Crystal structure of 3-benzyl-1-[(cyclo-hexyl-idene)amino]-thio-urea.

The conformation of the title compound, C14H19N3S, is partially determined by an intra-molecular N-H⋯N hydro-gen-bond inter-action, although the N-H⋯N angle of 108° is quite small. The cyclo-hexyl-idene ring has a chair conformation and its mean plane is inclined to the benzene ring by 46.30 (8)°. In the crystal, mol-ecules are linked by pairs of N-H⋯S hydrogen bonds, forming inversion dimers, with an R 2 (2)(8) ring motif. The dimers are reinforced by pairs of C-H⋯S hydrogen bonds, and are linked by further weak C-H⋯S hydrogen bonds, forming chains propagating along [100].

Related literature

For pharmacuetical properties of both thio­semicarbazones and their metal complexes, see: Kalinowski & Richardson (2005 ▸, 2007 ▸); Smee & Sidwell (2003 ▸); Pandeya et al. (1999 ▸); Beraldo & Gambino (2004 ▸); Chohan et al. (2004 ▸). For the synthesis of the title compound, see: Mague et al. (2014 ▸).

Experimental

Crystal data

C14H19N3S

M = 261.38

Triclinic,

a = 6.5537 (3) Å

b = 10.5247 (5) Å

c = 11.3403 (5) Å

α = 113.682 (1)°

β = 92.969 (2)°

γ = 106.610 (2)°

V = 673.96 (5) Å3

Z = 2

Cu Kα radiation

μ = 2.01 mm−1

T = 150 K

0.31 × 0.20 × 0.16 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.66, T max = 0.73

5045 measured reflections

2509 independent reflections

2403 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.086

S = 1.09

2509 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901502112X/su5234sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901502112X/su5234Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901502112X/su5234Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901502112X/su5234fig1.tif

The mol­ecular structure of the title compound, showing the atom-labeling scheme and 50% probability displacement ellipsoids.

Click here for additional data file.

a . DOI: 10.1107/S205698901502112X/su5234fig2.tif

The crystal packing of the title compound, viewed along the a axis. The N—H⋯S and C—H⋯S hydrogen bonds appear as dotted lines (see Table 1).

CCDC reference: 1435497

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

C14H19N3S	Z = 2
Mr = 261.38	F(000) = 280
Triclinic, P1	Dx = 1.288 Mg m−3
a = 6.5537 (3) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.5247 (5) Å	Cell parameters from 4705 reflections
c = 11.3403 (5) Å	θ = 4.3–72.1°
α = 113.682 (1)°	µ = 2.01 mm−1
β = 92.969 (2)°	T = 150 K
γ = 106.610 (2)°	Block, colourless
V = 673.96 (5) Å3	0.31 × 0.20 × 0.16 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2509 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2403 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.019
Detector resolution: 10.4167 pixels mm-1	θmax = 72.1°, θmin = 4.3°
ω scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −12→12
Tmin = 0.66, Tmax = 0.73	l = −13→13
5045 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)] = 0.034	Hydrogen site location: mixed
wR(F2) = 0.086	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0345P)2 + 0.3099P] where P = (Fo2 + 2Fc2)/3
2509 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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 - 1.5 times those of the attached atoms.

	x	y	z	Uiso*/Ueq
S1	0.84373 (6)	0.04432 (4)	0.36001 (3)	0.02549 (12)
N1	0.58096 (18)	0.18119 (13)	0.48809 (11)	0.0220 (3)
H1A	0.5393	0.2255	0.5652	0.026*
N2	0.83691 (18)	0.15744 (12)	0.61404 (11)	0.0206 (2)
H2A	0.9318	0.1107	0.6194	0.025*
N3	0.73740 (19)	0.21975 (13)	0.71731 (11)	0.0226 (3)
C1	0.5199 (2)	0.30572 (15)	0.35057 (12)	0.0199 (3)
C2	0.7361 (2)	0.39067 (16)	0.37044 (13)	0.0242 (3)
H2	0.8478	0.3640	0.4008	0.029*
C3	0.7893 (3)	0.51413 (17)	0.34603 (15)	0.0288 (3)
H3	0.9371	0.5720	0.3603	0.035*
C4	0.6271 (3)	0.55336 (17)	0.30082 (15)	0.0299 (3)
H4	0.6637	0.6373	0.2833	0.036*
C5	0.4118 (3)	0.46964 (17)	0.28133 (15)	0.0292 (3)
H5	0.3004	0.4962	0.2504	0.035*
C6	0.3582 (2)	0.34677 (16)	0.30689 (14)	0.0244 (3)
H6	0.2101	0.2904	0.2944	0.029*
C7	0.4581 (2)	0.16627 (15)	0.36986 (13)	0.0227 (3)
H7A	0.3018	0.1364	0.3735	0.027*
H7B	0.4804	0.0867	0.2930	0.027*
C8	0.7447 (2)	0.13093 (14)	0.49275 (13)	0.0192 (3)
C9	0.8216 (2)	0.25262 (15)	0.83473 (13)	0.0228 (3)
C10	1.0256 (2)	0.23519 (16)	0.88270 (13)	0.0238 (3)
H10A	1.1294	0.3329	0.9438	0.029*
H10B	1.0940	0.1919	0.8075	0.029*
C11	0.9736 (2)	0.13508 (17)	0.95292 (14)	0.0265 (3)
H11A	0.8894	0.0332	0.8882	0.032*
H11B	1.1105	0.1339	0.9930	0.032*
C12	0.8435 (2)	0.18855 (17)	1.05953 (14)	0.0281 (3)
H12A	0.8036	0.1182	1.0987	0.034*
H12B	0.9349	0.2853	1.1297	0.034*
C13	0.6383 (2)	0.20312 (18)	1.00518 (14)	0.0284 (3)
H13A	0.5616	0.2417	1.0773	0.034*
H13B	0.5406	0.1050	0.9405	0.034*
C14	0.6939 (3)	0.30723 (18)	0.93927 (15)	0.0297 (3)
H14A	0.5589	0.3111	0.8997	0.036*
H14B	0.7803	0.4079	1.0054	0.036*

	U11	U22	U33	U12	U13	U23
S1	0.0279 (2)	0.0337 (2)	0.02208 (19)	0.01730 (16)	0.00831 (13)	0.01400 (15)
N1	0.0244 (6)	0.0269 (6)	0.0220 (6)	0.0131 (5)	0.0072 (4)	0.0143 (5)
N2	0.0229 (6)	0.0239 (6)	0.0212 (6)	0.0113 (5)	0.0064 (4)	0.0131 (5)
N3	0.0276 (6)	0.0239 (6)	0.0229 (6)	0.0123 (5)	0.0088 (5)	0.0135 (5)
C1	0.0234 (7)	0.0219 (7)	0.0152 (6)	0.0089 (6)	0.0042 (5)	0.0079 (5)
C2	0.0228 (7)	0.0274 (7)	0.0234 (7)	0.0084 (6)	0.0031 (5)	0.0123 (6)
C3	0.0291 (7)	0.0267 (8)	0.0282 (7)	0.0043 (6)	0.0071 (6)	0.0129 (6)
C4	0.0425 (9)	0.0251 (7)	0.0286 (7)	0.0132 (7)	0.0121 (6)	0.0161 (6)
C5	0.0355 (8)	0.0308 (8)	0.0304 (8)	0.0182 (7)	0.0075 (6)	0.0172 (6)
C6	0.0241 (7)	0.0275 (7)	0.0249 (7)	0.0113 (6)	0.0054 (5)	0.0126 (6)
C7	0.0197 (6)	0.0241 (7)	0.0253 (7)	0.0067 (6)	0.0006 (5)	0.0125 (6)
C8	0.0188 (6)	0.0177 (6)	0.0231 (6)	0.0044 (5)	0.0045 (5)	0.0119 (5)
C9	0.0291 (7)	0.0214 (7)	0.0234 (7)	0.0108 (6)	0.0070 (5)	0.0130 (6)
C10	0.0250 (7)	0.0258 (7)	0.0209 (6)	0.0085 (6)	0.0043 (5)	0.0103 (6)
C11	0.0314 (7)	0.0296 (8)	0.0241 (7)	0.0150 (6)	0.0047 (6)	0.0139 (6)
C12	0.0339 (8)	0.0333 (8)	0.0225 (7)	0.0131 (7)	0.0067 (6)	0.0159 (6)
C13	0.0282 (7)	0.0366 (8)	0.0216 (7)	0.0122 (6)	0.0086 (6)	0.0126 (6)
C14	0.0369 (8)	0.0361 (8)	0.0250 (7)	0.0227 (7)	0.0099 (6)	0.0144 (6)

