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

Abstract

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 R ² ₂(8) loops.

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 ▶).

Experimental  

Crystal data  

• C₁₀H₁₉N₃S

• M _r = 213.34

• Orthorhombic,

• a = 13.6668 (10) Å

• b = 8.3356 (5) Å

• c = 21.4683 (16) Å

• V = 2445.7 (3) ų

• Z = 8

• Mo Kα radiation

• μ = 0.24 mm⁻¹

• T = 301 K

• 0.50 × 0.19 × 0.19 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 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

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 ▶).

Supplementary Material

CCDC reference: 1023476

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

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) .

supplementary crystallographic information

S5. Synthesis and crystallization

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).

S6. Refinement

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.

Figures

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

Crystal data

C10H19N3S	F(000) = 928
Mr = 213.34	Dx = 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

Bruker SMART APEX CCD area-detector diffractometer	3028 independent reflections
Radiation source: fine-focus sealed tube	2051 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
Detector resolution: 83.66 pixels mm-1	θmax = 28.3°, θmin = 2.9°
ω scan	h = −18→16
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −11→10
Tmin = 0.892, Tmax = 0.957	l = −28→27
31768 measured reflections

Refinement

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(Fo2) + (0.0583P)2 + 0.9515P] where P = (Fo2 + 2Fc2)/3
3028 reflections	(Δ/σ)max = 0.001
133 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.