1-(2-Amino­eth­yl)-3-phenyl­thio­urea

Pansuriya, P.; Friedrich, H.B.; Maguire, G.E.M.

doi:10.1107/S1600536811036476

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2621

https://doi.org/10.1107/S1600536811036476

Open

access

1-(2-Aminoethyl)-3-phenylthiourea

Pramod Pansuriya,^a Holger B. Friedrich ^a and Glenn E. M. Maguire ^a ^*

^aSchool of Chemistry, University of KwaZulu-Natal, Durban, 4000, South Africa
^*Correspondence e-mail: maguireg@ukzn.ac.za

(Received 10 May 2011; accepted 7 September 2011; online 14 September 2011)

In the crystal structure of the title compound, C₉H₁₃N₃S, molecules are linked through N—H⋯S and N—H⋯N hydrogen bonds, forming hydrogen-bonded tapes along the b axis. The dihedral angle between the phenyl ring and the thiourea group is 44.9 (2)°.

Related literature

For the synthesis of the title compund, see: Lee et al. (1985 ). For applications of thioureas, see: Tommasino et al. (1999 , 2000 ); Leung et al. (2008 ). For similar structures, see: Guo (2007 ); Okino et al. (2005 ).

Experimental

Crystal data

C₉H₁₃N₃S
M_r = 195.28
Monoclinic, P 2₁ /c
a = 8.5105 (2) Å
b = 11.5644 (3) Å
c = 9.9829 (3) Å
β = 93.580 (1)°
V = 980.59 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.52 × 0.51 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
11919 measured reflections
2365 independent reflections
1893 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.05
2365 reflections
134 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.898 (17)	2.445 (17)	3.3108 (12)	162.0 (12)
N2—H2N⋯N3ⁱⁱ	0.836 (15)	2.232 (15)	2.9974 (16)	152.5 (13)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036476/fy2013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036476/fy2013Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036476/fy2013Isup3.cml

checkCIF report

Comment top

Thioureas have been employed as ligands for metal complexes used in asymetric catalytic hydrogenation (Tommasino et al., 1999, 2000) as well as synthetic anion hosts (Leung et al., 2008). A number of single-crystal X-ray structures have been reported demonstrating a range of inter- and intra molecular hydrogen bonding motifs (Guo, 2007) and (Okino et al., 2005). The title compound is commercially available, but its structure determination (Fig. 1) has not been reported previously.

In the crystal, molecules are linked through intermolecular N—H···S and N—H···N hydrogen bonds (Table 1), forming hydrogen-bonded tapes lying parallel to the b axis (Fig. 2). The closest structural analogues all demonstrate intramolecular hydrogen bonding. The hydrogen atoms of the primary amino group are not involved in any short intermolecular contact.

Related literature top

For the synthesis of the title compund, see: Lee et al. (1985). For applications of thioureas, see: Tommasino et al. (1999, 2000); Leung et al. (2008). For similar structures, see: Guo (2007); Okino et al. (2005).

Experimental top

The title compound was synthesized as reported by Lee et al. (1985). A solution of phenyl isothiocyanate (6.75 g, 50 mmole) in diethylether (15 ml) was added dropwise at 15°C to a vigorously stirred solution of anhydrous ethylenediamine (6.01 g, 100 mmole) in isopropyl alcohol (100 ml) over a period of 30 min. The reaction mixture was stirred for 2 hrs at room temperature and quenched with water (200 ml). The reaction mixture was maintained overnight at room temperature. Then the reaction mixture was acidified with conc. HCl up to a pH of 2.6. The solvents were evaporated under vacuum and the residue was suspended in hot water for 30 min and the resulting precipitate was filtered. The filtrate was basified by the addition of caustic lye, and a precipitate formed. This in turn was filtered, washed with ice cold water and dried. The yield was 5.06 g. (75%).

Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation from ethyl acetate at room temperature. M.p. = 408–409 K.

Structure description top

For the synthesis of the title compund, see: Lee et al. (1985). For applications of thioureas, see: Tommasino et al. (1999, 2000); Leung et al. (2008). For similar structures, see: Guo (2007); Okino et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement elipsoids are drawn at 40% probability. Hydrogen atoms are shown as spheres of arbitrary radii.
	Fig. 2. Hydrogen bonding interations viewed on the ab plane. All hydrogens except those involved in bonding have been omitted for clarity.

