1-{[(Z)-Cyclo­pentyl­idene]amino}-3-phenyl­thio­urea

Mague, J.T.; Mohamed, S.K.; Akkurt, M.; Hassan, A.A.; Albayati, M.R.

doi:10.1107/S1600536814007028

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o515

doi:10.1107/S1600536814007028

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1-{[(Z)-Cyclopentylidene]amino}-3-phenylthiourea

Joel T. Mague,^a Shaaban K. Mohamed,^b,^c Mehmet Akkurt,^d Alaa A. Hassan ^c and Mustafa R. Albayati ^e ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^eKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

(Received 27 March 2014; accepted 29 March 2014; online 5 April 2014)

The sample of the title compound, C₁₂H₁₅N₃S, chosen for study consisted of triclinic crystals twinned by a 180° rotation about the a axis. The five-membered ring adopts a twisted conformation. The dihedral angle between the phenyl ring and the mean plane of the thiourea unit is 78.22 (8)°. In the crystal, molecules are linked via pairs of N—H⋯S hydrogen bonds forming inversion dimers.

CCDC reference: 994387

Related literature

For the use of thiourea as a building-block in the synthesis of heterocycles, see: Yin et al. (2008 ). For the diverse biological properties of thiourea-containing compounds and their metal complexes, see: Saeed et al. (2010 ); Solomon et al. (2010 ); Karakuş & Rollas (2002 ); Abdullah & Salh (2010 ). For the synthesis of the title compound, see: Akkurt et al. (2014 ). For structural studies on thiourea derivatives, see: Struga et al. (2009 ). For ring-puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₂H₁₅N₃S
M_r = 233.33
Triclinic, $[P \overline 1]$
a = 7.3997 (2) Å
b = 7.5790 (1) Å
c = 11.4657 (2) Å
α = 93.0220 (9)°
β = 105.4530 (9)°
γ = 104.7070 (8)°
V = 594.45 (2) Å³
Z = 2
Cu Kα radiation
μ = 2.21 mm⁻¹
T = 100 K
0.21 × 0.10 × 0.04 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ) T_min = 0.65, T_max = 0.92
11363 measured reflections
11360 independent reflections
9454 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.097
S = 1.03
11360 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1ⁱ	0.91	2.56	3.4636 (18)	172
Symmetry code: (i) -x+2, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2013 ); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT and CELL_NOW (Sheldrick, 2008a ); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008a ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).

Supporting information

CCDC reference: 994387

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814007028/sj5395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007028/sj5395Isup2.hkl

checkCIF report

Comment top

For the past few decades, thiourea derivatives have attracted great attention not only because they are important building blocks in the synthesis of heterocycles and organo-metal complexes (Yin et al., 2008) but also due to their broad spectrum of biological activities such as anti-bacterial, anti-cancer (Saeed et al., 2010), anti-malarial (Solomon et al., 2010), anti-tuberculosis (Karakuş & Rollas 2002) anti-convulsion, analgesic and HDL-elevating properties. In addition, metal complex of thiourea derivatives exhibit anti-inflammatory, anti-cancer and anti-fungal activities (Abdullah & Salh, 2010). Furthermore, the thiourea structure contains a central hydrophilic part and two hydrophobic moieties forming a butterfly-like conformation. This conformation is a part of the structure of an anti-HIV agent (Struga et al., 2009).

Fig. 1 shows a perspective view of the title compound (I). The five-membered ring (C1–C5) adopts a twisted conformation, [the puckering parameters (Cremer & Pople, 1975) are Q(2) = 0.316 (2) Å and ϕ(2) = 85.7 (4)°]. The dihedral angle between the phenyl ring and the least-squares plane of the thiourea moiety is 78.22 (8)°.

In the crystal structure, the molecules are connected by weak N—H···S interactions (Fig. 2 and Table 1).

Related literature top

For the use of thiourea as a building-block in the synthesis of heterocycles, see: Yin et al. (2008). For the diverse biological properties of thiourea-containing compounds and their metal complexes, see: Saeed et al. (2010); Solomon et al. (2010); Karakuş & Rollas (2002); Abdullah & Salh (2010). For the synthesis of the title compound, see: Akkurt et al. (2014). For structural studies on thiourea derivatives, see: Struga et al. (2009). For ring-puckering parameters, see: Cremer & Pople (1975).

Experimental top

The title compound was prepared according to our previously reported method (Akkurt et al., 2014). Colourless crystals suitable for X-ray diffraction were obtained by crystallization of (I) from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013) and CELL_NOW (Sheldrick, 2008a); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).

Figures top

	Fig. 1. Perspective view of I with 50% probability displacement ellipsoids.
	Fig. 2. Packing viewed down the a axis and showing N—H···S interactions.

1-{[(Z)-Cyclopentylidene]amino}-3-phenylthiourea top

Crystal data top

C₁₂H₁₅N₃S	Z = 2
M_r = 233.33	F(000) = 248
Triclinic, P1	D_x = 1.304 Mg m⁻³
a = 7.3997 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 7.5790 (1) Å	Cell parameters from 8773 reflections
c = 11.4657 (2) Å	θ = 4.0–70.0°
α = 93.0220 (9)°	µ = 2.21 mm⁻¹
β = 105.4530 (9)°	T = 100 K
γ = 104.7070 (8)°	Plate, colourless
V = 594.45 (2) Å³	0.21 × 0.10 × 0.04 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	11360 independent reflections
Radiation source: INCOATEC IµS micro–focus source	9454 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4167 pixels mm^-1	θ_max = 70.0°, θ_min = 4.0°
ω scans	h = −8→8
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −9→9
T_min = 0.65, T_max = 0.92	l = −13→13
11363 measured reflections

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)] = 0.040	Hydrogen site location: mixed
wR(F²) = 0.097	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.039P)² + 0.1956P] where P = (F_o² + 2F_c²)/3
11360 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₁₅N₃S	γ = 104.7070 (8)°
M_r = 233.33	V = 594.45 (2) Å³
Triclinic, P1	Z = 2
a = 7.3997 (2) Å	Cu Kα radiation
b = 7.5790 (1) Å	µ = 2.21 mm⁻¹
c = 11.4657 (2) Å	T = 100 K
α = 93.0220 (9)°	0.21 × 0.10 × 0.04 mm
β = 105.4530 (9)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	11360 independent reflections
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	9454 reflections with I > 2σ(I)
T_min = 0.65, T_max = 0.92	R_int = 0.026
11363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
11360 reflections	Δρ_min = −0.20 e Å⁻³
146 parameters

Special details top

Experimental. Analysis of 985 reflections having I/σ(I) > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008a) showed the crystal to belong to the triclinic system and to be twinned by a 180° rotation about the a axis. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen were placed in locations derived from a difference map and their parameters adjusted to give N—H = 0.91 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.89113 (8)	1.01459 (7)	0.81488 (4)	0.02372 (18)
N1	0.7313 (2)	0.5215 (2)	0.90890 (15)	0.0216 (4)
N2	0.8223 (3)	0.7082 (2)	0.91604 (15)	0.0213 (4)
H2	0.8859	0.7824	0.9880	0.026*
N3	0.7179 (2)	0.6693 (2)	0.70759 (14)	0.0226 (4)
H3	0.6668	0.5483	0.7126	0.027*
C1	0.7350 (3)	0.4552 (3)	1.01002 (18)	0.0201 (5)
C2	0.8303 (3)	0.5512 (3)	1.13816 (17)	0.0221 (5)
H2A	0.7989	0.6695	1.1480	0.027*
H2B	0.9739	0.5749	1.1600	0.027*
C3	0.7435 (3)	0.4160 (3)	1.21708 (19)	0.0274 (5)
H3A	0.8400	0.4244	1.2973	0.033*
H3B	0.6258	0.4424	1.2306	0.033*
C4	0.6913 (3)	0.2257 (3)	1.14529 (19)	0.0280 (5)
H4A	0.5820	0.1399	1.1656	0.034*
H4B	0.8049	0.1748	1.1635	0.034*
C5	0.6317 (3)	0.2559 (3)	1.01077 (19)	0.0242 (5)
H5A	0.6742	0.1736	0.9604	0.029*
H5B	0.4885	0.2326	0.9791	0.029*
C6	0.8052 (3)	0.7858 (3)	0.81110 (18)	0.0201 (5)
C7	0.6780 (3)	0.7262 (3)	0.58782 (18)	0.0240 (5)
C8	0.8249 (4)	0.7674 (3)	0.5318 (2)	0.0358 (6)
H8	0.9527	0.7619	0.5729	0.043*
C9	0.7831 (5)	0.8171 (4)	0.4146 (2)	0.0453 (7)
H9	0.8827	0.8458	0.3751	0.054*
C10	0.5971 (5)	0.8248 (3)	0.3557 (2)	0.0448 (7)
H10	0.5690	0.8582	0.2755	0.054*
C11	0.4526 (4)	0.7845 (3)	0.4123 (2)	0.0410 (7)
H11	0.3249	0.7906	0.3714	0.049*
C12	0.4930 (4)	0.7346 (3)	0.5295 (2)	0.0309 (5)
H12	0.3933	0.7066	0.5690	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0326 (3)	0.0182 (3)	0.0185 (3)	0.0051 (2)	0.0058 (2)	0.0045 (2)
N1	0.0248 (10)	0.0173 (9)	0.0231 (9)	0.0043 (8)	0.0089 (8)	0.0044 (7)
N2	0.0278 (10)	0.0178 (9)	0.0159 (9)	0.0025 (7)	0.0058 (7)	0.0029 (7)
N3	0.0303 (10)	0.0178 (9)	0.0165 (9)	0.0016 (8)	0.0056 (8)	0.0036 (7)
C1	0.0203 (11)	0.0204 (11)	0.0229 (11)	0.0082 (9)	0.0091 (9)	0.0057 (9)
C2	0.0244 (11)	0.0220 (11)	0.0208 (11)	0.0067 (9)	0.0070 (9)	0.0062 (9)
C3	0.0293 (12)	0.0298 (12)	0.0225 (11)	0.0056 (10)	0.0078 (10)	0.0104 (9)
C4	0.0264 (12)	0.0257 (12)	0.0333 (13)	0.0064 (10)	0.0097 (10)	0.0135 (10)
C5	0.0263 (12)	0.0198 (11)	0.0276 (12)	0.0053 (9)	0.0104 (10)	0.0053 (9)
C6	0.0197 (11)	0.0235 (11)	0.0196 (10)	0.0076 (9)	0.0076 (9)	0.0062 (9)
C7	0.0369 (13)	0.0156 (10)	0.0161 (10)	0.0031 (10)	0.0064 (10)	0.0015 (8)
C8	0.0437 (15)	0.0386 (14)	0.0242 (12)	0.0061 (12)	0.0133 (11)	0.0051 (10)
C9	0.073 (2)	0.0360 (14)	0.0241 (13)	−0.0004 (14)	0.0238 (14)	0.0033 (11)
C10	0.088 (2)	0.0192 (12)	0.0158 (12)	0.0041 (13)	0.0058 (14)	0.0039 (9)
C11	0.0595 (18)	0.0246 (13)	0.0279 (13)	0.0113 (12)	−0.0054 (13)	0.0043 (10)
C12	0.0402 (15)	0.0224 (11)	0.0269 (12)	0.0075 (11)	0.0054 (11)	0.0040 (9)

Geometric parameters (Å, º) top

S1—C6	1.682 (2)	C4—C5	1.533 (3)
N1—C1	1.284 (2)	C4—H4A	0.9900
N1—N2	1.392 (2)	C4—H4B	0.9900
N2—C6	1.357 (2)	C5—H5A	0.9900
N2—H2	0.9098	C5—H5B	0.9900
N3—C6	1.341 (3)	C7—C12	1.373 (3)
N3—C7	1.439 (2)	C7—C8	1.382 (3)
N3—H3	0.9098	C8—C9	1.391 (3)
C1—C2	1.503 (3)	C8—H8	0.9500
C1—C5	1.512 (3)	C9—C10	1.379 (4)
C2—C3	1.535 (3)	C9—H9	0.9500
C2—H2A	0.9900	C10—C11	1.373 (4)
C2—H2B	0.9900	C10—H10	0.9500
C3—C4	1.526 (3)	C11—C12	1.391 (3)
C3—H3A	0.9900	C11—H11	0.9500
C3—H3B	0.9900	C12—H12	0.9500

C1—N1—N2	117.12 (17)	C1—C5—C4	104.55 (17)
C6—N2—N1	118.43 (17)	C1—C5—H5A	110.8
C6—N2—H2	118.3	C4—C5—H5A	110.8
N1—N2—H2	123.1	C1—C5—H5B	110.8
C6—N3—C7	123.96 (16)	C4—C5—H5B	110.8
C6—N3—H3	118.7	H5A—C5—H5B	108.9
C7—N3—H3	116.9	N3—C6—N2	115.83 (18)
N1—C1—C2	128.72 (18)	N3—C6—S1	123.58 (14)
N1—C1—C5	120.66 (18)	N2—C6—S1	120.59 (16)
C2—C1—C5	110.61 (16)	C12—C7—C8	120.89 (19)
C1—C2—C3	104.01 (17)	C12—C7—N3	119.41 (19)
C1—C2—H2A	111.0	C8—C7—N3	119.68 (19)
C3—C2—H2A	111.0	C7—C8—C9	119.1 (2)
C1—C2—H2B	111.0	C7—C8—H8	120.4
C3—C2—H2B	111.0	C9—C8—H8	120.4
H2A—C2—H2B	109.0	C10—C9—C8	120.0 (3)
C4—C3—C2	105.41 (17)	C10—C9—H9	120.0
C4—C3—H3A	110.7	C8—C9—H9	120.0
C2—C3—H3A	110.7	C11—C10—C9	120.4 (2)
C4—C3—H3B	110.7	C11—C10—H10	119.8
C2—C3—H3B	110.7	C9—C10—H10	119.8
H3A—C3—H3B	108.8	C10—C11—C12	120.0 (2)
C3—C4—C5	105.07 (16)	C10—C11—H11	120.0
C3—C4—H4A	110.7	C12—C11—H11	120.0
C5—C4—H4A	110.7	C7—C12—C11	119.6 (2)
C3—C4—H4B	110.7	C7—C12—H12	120.2
C5—C4—H4B	110.7	C11—C12—H12	120.2
H4A—C4—H4B	108.8

C1—N1—N2—C6	−173.97 (17)	N1—N2—C6—N3	−6.8 (3)
N2—N1—C1—C2	−1.9 (3)	N1—N2—C6—S1	173.42 (14)
N2—N1—C1—C5	177.10 (17)	C6—N3—C7—C12	−100.6 (2)
N1—C1—C2—C3	166.7 (2)	C6—N3—C7—C8	80.9 (3)
C5—C1—C2—C3	−12.4 (2)	C12—C7—C8—C9	−0.3 (3)
C1—C2—C3—C4	27.7 (2)	N3—C7—C8—C9	178.2 (2)
C2—C3—C4—C5	−32.9 (2)	C7—C8—C9—C10	0.0 (4)
N1—C1—C5—C4	173.24 (18)	C8—C9—C10—C11	0.3 (4)
C2—C1—C5—C4	−7.6 (2)	C9—C10—C11—C12	−0.3 (4)
C3—C4—C5—C1	24.8 (2)	C8—C7—C12—C11	0.3 (3)
C7—N3—C6—N2	176.88 (18)	N3—C7—C12—C11	−178.16 (19)
C7—N3—C6—S1	−3.4 (3)	C10—C11—C12—C7	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.91	2.56	3.4636 (18)	172

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.91	2.56	3.4636 (18)	172

Symmetry code: (i) −x+2, −y+2, −z+2.

Acknowledgements

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer is gratefully acknowledged.

References

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