Crystal structure of 4-cyclo­hexyl-1-(propan-2-yl­idene)thio­semicarbazide

Yamin, B.M.; Rodis, M.L.; Chee, D.N.B.A.

doi:10.1107/S160053681402025X

organic compounds

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Volume 70| Part 10| October 2014| Page o1109

doi:10.1107/S160053681402025X

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Crystal structure of 4-cyclohexyl-1-(propan-2-ylidene)thiosemicarbazide

Bohari M Yamin,^a Monica Lulo Rodis ^b and Dayang N. B. A Chee ^b ^*

^aSchool of Chemical Sciences and Food Technology, Faculty of Resource Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi Selangor, Malaysia, and ^bDepartment of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan Serawak, Malaysia
^*Correspondence e-mail: dnorafizan@frst.unimas.my

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 4 September 2014; accepted 9 September 2014; online 13 September 2014)

In the title compound, C₁₀H₁₉N₃S, the cyclohexyl group adopts a chair conformation and adopts a position approximately syn to the thione S atom. The CN₂S thiourea moiety makes dihedral angle of 13.13 (10)° with the propan-2-ylideneamino group. An intramolecular N—H⋯N hydrogen bond is noted. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R²₂(8) loops.

Keywords: crystal structure; thiosemicarbazide; thiourea; biological activity; hydrogen bonding.

CCDC reference: 1023476

1. Related literature

For the applications and biological activity of thiosemicarbazide derivatives, see: Brokl et al. (1974 ), Jiang et al. (2006 ). For the crystal structures of related compounds, see: Affan et al. (2011 ); Miroslaw et al. (2011 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₉N₃S
M_r = 213.34
Orthorhombic, P b c a
a = 13.6668 (10) Å
b = 8.3356 (5) Å
c = 21.4683 (16) Å
V = 2445.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 301 K
0.50 × 0.19 × 0.19 mm

2.2. Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.892, T_max = 0.957
31768 measured reflections
3028 independent reflections
2051 reflections with I > 2σ(I)
R_int = 0.061

2.3. Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.135
S = 1.04
3028 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯N3	0.86	2.18	2.592 (2)	109
N2—H2C⋯S1ⁱ	0.86	2.80	3.6170 (18)	158
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1023476

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681402025X/tk5341sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681402025X/tk5341Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681402025X/tk5341Isup3.cml

checkCIF report

Synthesis and crystallization top

A mixture of 4-cyclohexylthiosemicarbazide (0.174 g, 1 mmol), KOH (0.112 g, 0.05 mmol) and diphenyltin(IV) chloride (0.344 g, 1 mmol) in methanol was heated under reflux for 4–5 h. The reaction mixture was allowed to cool to room temperature for 1 h. The white precipitate formed was filtered and washed with acetone. Crystals suitable for X-ray study were obtained by recrystallization from acetone (0.240 g, 42% yield). M.pt = 390–393 K. IR (KBr): v_{NH-cyclohexyl} (3336), v_S=C—NH (3221), v_cyclohexyl (2929,2850), v_C=N (1527), v_C=S (1263,881), v_N—N (1106) cm^-1. All the chemicals were purchased from Sigma Aldrich (Germany).

Refinement top

Non-methine C-bound H atoms were positioned geometrically with C—H = 0.96–0.97 Å, and with U_iso(H)= 1.2–1.5U_eq(C). The N-bound H atoms were positioned geometrically with N—H = 0.86 Å, and with U_iso(H)= 1.2U_eq(N). The methine-bound H atom was located from a Fourier map and refined isotropically. A rotating model was applied in the refinement of the methyl hydrogen atoms.

Related literature top

For the applications and biological activity of thiosemicarbazide, see: Brokl et al. (1974), Jiang et al. (2006). For the crystal structures of related compounds, see: Affan et al. (2011); Miroslaw et al. (2011).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. The crystal packing of (I) viewed down the c axis. The dashed lines indicate intermolecular hydrogen bonds

4-Cyclohexyl-1-(propan-2-ylidene)thiosemicarbazide top

Crystal data top

C₁₀H₁₉N₃S	F(000) = 928
M_r = 213.34	D_x = 1.159 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7621 reflections
a = 13.6668 (10) Å	θ = 2.9–28.3°
b = 8.3356 (5) Å	µ = 0.24 mm⁻¹
c = 21.4683 (16) Å	T = 301 K
V = 2445.7 (3) Å³	Block, yellow
Z = 8	0.50 × 0.19 × 0.19 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3028 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 83.66 pixels mm^-1	θ_max = 28.3°, θ_min = 2.9°
ω scan	h = −18→16
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −11→10
T_min = 0.892, T_max = 0.957	l = −28→27
31768 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0583P)² + 0.9515P] where P = (F_o² + 2F_c²)/3
3028 reflections	(Δ/σ)_max = 0.001
133 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₁₉N₃S	V = 2445.7 (3) Å³
M_r = 213.34	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.6668 (10) Å	µ = 0.24 mm⁻¹
b = 8.3356 (5) Å	T = 301 K
c = 21.4683 (16) Å	0.50 × 0.19 × 0.19 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3028 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2051 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.957	R_int = 0.061
31768 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.25 e Å⁻³
3028 reflections	Δρ_min = −0.30 e Å⁻³
133 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	0.59037 (4)	0.01795 (7)	0.41721 (3)	0.0582 (2)
N1	0.51795 (12)	0.26158 (19)	0.35150 (7)	0.0477 (4)
H1D	0.4748	0.3363	0.3483	0.057*
N2	0.46292 (11)	0.23807 (19)	0.45107 (7)	0.0447 (4)
H2C	0.4630	0.1942	0.4873	0.054*
N3	0.40374 (11)	0.36924 (19)	0.43836 (7)	0.0462 (4)
C1	0.67225 (14)	0.3396 (2)	0.30141 (9)	0.0489 (5)
H1A	0.7093	0.3119	0.3384	0.059*
H1B	0.6530	0.4513	0.3048	0.059*
C2	0.73660 (16)	0.3179 (3)	0.24406 (11)	0.0580 (6)
H2A	0.7914	0.3916	0.2463	0.070*
H2B	0.7625	0.2096	0.2436	0.070*
C3	0.68044 (18)	0.3477 (3)	0.18483 (10)	0.0623 (6)
H3A	0.7223	0.3261	0.1493	0.075*
H3B	0.6609	0.4595	0.1830	0.075*
C4	0.59057 (17)	0.2423 (3)	0.18135 (10)	0.0589 (6)
H4A	0.6104	0.1308	0.1786	0.071*
H4B	0.5538	0.2682	0.1440	0.071*
C5	0.52547 (14)	0.2654 (3)	0.23839 (9)	0.0488 (5)
H5A	0.5001	0.3741	0.2387	0.059*
H5B	0.4704	0.1923	0.2361	0.059*
C6	0.58140 (13)	0.2352 (2)	0.29786 (8)	0.0393 (4)
H1C	0.6010 (13)	0.123 (2)	0.2991 (8)	0.041 (5)*
C7	0.52063 (13)	0.1809 (2)	0.40478 (8)	0.0387 (4)
C8	0.36147 (14)	0.4386 (2)	0.48408 (9)	0.0426 (4)
C9	0.29760 (19)	0.5788 (3)	0.46846 (11)	0.0714 (7)
H9A	0.2964	0.5937	0.4241	0.107*
H9B	0.3231	0.6736	0.4880	0.107*
H9C	0.2324	0.5591	0.4832	0.107*
C10	0.36946 (17)	0.3939 (3)	0.55073 (9)	0.0549 (5)
H10A	0.4361	0.3671	0.5602	0.082*
H10B	0.3283	0.3030	0.5590	0.082*
H10C	0.3491	0.4825	0.5761	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0625 (4)	0.0585 (3)	0.0536 (3)	0.0258 (3)	0.0105 (3)	0.0124 (2)
N1	0.0531 (9)	0.0453 (9)	0.0446 (9)	0.0189 (7)	0.0155 (8)	0.0074 (7)
N2	0.0499 (9)	0.0451 (9)	0.0391 (9)	0.0104 (7)	0.0105 (7)	0.0057 (7)
N3	0.0469 (9)	0.0448 (9)	0.0468 (9)	0.0105 (7)	0.0142 (7)	0.0068 (7)
C1	0.0468 (11)	0.0532 (11)	0.0467 (11)	0.0001 (9)	−0.0012 (9)	−0.0088 (9)
C2	0.0457 (11)	0.0557 (12)	0.0725 (15)	−0.0087 (10)	0.0167 (11)	−0.0103 (11)
C3	0.0777 (15)	0.0583 (13)	0.0509 (13)	−0.0037 (11)	0.0270 (12)	−0.0024 (10)
C4	0.0682 (14)	0.0682 (14)	0.0403 (11)	0.0013 (11)	−0.0001 (10)	−0.0082 (10)
C5	0.0443 (11)	0.0535 (11)	0.0486 (12)	0.0024 (9)	0.0008 (9)	−0.0040 (9)
C6	0.0428 (10)	0.0348 (9)	0.0403 (10)	0.0084 (8)	0.0083 (8)	−0.0016 (7)
C7	0.0358 (9)	0.0391 (9)	0.0410 (10)	0.0015 (7)	0.0050 (8)	−0.0017 (8)
C8	0.0429 (10)	0.0390 (9)	0.0460 (11)	0.0000 (8)	0.0128 (8)	0.0011 (8)
C9	0.0828 (16)	0.0633 (14)	0.0682 (15)	0.0310 (13)	0.0326 (13)	0.0157 (12)
C10	0.0661 (13)	0.0528 (11)	0.0458 (12)	0.0046 (11)	0.0055 (10)	−0.0092 (9)

Geometric parameters (Å, º) top

S1—C7	1.6803 (18)	C3—H3B	0.9700
N1—C7	1.328 (2)	C4—C5	1.526 (3)
N1—C6	1.458 (2)	C4—H4A	0.9700
N1—H1D	0.8600	C4—H4B	0.9700
N2—C7	1.355 (2)	C5—C6	1.509 (3)
N2—N3	1.387 (2)	C5—H5A	0.9700
N2—H2C	0.8600	C5—H5B	0.9700
N3—C8	1.277 (2)	C6—H1C	0.973 (19)
C1—C6	1.518 (3)	C8—C10	1.483 (3)
C1—C2	1.524 (3)	C8—C9	1.497 (3)
C1—H1A	0.9700	C9—H9A	0.9600
C1—H1B	0.9700	C9—H9B	0.9600
C2—C3	1.506 (3)	C9—H9C	0.9600
C2—H2A	0.9700	C10—H10A	0.9600
C2—H2B	0.9700	C10—H10B	0.9600
C3—C4	1.512 (3)	C10—H10C	0.9600
C3—H3A	0.9700

C7—N1—C6	125.98 (15)	C6—C5—C4	111.24 (16)
C7—N1—H1D	117.0	C6—C5—H5A	109.4
C6—N1—H1D	117.0	C4—C5—H5A	109.4
C7—N2—N3	118.20 (15)	C6—C5—H5B	109.4
C7—N2—H2C	120.9	C4—C5—H5B	109.4
N3—N2—H2C	120.9	H5A—C5—H5B	108.0
C8—N3—N2	118.00 (16)	N1—C6—C5	109.97 (14)
C6—C1—C2	111.30 (16)	N1—C6—C1	111.11 (15)
C6—C1—H1A	109.4	C5—C6—C1	111.16 (16)
C2—C1—H1A	109.4	N1—C6—H1C	106.7 (11)
C6—C1—H1B	109.4	C5—C6—H1C	108.9 (11)
C2—C1—H1B	109.4	C1—C6—H1C	108.9 (11)
H1A—C1—H1B	108.0	N1—C7—N2	115.93 (16)
C3—C2—C1	111.62 (18)	N1—C7—S1	124.19 (14)
C3—C2—H2A	109.3	N2—C7—S1	119.87 (14)
C1—C2—H2A	109.3	N3—C8—C10	126.46 (18)
C3—C2—H2B	109.3	N3—C8—C9	116.44 (18)
C1—C2—H2B	109.3	C10—C8—C9	117.10 (17)
H2A—C2—H2B	108.0	C8—C9—H9A	109.5
C2—C3—C4	111.10 (18)	C8—C9—H9B	109.5
C2—C3—H3A	109.4	H9A—C9—H9B	109.5
C4—C3—H3A	109.4	C8—C9—H9C	109.5
C2—C3—H3B	109.4	H9A—C9—H9C	109.5
C4—C3—H3B	109.4	H9B—C9—H9C	109.5
H3A—C3—H3B	108.0	C8—C10—H10A	109.5
C3—C4—C5	111.13 (17)	C8—C10—H10B	109.5
C3—C4—H4A	109.4	H10A—C10—H10B	109.5
C5—C4—H4A	109.4	C8—C10—H10C	109.5
C3—C4—H4B	109.4	H10A—C10—H10C	109.5
C5—C4—H4B	109.4	H10B—C10—H10C	109.5
H4A—C4—H4B	108.0

C7—N2—N3—C8	−169.08 (17)	C2—C1—C6—N1	−177.51 (16)
C6—C1—C2—C3	54.9 (2)	C2—C1—C6—C5	−54.7 (2)
C1—C2—C3—C4	−55.4 (2)	C6—N1—C7—N2	172.31 (17)
C2—C3—C4—C5	55.8 (2)	C6—N1—C7—S1	−7.2 (3)
C3—C4—C5—C6	−55.9 (2)	N3—N2—C7—N1	2.8 (2)
C7—N1—C6—C5	145.50 (19)	N3—N2—C7—S1	−177.70 (13)
C7—N1—C6—C1	−91.0 (2)	N2—N3—C8—C10	0.4 (3)
C4—C5—C6—N1	178.77 (16)	N2—N3—C8—C9	−179.53 (18)
C4—C5—C6—C1	55.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···N3	0.86	2.18	2.592 (2)	109
C6—H1C···S1	0.97 (3)	2.69 (2)	3.142 (2)	108.9 (12)
C10—H10A···N2	0.96	2.40	2.811 (3)	106
N2—H2C···S1ⁱ	0.86	2.80	3.6170 (18)	158

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···N3	0.86	2.18	2.592 (2)	109
N2—H2C···S1ⁱ	0.86	2.80	3.6170 (18)	158

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors thank the Ministry of Science, Technology and Innovation (MOSTI), for a research grant [RAGS/ST01(1)/1040/2013 (07)] and to The Centre of Instrumentation (CRIM), Universiti Kebangsaan Malaysia, for use of the X-ray crystallographic facility.

References

Affan, M. A., Salam, M. A., Ahmad, F. B., Ng, S. W. & Tiekink, E. R. T. (2011). Acta Cryst. E67, o1193. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brokl, M., Dour, S. J. & Kerst, A. (1974). US Patent US3830917A. Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Jiang, Z. G., Lebowitz, M. S. & Ghanbari, H. A. (2006). CNS Drug Rev. 12, 72–90. Web of Science CrossRef Google Scholar
Miroslaw, B., Szulczyk, D., Koziol, A. E. & Struga, M. (2011). Acta Cryst. E67, o3010. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 10| October 2014| Page o1109

doi:10.1107/S160053681402025X

Open

access