3-[(Cyclo­hexyl­idene)amino]-1-(4-methyl­phen­yl)thio­urea

Zhang, Y.-L.; Zhang, X.-W.; Zhang, F.-J.

doi:10.1107/S1600536811015510

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1268

doi:10.1107/S1600536811015510

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3-[(Cyclohexylidene)amino]-1-(4-methylphenyl)thiourea

Yan-Ling Zhang,^a ^* Xiao-Wei Zhang ^a and Fu-Juan Zhang ^a

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China
^*Correspondence e-mail: zhangyanling315@126.com

(Received 21 April 2011; accepted 25 April 2011; online 29 April 2011)

In the title compound, C₁₄H₁₉N₃S, the cyclohexane ring has a chair conformation. The almost planar aminothiourea unit (r.m.s. deviation = 0.0062 Å) is aligned at a dihedral angle of 45.23 (8)° with respect to the benzene ring. Intermolecular N—H⋯N and N—H⋯S hydrogen bonding stabilizes the crystal structure.

Related literature

For related structures and the biological applications of thiosemicarbazones, see: Hu et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₉N₃S
M_r = 261.38
Orthorhombic, I b c a
a = 14.9151 (4) Å
b = 22.5593 (5) Å
c = 17.1642 (3) Å
V = 5775.3 (2) Å³
Z = 16
Cu Kα radiation
μ = 1.87 mm⁻¹
T = 291 K
0.40 × 0.25 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.521, T_max = 0.652
7202 measured reflections
2583 independent reflections
2024 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.162
S = 1.02
2583 reflections
172 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.89 (3)	2.48 (3)	3.268 (3)	148 (2)
N2—H2⋯S1ⁱⁱ	0.86 (3)	2.70 (3)	3.531 (2)	164 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, -z]$ ; (ii) $[x, -y, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015510/xu5197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015510/xu5197Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811015510/xu5197Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones have attracted much attention as they show potential application in the biological field (Hu et al., 2006). There are a few single-crystal reports about them. Detailed information on their molecular and crystal structures is necessary to understand their anticancer activity. The molecular structure of (I) is shown in Fig 1. The cyclohexane ring adopts a chair conformation. The almost planar aminothiourea unit (r.m.s. deviation = 0.0062 Å) is aligned at a dihedral angle of 45.23 (8)° with respect to the plane of the benzene ring. In the crystal structure of the title compound, there are N—H···N an N—H···S hydrogen-bond interactions (Table 1).

Related literature top

For related structures and the biological applications of thiosemicarbazones, see: Hu et al. (2006).

Experimental top

N-(p-Tolyl)thiosemicarbazide (1.8 g, 10 mmol) and cyclohexanone (0.98 g, 10 mmol) was dissolved in 95% ethanol (15 ml) and the solution was refluxed for 0.5 h. Fine colorless crystals appeared on cooling. They were filtered and washed by 95% ethanol to give 1.6 g of the title compound in 61.5% yield. Single crystals suitable for X-ray measurements were obtained from methanol by slow evaporation at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at 30% probability level.