1-(2-Aminoethyl)-3-phenylthiourea top

Crystal data top

C₉H₁₃N₃S	F(000) = 416
M_r = 195.28	D_x = 1.323 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4309 reflections
a = 8.5105 (2) Å	θ = 2.4–28.3°
b = 11.5644 (3) Å	µ = 0.29 mm⁻¹
c = 9.9829 (3) Å	T = 173 K
β = 93.580 (1)°	Plate, colourless
V = 980.59 (5) Å³	0.52 × 0.51 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1893 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 28.0°, θ_min = 2.4°
φ and ω scans	h = −11→11
11919 measured reflections	k = −15→15
2365 independent reflections	l = −13→13

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0456P)² + 0.1114P] where P = (F_o² + 2F_c²)/3
2365 reflections	(Δ/σ)_max = 0.001
134 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₉H₁₃N₃S	V = 980.59 (5) Å³
M_r = 195.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5105 (2) Å	µ = 0.29 mm⁻¹
b = 11.5644 (3) Å	T = 173 K
c = 9.9829 (3) Å	0.52 × 0.51 × 0.25 mm
β = 93.580 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1893 reflections with I > 2σ(I)
11919 measured reflections	R_int = 0.042
2365 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.25 e Å⁻³
2365 reflections	Δρ_min = −0.31 e Å⁻³
134 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
C1	0.70454 (14)	0.28612 (11)	−0.12947 (13)	0.0231 (3)
C2	0.67903 (16)	0.18764 (12)	−0.20730 (13)	0.0276 (3)
H2	0.5781	0.1523	−0.2139	0.033*
C3	0.80133 (18)	0.14084 (13)	−0.27550 (14)	0.0337 (3)
H3	0.7842	0.0726	−0.3273	0.040*
C4	0.94801 (17)	0.19291 (15)	−0.26863 (15)	0.0384 (4)
H4	1.0311	0.1611	−0.3162	0.046*
C5	0.97292 (15)	0.29189 (15)	−0.19184 (15)	0.0349 (4)
H5	1.0734	0.3280	−0.1872	0.042*
C6	0.85235 (14)	0.33857 (13)	−0.12171 (14)	0.0279 (3)
H6	0.8704	0.4060	−0.0686	0.033*
C7	0.46708 (13)	0.29317 (11)	0.00584 (13)	0.0232 (3)
C8	0.35806 (15)	0.12066 (11)	0.11161 (14)	0.0258 (3)
H8A	0.3210	0.1745	0.1800	0.031*
H8B	0.4109	0.0549	0.1593	0.031*
C9	0.21718 (15)	0.07587 (12)	0.02639 (14)	0.0283 (3)
H9A	0.1427	0.0379	0.0848	0.034*
H9B	0.1620	0.1415	−0.0196	0.034*
N1	0.58075 (12)	0.34090 (10)	−0.06492 (12)	0.0252 (3)
N2	0.47210 (12)	0.18047 (9)	0.03209 (11)	0.0235 (2)
S1	0.32346 (4)	0.38159 (3)	0.06009 (4)	0.02980 (13)
N3	0.26714 (14)	−0.00755 (11)	−0.07427 (13)	0.0323 (3)
H1N	0.5828 (17)	0.4185 (15)	−0.0621 (15)	0.031 (4)*
H2N	0.5532 (17)	0.1426 (13)	0.0186 (15)	0.027 (4)*
H3NA	0.298 (2)	0.0311 (17)	−0.147 (2)	0.056 (6)*
H3NB	0.186 (2)	−0.0499 (16)	−0.1047 (18)	0.049 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0229 (6)	0.0241 (7)	0.0226 (6)	0.0037 (5)	0.0050 (5)	0.0048 (5)
C2	0.0300 (7)	0.0281 (7)	0.0253 (7)	0.0017 (5)	0.0051 (5)	0.0027 (6)
C3	0.0454 (8)	0.0328 (8)	0.0237 (7)	0.0089 (6)	0.0090 (6)	0.0002 (6)
C4	0.0348 (8)	0.0516 (10)	0.0301 (8)	0.0151 (7)	0.0128 (6)	0.0063 (7)
C5	0.0222 (6)	0.0520 (10)	0.0310 (8)	0.0032 (6)	0.0065 (5)	0.0080 (7)
C6	0.0246 (6)	0.0333 (8)	0.0260 (7)	−0.0006 (5)	0.0036 (5)	0.0032 (6)
C7	0.0203 (6)	0.0219 (7)	0.0275 (7)	−0.0019 (5)	0.0028 (5)	−0.0025 (5)
C8	0.0274 (6)	0.0219 (7)	0.0287 (7)	−0.0015 (5)	0.0075 (5)	0.0018 (5)
C9	0.0235 (6)	0.0244 (7)	0.0373 (8)	0.0010 (5)	0.0047 (5)	0.0031 (6)
N1	0.0227 (5)	0.0176 (6)	0.0362 (7)	0.0001 (4)	0.0095 (5)	−0.0001 (5)
N2	0.0215 (5)	0.0192 (6)	0.0307 (6)	0.0012 (4)	0.0073 (4)	0.0000 (5)
S1	0.02171 (17)	0.0211 (2)	0.0478 (2)	0.00148 (12)	0.01190 (14)	−0.00020 (15)
N3	0.0303 (6)	0.0302 (7)	0.0362 (7)	−0.0015 (5)	−0.0006 (5)	−0.0048 (6)

Geometric parameters (Å, º) top

C1—C2	1.3881 (19)	C7—N1	1.3509 (16)
C1—C6	1.3943 (17)	C7—S1	1.7074 (12)
C1—N1	1.4181 (15)	C8—N2	1.4651 (16)
C2—C3	1.3887 (19)	C8—C9	1.5173 (19)
C2—H2	0.9500	C8—H8A	0.9900
C3—C4	1.384 (2)	C8—H8B	0.9900
C3—H3	0.9500	C9—N3	1.4747 (18)
C4—C5	1.387 (2)	C9—H9A	0.9900
C4—H4	0.9500	C9—H9B	0.9900
C5—C6	1.3871 (18)	N1—H1N	0.898 (17)
C5—H5	0.9500	N2—H2N	0.836 (15)
C6—H6	0.9500	N3—H3NA	0.91 (2)
C7—N2	1.3296 (17)	N3—H3NB	0.882 (19)

C2—C1—C6	119.80 (12)	N2—C8—C9	112.61 (11)
C2—C1—N1	121.75 (11)	N2—C8—H8A	109.1
C6—C1—N1	118.27 (12)	C9—C8—H8A	109.1
C1—C2—C3	119.89 (13)	N2—C8—H8B	109.1
C1—C2—H2	120.1	C9—C8—H8B	109.1
C3—C2—H2	120.1	H8A—C8—H8B	107.8
C4—C3—C2	120.50 (14)	N3—C9—C8	110.73 (10)
C4—C3—H3	119.7	N3—C9—H9A	109.5
C2—C3—H3	119.7	C8—C9—H9A	109.5
C3—C4—C5	119.53 (13)	N3—C9—H9B	109.5
C3—C4—H4	120.2	C8—C9—H9B	109.5
C5—C4—H4	120.2	H9A—C9—H9B	108.1
C4—C5—C6	120.53 (13)	C7—N1—C1	129.17 (11)
C4—C5—H5	119.7	C7—N1—H1N	113.9 (9)
C6—C5—H5	119.7	C1—N1—H1N	116.5 (9)
C5—C6—C1	119.73 (14)	C7—N2—C8	123.73 (11)
C5—C6—H6	120.1	C7—N2—H2N	119.9 (10)
C1—C6—H6	120.1	C8—N2—H2N	115.0 (10)
N2—C7—N1	119.23 (11)	C9—N3—H3NA	109.6 (12)
N2—C7—S1	122.64 (9)	C9—N3—H3NB	110.3 (11)
N1—C7—S1	118.12 (10)	H3NA—N3—H3NB	104.6 (17)

C6—C1—C2—C3	0.9 (2)	N2—C8—C9—N3	60.48 (15)
N1—C1—C2—C3	176.02 (12)	N2—C7—N1—C1	6.3 (2)
C1—C2—C3—C4	−1.3 (2)	S1—C7—N1—C1	−174.59 (10)
C2—C3—C4—C5	0.7 (2)	C2—C1—N1—C7	44.9 (2)
C3—C4—C5—C6	0.3 (2)	C6—C1—N1—C7	−139.94 (14)
C4—C5—C6—C1	−0.6 (2)	N1—C7—N2—C8	177.90 (12)
C2—C1—C6—C5	0.0 (2)	S1—C7—N2—C8	−1.17 (18)
N1—C1—C6—C5	−175.28 (12)	C9—C8—N2—C7	89.72 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.898 (17)	2.445 (17)	3.3108 (12)	162.0 (12)
N2—H2N···N3ⁱⁱ	0.836 (15)	2.232 (15)	2.9974 (16)	152.5 (13)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₃N₃S
M_r	195.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.5105 (2), 11.5644 (3), 9.9829 (3)
β (°)	93.580 (1)
V (Å³)	980.59 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.52 × 0.51 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11919, 2365, 1893
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.05
No. of reflections	2365
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.31

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.898 (17)	2.445 (17)	3.3108 (12)	162.0 (12)
N2—H2N···N3ⁱⁱ	0.836 (15)	2.232 (15)	2.9974 (16)	152.5 (13)

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

Acknowledgements

The authors wish to thank Dr Manuel Fernandes from the Chemistry Department of the University of the Witwatersrand for his assistance with the data collection and refinement, and c*change for support.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Guo, H.-M. (2007). Acta Cryst. E63, o2781. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, K. N., Fesus, L., Yancey, S. T., Girardg, J. E. & Chung, S. I. (1985). J. Biol. Chem. 260, 14689–14694. CAS PubMed Google Scholar
Leung, A. N., Degenhardt, D. A. & Bühlmann, P. (2008). Tetrahedron, 64, 2530–2536. Web of Science CrossRef CAS Google Scholar
Okino, T., Hoashi, Y., Furukawa, T., Xu, X. & Takemoto, Y. (2005). J. Am. Chem. Soc. 127, 119–125. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tommasino, M. L., Thomazeau, C., Touchard, F. & Lemaire, M. (1999). Tetrahedron Asymmetry 11, 1813–1819. Web of Science CrossRef Google Scholar
Tommasino, M. L., Thomazeau, C., Touchard, F. & Lemaire, M. (2000). Tetrahedron:Asymmetry 11, 4835–4841. Web of Science CrossRef CAS Google Scholar