	1.196 (2)	C2—C3	1.377 (3)
N2—C9	1.447 (2)	C2—H2B	0.9300
N2—H2A	0.8600	C3—H3A	0.9300
C17—O3	1.320 (2)	C20—H20A	0.9600
O3—H3	0.8000	C20—H20B	0.9600
C17—C9	1.518 (3)	C20—H20C	0.9600
C7—C6	1.491 (3)	C16—C15	1.393 (4)
C5—C4	1.385 (3)	C16—H16A	0.9300
C5—C6	1.402 (3)	C12—C13	1.392 (5)
C5—C20	1.497 (3)	C12—H12A	0.9300
C1—C2	1.372 (3)	C13—C14	1.370 (5)
C1—C6	1.389 (3)	C13—H13A	0.9300
C1—H1B	0.9300	C14—C15	1.360 (5)
C9—C10	1.533 (3)	C14—H14A	0.9300
C9—H9A	0.9800	C15—H15B	0.9300
C11—C16	1.383 (4)
C17—O3—H3	113.00	C5—C4—H4A	118.9
C7—N1—C8	128.09 (16)	C11—C10—C9	115.26 (16)
C7—N1—H1A	116.0	C11—C10—H10A	108.5
C8—N1—H1A	116.0	C9—C10—H10A	108.5
N2—C8—N1	116.69 (16)	C11—C10—H10B	108.5
N2—C8—S1	124.00 (14)	C9—C10—H10B	108.5
N1—C8—S1	119.31 (14)	H10A—C10—H10B	107.5
C8—N2—C9	124.64 (15)	C1—C2—C3	119.8 (2)
C8—N2—H2A	117.7	C1—C2—H2B	120.1
C9—N2—H2A	117.7	C3—C2—H2B	120.1
O2—C17—O3	124.3 (2)	C2—C3—C4	119.7 (2)
O2—C17—C9	124.73 (17)	C2—C3—H3A	120.2
O3—C17—C9	110.95 (16)	C4—C3—H3A	120.2
O1—C7—N1	121.69 (17)	C5—C20—H20A	109.5
O1—C7—C6	122.44 (16)	C5—C20—H20B	109.5
N1—C7—C6	115.85 (16)	H20A—C20—H20B	109.5
C4—C5—C6	117.07 (19)	C5—C20—H20C	109.5
C4—C5—C20	119.74 (18)	H20A—C20—H20C	109.5
C6—C5—C20	123.18 (18)	H20B—C20—H20C	109.5
C2—C1—C6	120.47 (19)	C11—C16—C15	120.8 (3)
C2—C1—H1B	119.8	C11—C16—H16A	119.6
C6—C1—H1B	119.8	C15—C16—H16A	119.6
C1—C6—C5	120.71 (18)	C11—C12—C13	120.6 (3)
C1—C6—C7	118.66 (16)	C11—C12—H12A	119.7
C5—C6—C7	120.56 (17)	C13—C12—H12A	119.7
N2—C9—C17	110.12 (16)	C14—C13—C12	119.9 (3)
N2—C9—C10	111.37 (17)	C14—C13—H13A	120.1
C17—C9—C10	109.96 (16)	C12—C13—H13A	120.1
N2—C9—H9A	108.4	C15—C14—C13	120.5 (3)
C17—C9—H9A	108.4	C15—C14—H14A	119.8
C10—C9—H9A	108.4	C13—C14—H14A	119.8
C16—C11—C12	118.3 (2)	C14—C15—C16	120.0 (4)
C16—C11—C10	120.4 (2)	C14—C15—H15B	120.0
C12—C11—C10	121.3 (3)	C16—C15—H15B	120.0
C3—C4—C5	122.27 (19)	C14—C15—H3	139.4
C3—C4—H4A	118.9	H15B—C15—H3	93.7
C7—N1—C8—N2	−6.9 (3)	O2—C17—C9—C10	109.4 (2)
C7—N1—C8—S1	172.36 (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—C9	2.3 (3)	C20—C5—C4—C3	−179.9 (2)
C8—N1—C7—O1	1.3 (3)	C16—C11—C10—C9	88.8 (2)
C8—N1—C7—C6	179.99 (17)	C12—C11—C10—C9	−91.7 (2)
C2—C1—C6—C5	1.0 (3)	N2—C9—C10—C11	65.7 (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—C1	179.0 (2)	C1—C2—C3—C4	−0.4 (4)
C4—C5—C6—C7	176.29 (17)	C5—C4—C3—C2	0.8 (4)
C20—C5—C6—C7	−4.1 (3)	C12—C11—C16—C15	0.7 (3)
O1—C7—C6—C1	129.8 (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—C13	179.8 (2)
N1—C7—C6—C5	134.26 (18)	C11—C12—C13—C14	0.7 (4)
C8—N2—C9—C17	−103.6 (2)	C12—C13—C14—C15	−0.9 (5)
C8—N2—C9—C10	134.17 (19)	C13—C14—C15—C16	1.0 (5)
O2—C17—C9—N2	−13.7 (3)	C11—C16—C15—C14	−0.9 (4)
O3—C17—C9—N2	168.75 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	1.95	2.636 (2)	135
C9—H9A···S1	0.98	2.60	3.091 (2)	111
C20—H20B···O1	0.96	2.54	2.994 (3)	109
C1—H1B···O2^i	0.93	2.50	3.187 (3)	130
C2—H2B···O1^i	0.93	2.50	3.409 (3)	165
N1—H1A···O2^i	0.86	2.46	3.237 (2)	150
O3—H3···S1^ii	0.80	2.34	3.1361 (17)	177
C9—H9A···O2^iii	0.98	2.58	3.338 (2)	134

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