3-[(Cyclohexylidene)amino]-1-(4-methylphenyl)thiourea top

Crystal data top

C₁₄H₁₉N₃S	F(000) = 2240
M_r = 261.38	D_x = 1.202 Mg m⁻³
Orthorhombic, Ibca	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -I 2b 2c	Cell parameters from 2807 reflections
a = 14.9151 (4) Å	θ = 3.2–70.3°
b = 22.5593 (5) Å	µ = 1.87 mm⁻¹
c = 17.1642 (3) Å	T = 291 K
V = 5775.3 (2) Å³	Prismatic, colorless
Z = 16	0.40 × 0.25 × 0.25 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2583 independent reflections
Radiation source: fine-focus sealed tube	2024 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 67.1°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	h = −7→17
T_min = 0.521, T_max = 0.652	k = −26→26
7202 measured reflections	l = −19→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.1042P)² + 0.7804P] where P = (F_o² + 2F_c²)/3
2583 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₄H₁₉N₃S	V = 5775.3 (2) Å³
M_r = 261.38	Z = 16
Orthorhombic, Ibca	Cu Kα radiation
a = 14.9151 (4) Å	µ = 1.87 mm⁻¹
b = 22.5593 (5) Å	T = 291 K
c = 17.1642 (3) Å	0.40 × 0.25 × 0.25 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2583 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	2024 reflections with I > 2σ(I)
T_min = 0.521, T_max = 0.652	R_int = 0.032
7202 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.37 e Å⁻³
2583 reflections	Δρ_min = −0.25 e Å⁻³
172 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
S1	0.88952 (5)	0.07068 (3)	0.17935 (3)	0.0599 (3)
N1	0.84361 (13)	0.02381 (8)	0.04022 (10)	0.0481 (5)
N2	0.78485 (14)	−0.01953 (8)	0.14881 (10)	0.0498 (5)
N3	0.74084 (15)	−0.05790 (8)	0.09883 (10)	0.0514 (5)
C1	0.89252 (14)	0.06343 (9)	−0.00784 (12)	0.0450 (5)
C2	0.89188 (19)	0.12432 (11)	0.00239 (14)	0.0557 (6)
H2A	0.8572	0.1413	0.0414	0.067*
C3	0.94341 (19)	0.15961 (10)	−0.04609 (14)	0.0597 (6)
H3	0.9435	0.2004	−0.0385	0.072*
C4	0.99514 (19)	0.13567 (10)	−0.10592 (13)	0.0544 (6)
C5	0.99072 (18)	0.07526 (10)	−0.11773 (13)	0.0520 (5)
H5	1.0221	0.0585	−0.1590	0.062*
C6	0.94050 (17)	0.03922 (10)	−0.06944 (12)	0.0505 (5)
H6	0.9388	−0.0014	−0.0782	0.061*
C7	1.0565 (2)	0.17332 (13)	−0.15541 (18)	0.0741 (8)
H7A	1.0221	0.1928	−0.1951	0.111*
H7B	1.1011	0.1486	−0.1793	0.111*
H7C	1.0853	0.2025	−0.1233	0.111*
C8	0.83781 (15)	0.02349 (9)	0.11831 (12)	0.0460 (5)
C9	0.68926 (18)	−0.09724 (10)	0.12732 (14)	0.0538 (6)
C10	0.6399 (2)	−0.13589 (14)	0.07092 (18)	0.0749 (8)
H10A	0.6617	−0.1284	0.0186	0.090*
H10B	0.5765	−0.1262	0.0723	0.090*
C11	0.6526 (3)	−0.20137 (15)	0.0908 (2)	0.0911 (11)
H11A	0.6166	−0.2254	0.0559	0.109*
H11B	0.7149	−0.2122	0.0835	0.109*
C12	0.6250 (3)	−0.21354 (16)	0.1747 (2)	0.0961 (11)
H12A	0.5615	−0.2058	0.1808	0.115*
H12B	0.6358	−0.2549	0.1869	0.115*
C13	0.6773 (2)	−0.17499 (16)	0.2301 (2)	0.0873 (10)
H13A	0.7401	−0.1861	0.2279	0.105*
H13B	0.6563	−0.1820	0.2827	0.105*
C14	0.6686 (2)	−0.10938 (14)	0.21164 (16)	0.0694 (7)
H14A	0.6081	−0.0963	0.2232	0.083*
H14B	0.7096	−0.0870	0.2443	0.083*
H1	0.8188 (16)	−0.0081 (12)	0.0192 (16)	0.052 (7)*
H2	0.799 (2)	−0.0305 (14)	0.195 (2)	0.075 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0824 (5)	0.0632 (4)	0.0341 (3)	−0.0172 (3)	−0.0022 (3)	−0.0052 (2)
N1	0.0605 (11)	0.0528 (9)	0.0309 (8)	−0.0072 (9)	−0.0017 (8)	−0.0002 (7)
N2	0.0634 (11)	0.0556 (10)	0.0305 (8)	−0.0083 (9)	0.0003 (9)	0.0003 (7)
N3	0.0674 (12)	0.0519 (9)	0.0349 (9)	−0.0070 (9)	−0.0031 (9)	−0.0016 (7)
C1	0.0521 (12)	0.0514 (11)	0.0316 (10)	−0.0003 (9)	−0.0032 (9)	0.0030 (8)
C2	0.0735 (15)	0.0532 (11)	0.0403 (11)	0.0110 (11)	0.0104 (11)	0.0009 (9)
C3	0.0864 (17)	0.0448 (11)	0.0478 (12)	0.0051 (11)	0.0066 (13)	0.0030 (9)
C4	0.0675 (14)	0.0561 (12)	0.0395 (11)	0.0009 (11)	0.0037 (11)	0.0078 (9)
C5	0.0638 (13)	0.0580 (12)	0.0344 (10)	0.0066 (11)	0.0062 (10)	0.0002 (9)
C6	0.0673 (14)	0.0482 (10)	0.0358 (10)	0.0004 (10)	−0.0008 (10)	−0.0013 (8)
C7	0.094 (2)	0.0640 (14)	0.0641 (16)	−0.0064 (15)	0.0204 (16)	0.0083 (13)
C8	0.0529 (12)	0.0526 (11)	0.0323 (10)	0.0015 (9)	0.0001 (9)	−0.0013 (8)
C9	0.0626 (14)	0.0548 (11)	0.0441 (12)	−0.0055 (11)	−0.0049 (11)	0.0044 (9)
C10	0.092 (2)	0.0761 (16)	0.0568 (15)	−0.0252 (16)	−0.0137 (15)	0.0025 (13)
C11	0.114 (3)	0.0713 (17)	0.088 (2)	−0.0287 (19)	0.002 (2)	−0.0052 (16)
C12	0.109 (3)	0.0764 (19)	0.103 (3)	−0.0260 (19)	0.007 (2)	0.0240 (19)
C13	0.088 (2)	0.102 (2)	0.0714 (19)	−0.0172 (19)	0.0029 (17)	0.0367 (18)
C14	0.0722 (16)	0.0869 (18)	0.0490 (14)	−0.0193 (15)	0.0081 (13)	0.0049 (13)

Geometric parameters (Å, º) top

S1—C8	1.681 (2)	C7—H7A	0.9600
N1—C8	1.343 (3)	C7—H7B	0.9600
N1—C1	1.418 (3)	C7—H7C	0.9600
N1—H1	0.89 (3)	C9—C10	1.497 (4)
N2—C8	1.356 (3)	C9—C14	1.505 (3)
N2—N3	1.384 (3)	C10—C11	1.528 (5)
N2—H2	0.86 (3)	C10—H10A	0.9700
N3—C9	1.272 (3)	C10—H10B	0.9700
C1—C2	1.385 (3)	C11—C12	1.523 (5)
C1—C6	1.389 (3)	C11—H11A	0.9700
C2—C3	1.385 (4)	C11—H11B	0.9700
C2—H2A	0.9300	C12—C13	1.506 (5)
C3—C4	1.393 (4)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.379 (3)	C13—C14	1.519 (5)
C4—C7	1.510 (4)	C13—H13A	0.9700
C5—C6	1.382 (3)	C13—H13B	0.9700
C5—H5	0.9300	C14—H14A	0.9700
C6—H6	0.9300	C14—H14B	0.9700

C8—N1—C1	128.10 (19)	N3—C9—C10	117.1 (2)
C8—N1—H1	112.0 (17)	N3—C9—C14	128.3 (2)
C1—N1—H1	119.4 (17)	C10—C9—C14	114.6 (2)
C8—N2—N3	118.98 (17)	C9—C10—C11	111.0 (3)
C8—N2—H2	115 (2)	C9—C10—H10A	109.4
N3—N2—H2	121 (2)	C11—C10—H10A	109.4
C9—N3—N2	119.01 (19)	C9—C10—H10B	109.4
C2—C1—C6	119.4 (2)	C11—C10—H10B	109.4
C2—C1—N1	123.2 (2)	H10A—C10—H10B	108.0
C6—C1—N1	117.39 (19)	C12—C11—C10	110.6 (3)
C3—C2—C1	119.4 (2)	C12—C11—H11A	109.5
C3—C2—H2A	120.3	C10—C11—H11A	109.5
C1—C2—H2A	120.3	C12—C11—H11B	109.5
C2—C3—C4	121.8 (2)	C10—C11—H11B	109.5
C2—C3—H3	119.1	H11A—C11—H11B	108.1
C4—C3—H3	119.1	C13—C12—C11	110.7 (3)
C5—C4—C3	117.7 (2)	C13—C12—H12A	109.5
C5—C4—C7	120.1 (2)	C11—C12—H12A	109.5
C3—C4—C7	122.1 (2)	C13—C12—H12B	109.5
C4—C5—C6	121.3 (2)	C11—C12—H12B	109.5
C4—C5—H5	119.4	H12A—C12—H12B	108.1
C6—C5—H5	119.4	C12—C13—C14	112.8 (3)
C5—C6—C1	120.3 (2)	C12—C13—H13A	109.0
C5—C6—H6	119.8	C14—C13—H13A	109.0
C1—C6—H6	119.8	C12—C13—H13B	109.0
C4—C7—H7A	109.5	C14—C13—H13B	109.0
C4—C7—H7B	109.5	H13A—C13—H13B	107.8
H7A—C7—H7B	109.5	C9—C14—C13	111.1 (3)
C4—C7—H7C	109.5	C9—C14—H14A	109.4
H7A—C7—H7C	109.5	C13—C14—H14A	109.4
H7B—C7—H7C	109.5	C9—C14—H14B	109.4
N1—C8—N2	115.25 (19)	C13—C14—H14B	109.4
N1—C8—S1	126.08 (17)	H14A—C14—H14B	108.0
N2—C8—S1	118.67 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.89 (3)	2.48 (3)	3.268 (3)	148 (2)
N2—H2···S1ⁱⁱ	0.86 (3)	2.70 (3)	3.531 (2)	164 (3)

Symmetry codes: (i) −x+3/2, y, −z; (ii) x, −y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₉N₃S
M_r	261.38
Crystal system, space group	Orthorhombic, Ibca
Temperature (K)	291
a, b, c (Å)	14.9151 (4), 22.5593 (5), 17.1642 (3)
V (Å³)	5775.3 (2)
Z	16
Radiation type	Cu Kα
µ (mm⁻¹)	1.87
Crystal size (mm)	0.40 × 0.25 × 0.25

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.521, 0.652
No. of measured, independent and observed [I > 2σ(I)] reflections	7202, 2583, 2024
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.162, 1.02
No. of reflections	2583
No. of parameters	172
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.25

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.89 (3)	2.48 (3)	3.268 (3)	148 (2)
N2—H2···S1ⁱⁱ	0.86 (3)	2.70 (3)	3.531 (2)	164 (3)

Symmetry codes: (i) −x+3/2, y, −z; (ii) x, −y, −z+1/2.

Acknowledgements

The authors thank the Natural Science Foundation of the Education Department of Henan Province, China (2010B150029), the Natural Science Foundation of Henan Province, China (112102310538, 082300420110) and the Scientific Research Foundation of Xuchang University, China (2009086) for supporting this work.

References

Hu, W.-X., Zhou, W., Xia, C.-N. & Wen, X. (2006). Bioorg. Med. Chem. Lett. 16, 2213–2218. Web of Science CrossRef PubMed CAS Google Scholar
Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar