1-{[(Z)-Cyclo-pentyl-idene]amino}-3-phenyl-thio-urea.

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 thio-urea unit is 78.22 (8)°. In the crystal, molecules are linked via pairs of N-H⋯S hydrogen bonds forming inversion dimers.

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 = 233.33

Triclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.097

S = 1.03

11360 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.20 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814007028/sj5395sup1.cif

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

CCDC reference: 994387

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H15N3S	Z = 2
Mr = 233.33	F(000) = 248
Triclinic, P1	Dx = 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

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	Rint = 0.026
Detector resolution: 10.4167 pixels mm-1	θmax = 70.0°, θmin = 4.0°
ω scans	h = −8→8
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009)	k = −9→9
Tmin = 0.65, Tmax = 0.92	l = −13→13
11363 measured reflections

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(Fo2) + (0.039P)2 + 0.1956P] where P = (Fo2 + 2Fc2)/3
11360 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .