2-(3-Benzoyl­thio­ureido)-3-phenyl­propanoic acid

Chong, Y.Y.; Mohamed Tahir, M.I.; Kassim, M.B.

doi:10.1107/S2414314616010919

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161091

https://doi.org/10.1107/S2414314616010919

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2-(3-Benzoylthioureido)-3-phenylpropanoic acid

Yan Yi Chong,^a Mohamed Ibrahim Mohamed Tahir ^b and Mohammad B. Kassim ^a,^c ^*

^aSchool of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia, ^bDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia, and ^cFuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
^*Correspondence e-mail: mb_kassim@ukm.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 28 June 2016; accepted 6 July 2016; online 7 July 2016)

In the title compound, C₁₇H₁₆N₂O₃S, the phenylpropanoic acid and the benzoyl moieties adopt a cis–trans conformation, respectively, with respect to the thiono S atom across the C—N bonds. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring. The crystal structure features carboxylic acid inversion dimers and pairwise N—H⋯S hydrogen bonds, which together generate [20-1] chains. Weak C—H⋯O hydrogen bonds are also observed.

Keywords: crystal structure; benzoylthioureido acid; thiourea; hydrogen bonding.

CCDC reference: 1490858

Structure description

The title compound (Fig. 1) adopts a cis–trans conformation with respect to the positions of the phenylpropanoic acid and benzoyl groups, relative to the S atom across the C8—N2 and C8—N1 bonds, respectively. The C8—S1, C7—O1, N1—C7, N1—C8 and N2—C8 bond lengths are similar to the corresponding bond lengths in related structures (Hassan et al., 2008 , 2009 ). The plane through the central thiourea unit (S1/N1/N2/C8/C9) forms dihedral angles of 14.90 (6) and 50.41 (6)°, with respect to the phenyl rings of the phenylpropanoic acid (C11–C16) and benzoyl (C1–C6) groups, respectively. The latter angle is larger than that previously reported for methyl 2-(3-benzoylthioureido)acetate (Hassan et al., 2009). The phenyl rings of the phenylpropanoic acid and benzoyl groups subtend a dihedral angle of 36.06 (8)°. An intramolecular hydrogen bond, N2—H2A⋯O1, generates an S(6) ring.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bond is shown as a dashed line.

The crystal structure (Fig. 2) features carboxylic-acid inversion dimers linked by pairs of O3—H3a⋯O2 hydrogen bonds (Table 1). The dimers are linked by pairwise N1—H1A⋯S1 hydrogen bonds, generating [20 $[\overline{1}]$ ] chains. Weak C16—H11⋯O1 hydrogen bonds are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86 (2)	1.98 (2)	2.6480 (16)	134.1 (16)
N1—H1A⋯S1ⁱ	0.790 (19)	2.571 (19)	3.3496 (13)	168.9 (18)
O3—H3A⋯O2ⁱⁱ	0.87 (2)	1.81 (2)	2.6696 (14)	175 (2)
C16—H16⋯O1ⁱⁱⁱ	0.93	2.54	3.4026 (18)	155
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+1, -z+1.

Figure 2
Partial packing view of 2-(3-benzoylthioureido)-3-phenylpropanoic acid, showing the zigzag chain formed by N—H⋯S, C—H⋯O and O—H⋯O hydrogen bonds which are shown as dashed lines [Symmetry codes: (i) −x, −y + 1, −z + 2; (ii) −x + 2, −y + 1, −z + 1; (iii) −x + 1, −y + 1, −z + 1.]

Synthesis and crystallization

The title compound was synthesized according to a previously reported method (Ngah et al., 2005 ) with modification. Instead of 2-aminopropionic acid, 2-amino-3-phenylpropanoic acid was used for this reaction. Colourless plates were obtained by recrystallization from ethanol solution at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₆N₂O₃S
M_r	328.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	5.8750 (2), 25.9891 (12), 10.3089 (4)
β (°)	90.761 (4)
V (Å³)	1573.89 (11)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.97
Crystal size (mm)	0.25 × 0.09 × 0.05

Data collection
Diffractometer	Area
Absorption correction	Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.638, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	10980, 3045, 2824
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.04
No. of reflections	3045
No. of parameters	220
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.23
Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), OLEX2 (Dolomanov et al., 2009 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1490858

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616010919/hb4065sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010919/hb4065Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010919/hb4065Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

2-(3-Benzoylthioureido)-3-phenylpropanoic acid top

Crystal data top

C₁₇H₁₆N₂O₃S	F(000) = 688
M_r = 328.38	D_x = 1.386 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 423 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 5.8750 (2) Å	Cell parameters from 5690 reflections
b = 25.9891 (12) Å	θ = 3–71°
c = 10.3089 (4) Å	µ = 1.97 mm⁻¹
β = 90.761 (4)°	T = 100 K
V = 1573.89 (11) Å³	Plate, colourless
Z = 4	0.25 × 0.09 × 0.05 mm

Data collection top

Area diffractometer	3045 independent reflections
Radiation source: fine-focus sealed tube	2824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω/2θ scans	θ_max = 71.4°, θ_min = 3.4°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −7→7
T_min = 0.638, T_max = 0.908	k = −29→31
10980 measured reflections	l = −11→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0574P)² + 0.745P] where P = (F_o² + 2F_c²)/3
3045 reflections	(Δ/σ)_max = 0.001
220 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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

	x	y	z	U_iso*/U_eq
S1	0.27806 (6)	0.545305 (13)	0.95051 (3)	0.01781 (13)
O1	0.22425 (17)	0.42118 (4)	0.64014 (9)	0.0181 (2)
O2	0.75216 (16)	0.48331 (4)	0.56133 (10)	0.0160 (2)
O3	0.97354 (17)	0.54898 (4)	0.62633 (10)	0.0161 (2)
N1	0.1462 (2)	0.45848 (5)	0.83583 (12)	0.0153 (3)
N2	0.4436 (2)	0.50147 (5)	0.73866 (12)	0.0145 (3)
C1	−0.1982 (3)	0.36410 (6)	0.67098 (15)	0.0203 (3)
H1	−0.1854	0.3781	0.5883	0.024*
C2	−0.3611 (3)	0.32678 (6)	0.69518 (17)	0.0254 (4)
H2	−0.4607	0.3165	0.6293	0.031*
C3	−0.3758 (3)	0.30477 (6)	0.81781 (18)	0.0250 (3)
H3	−0.4849	0.2797	0.8337	0.030*
C4	−0.2279 (3)	0.32014 (6)	0.91634 (16)	0.0220 (3)
H4	−0.2360	0.3049	0.9977	0.026*
C5	−0.0675 (3)	0.35843 (5)	0.89373 (15)	0.0179 (3)
H5	0.0299	0.3691	0.9603	0.022*
C6	−0.0534 (2)	0.38063 (5)	0.77145 (14)	0.0157 (3)
C7	0.1188 (2)	0.42121 (5)	0.74175 (14)	0.0145 (3)
C8	0.2955 (2)	0.50034 (5)	0.83430 (13)	0.0147 (3)
C9	0.6127 (2)	0.54169 (5)	0.72320 (13)	0.0139 (3)
H9	0.6863	0.5489	0.8071	0.017*
C10	0.5081 (2)	0.59226 (5)	0.66649 (14)	0.0155 (3)
H10A	0.4980	0.5893	0.5728	0.019*
H10B	0.3547	0.5962	0.6987	0.019*
C11	0.6439 (2)	0.63986 (5)	0.70080 (14)	0.0156 (3)
C12	0.6241 (3)	0.66130 (6)	0.82414 (15)	0.0205 (3)
H12	0.5286	0.6460	0.8842	0.025*
C13	0.7457 (3)	0.70522 (6)	0.85818 (15)	0.0231 (3)
H13	0.7292	0.7195	0.9402	0.028*
C14	0.8916 (3)	0.72781 (6)	0.77023 (16)	0.0233 (3)
H14	0.9739	0.7571	0.7932	0.028*
C15	0.9138 (3)	0.70643 (6)	0.64755 (16)	0.0221 (3)
H15	1.0122	0.7213	0.5884	0.027*
C16	0.7893 (3)	0.66287 (6)	0.61291 (14)	0.0191 (3)
H16	0.8036	0.6490	0.5302	0.023*
C17	0.7876 (2)	0.52116 (5)	0.62938 (13)	0.0136 (3)
H1A	0.060 (3)	0.4587 (7)	0.894 (2)	0.018 (5)*
H2A	0.440 (3)	0.4775 (8)	0.6817 (19)	0.022 (5)*
H3A	1.055 (4)	0.5387 (9)	0.562 (2)	0.036 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0200 (2)	0.0174 (2)	0.0163 (2)	−0.00387 (12)	0.00715 (14)	−0.00508 (12)
O1	0.0211 (5)	0.0186 (5)	0.0147 (5)	−0.0030 (4)	0.0044 (4)	−0.0023 (4)
O2	0.0157 (5)	0.0152 (5)	0.0173 (5)	−0.0006 (4)	0.0040 (4)	−0.0022 (4)
O3	0.0128 (5)	0.0187 (5)	0.0170 (5)	−0.0017 (4)	0.0035 (4)	−0.0022 (4)
N1	0.0167 (6)	0.0157 (6)	0.0137 (6)	−0.0026 (4)	0.0062 (5)	−0.0014 (4)
N2	0.0158 (6)	0.0137 (6)	0.0140 (6)	−0.0015 (5)	0.0028 (4)	−0.0031 (5)
C1	0.0209 (7)	0.0172 (7)	0.0227 (8)	0.0006 (6)	−0.0022 (6)	0.0008 (6)
C2	0.0194 (7)	0.0199 (8)	0.0368 (9)	−0.0012 (6)	−0.0058 (7)	−0.0010 (7)
C3	0.0189 (8)	0.0156 (7)	0.0406 (9)	−0.0027 (6)	0.0081 (7)	0.0012 (7)
C4	0.0261 (8)	0.0152 (7)	0.0251 (8)	0.0023 (6)	0.0109 (6)	0.0012 (6)
C5	0.0199 (7)	0.0142 (7)	0.0198 (7)	0.0021 (5)	0.0047 (6)	−0.0024 (5)
C6	0.0144 (7)	0.0129 (7)	0.0198 (7)	0.0023 (5)	0.0035 (5)	−0.0015 (5)
C7	0.0143 (7)	0.0138 (7)	0.0155 (7)	0.0020 (5)	−0.0002 (5)	0.0007 (5)
C8	0.0151 (7)	0.0143 (7)	0.0149 (7)	0.0016 (5)	0.0010 (5)	0.0001 (5)
C9	0.0134 (7)	0.0154 (7)	0.0129 (6)	−0.0013 (5)	0.0015 (5)	−0.0014 (5)
C10	0.0137 (6)	0.0164 (7)	0.0164 (7)	0.0007 (5)	0.0016 (5)	−0.0013 (5)
C11	0.0139 (6)	0.0144 (7)	0.0185 (7)	0.0021 (5)	−0.0006 (5)	0.0005 (5)
C12	0.0234 (8)	0.0186 (7)	0.0196 (7)	−0.0017 (6)	0.0045 (6)	−0.0004 (6)
C13	0.0302 (8)	0.0199 (8)	0.0193 (8)	−0.0008 (6)	−0.0003 (6)	−0.0052 (6)
C14	0.0254 (8)	0.0164 (8)	0.0279 (8)	−0.0040 (6)	−0.0037 (6)	−0.0010 (6)
C15	0.0223 (8)	0.0193 (8)	0.0248 (8)	−0.0037 (6)	0.0042 (6)	0.0037 (6)
C16	0.0223 (7)	0.0172 (7)	0.0177 (7)	0.0011 (6)	0.0010 (6)	−0.0006 (6)
C17	0.0135 (7)	0.0145 (7)	0.0127 (6)	0.0012 (5)	−0.0006 (5)	0.0020 (5)

Geometric parameters (Å, º) top

S1—C8	1.6778 (14)	C5—C6	1.390 (2)
O1—C7	1.2242 (18)	C5—H5	0.9300
O2—C17	1.2245 (18)	C6—C7	1.4956 (19)
O3—C17	1.3108 (17)	C9—C17	1.5172 (19)
O3—H3A	0.87 (2)	C9—C10	1.5612 (19)
N1—C7	1.3787 (19)	C9—H9	0.9800
N1—C8	1.3977 (18)	C10—C11	1.5114 (19)
N1—H1A	0.79 (2)	C10—H10A	0.9700
N2—C8	1.3240 (19)	C10—H10B	0.9700
N2—C9	1.4522 (18)	C11—C16	1.389 (2)
N2—H2A	0.85 (2)	C11—C12	1.395 (2)
C1—C2	1.388 (2)	C12—C13	1.389 (2)
C1—C6	1.399 (2)	C12—H12	0.9300
C1—H1	0.9300	C13—C14	1.386 (2)
C2—C3	1.391 (2)	C13—H13	0.9300
C2—H2	0.9300	C14—C15	1.389 (2)
C3—C4	1.386 (2)	C14—H14	0.9300
C3—H3	0.9300	C15—C16	1.392 (2)
C4—C5	1.392 (2)	C15—H15	0.9300
C4—H4	0.9300	C16—H16	0.9300

C17—O3—H3A	108.5 (15)	N2—C9—C10	112.38 (11)
C7—N1—C8	127.33 (13)	C17—C9—C10	108.90 (11)
C7—N1—H1A	117.9 (13)	N2—C9—H9	109.6
C8—N1—H1A	114.4 (13)	C17—C9—H9	109.6
C8—N2—C9	123.71 (12)	C10—C9—H9	109.6
C8—N2—H2A	118.9 (13)	C11—C10—C9	113.41 (11)
C9—N2—H2A	117.4 (13)	C11—C10—H10A	108.9
C2—C1—C6	119.71 (15)	C9—C10—H10A	108.9
C2—C1—H1	120.1	C11—C10—H10B	108.9
C6—C1—H1	120.1	C9—C10—H10B	108.9
C1—C2—C3	120.12 (15)	H10A—C10—H10B	107.7
C1—C2—H2	119.9	C16—C11—C12	118.83 (14)
C3—C2—H2	119.9	C16—C11—C10	121.81 (13)
C4—C3—C2	120.10 (14)	C12—C11—C10	119.36 (13)
C4—C3—H3	120.0	C13—C12—C11	120.65 (14)
C2—C3—H3	120.0	C13—C12—H12	119.7
C3—C4—C5	120.15 (15)	C11—C12—H12	119.7
C3—C4—H4	119.9	C14—C13—C12	120.21 (15)
C5—C4—H4	119.9	C14—C13—H13	119.9
C6—C5—C4	119.81 (14)	C12—C13—H13	119.9
C6—C5—H5	120.1	C13—C14—C15	119.51 (14)
C4—C5—H5	120.1	C13—C14—H14	120.2
C5—C6—C1	120.05 (14)	C15—C14—H14	120.2
C5—C6—C7	121.81 (13)	C14—C15—C16	120.23 (15)
C1—C6—C7	118.11 (13)	C14—C15—H15	119.9
O1—C7—N1	123.14 (13)	C16—C15—H15	119.9
O1—C7—C6	121.74 (13)	C11—C16—C15	120.57 (14)
N1—C7—C6	115.12 (12)	C11—C16—H16	119.7
N2—C8—N1	116.39 (12)	C15—C16—H16	119.7
N2—C8—S1	124.28 (11)	O2—C17—O3	124.38 (13)
N1—C8—S1	119.32 (11)	O2—C17—C9	122.44 (12)
N2—C9—C17	106.66 (11)	O3—C17—C9	113.15 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86 (2)	1.98 (2)	2.6480 (16)	134.1 (16)
N1—H1A···S1ⁱ	0.790 (19)	2.571 (19)	3.3496 (13)	168.9 (18)
O3—H3A···O2ⁱⁱ	0.87 (2)	1.81 (2)	2.6696 (14)	175 (2)
C16—H16···O1ⁱⁱⁱ	0.93	2.54	3.4026 (18)	155

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

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia for research grants (OUP-2012–073 and UKM-PTS-016–2010), the Ministry of Higher Education for the UKM-ST-06-FRGS0111–2009 grant and MyMaster funding for CYY.

References

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