S1—C8	1.6898 (13)	C6—H6	0.9500
N1—C8	1.3323 (17)	C7—H7A	0.9900
N1—C7	1.4551 (17)	C7—H7B	0.9900
N1—H1A	0.9098	C9—C10	1.5041 (19)
N2—C8	1.3580 (17)	C9—C14	1.5053 (19)
N2—N3	1.3905 (16)	C10—C11	1.5353 (19)
N2—H2A	0.9098	C10—H10A	0.9900
N3—C9	1.2814 (18)	C10—H10B	0.9900
C1—C6	1.3911 (19)	C11—C12	1.530 (2)
C1—C2	1.392 (2)	C11—H11A	0.9900
C1—C7	1.5144 (18)	C11—H11B	0.9900
C2—C3	1.388 (2)	C12—C13	1.523 (2)
C2—H2	0.9500	C12—H12A	0.9900
C3—C4	1.389 (2)	C12—H12B	0.9900
C3—H3	0.9500	C13—C14	1.533 (2)
C4—C5	1.384 (2)	C13—H13A	0.9900
C4—H4	0.9500	C13—H13B	0.9900
C5—C6	1.390 (2)	C14—H14A	0.9900
C5—H5	0.9500	C14—H14B	0.9900
C8—N1—C7	125.66 (12)	N3—C9—C10	128.89 (13)
C8—N1—H1A	117.0	N3—C9—C14	116.47 (12)
C7—N1—H1A	117.3	C10—C9—C14	114.51 (12)
C8—N2—N3	116.90 (11)	C9—C10—C11	110.25 (12)
C8—N2—H2A	117.8	C9—C10—H10A	109.6
N3—N2—H2A	122.8	C11—C10—H10A	109.6
C9—N3—N2	119.80 (12)	C9—C10—H10B	109.6
C6—C1—C2	119.17 (13)	C11—C10—H10B	109.6
C6—C1—C7	119.45 (12)	H10A—C10—H10B	108.1
C2—C1—C7	121.32 (12)	C12—C11—C10	111.12 (12)
C3—C2—C1	120.32 (13)	C12—C11—H11A	109.4
C3—C2—H2	119.8	C10—C11—H11A	109.4
C1—C2—H2	119.8	C12—C11—H11B	109.4
C2—C3—C4	120.19 (14)	C10—C11—H11B	109.4
C2—C3—H3	119.9	H11A—C11—H11B	108.0
C4—C3—H3	119.9	C13—C12—C11	111.75 (12)
C5—C4—C3	119.75 (13)	C13—C12—H12A	109.3
C5—C4—H4	120.1	C11—C12—H12A	109.3
C3—C4—H4	120.1	C13—C12—H12B	109.3
C4—C5—C6	120.13 (14)	C11—C12—H12B	109.3
C4—C5—H5	119.9	H12A—C12—H12B	107.9
C6—C5—H5	119.9	C12—C13—C14	110.59 (12)
C5—C6—C1	120.42 (14)	C12—C13—H13A	109.5
C5—C6—H6	119.8	C14—C13—H13A	109.5
C1—C6—H6	119.8	C12—C13—H13B	109.5
N1—C7—C1	113.77 (11)	C14—C13—H13B	109.5
N1—C7—H7A	108.8	H13A—C13—H13B	108.1
C1—C7—H7A	108.8	C9—C14—C13	109.31 (12)
N1—C7—H7B	108.8	C9—C14—H14A	109.8
C1—C7—H7B	108.8	C13—C14—H14A	109.8
H7A—C7—H7B	107.7	C9—C14—H14B	109.8
N1—C8—N2	115.81 (12)	C13—C14—H14B	109.8
N1—C8—S1	123.98 (10)	H14A—C14—H14B	108.3
N2—C8—S1	120.18 (10)
C8—N2—N3—C9	−177.30 (12)	C7—N1—C8—S1	1.96 (19)
C6—C1—C2—C3	−0.4 (2)	N3—N2—C8—N1	6.42 (17)
C7—C1—C2—C3	176.86 (13)	N3—N2—C8—S1	−175.61 (9)
C1—C2—C3—C4	−0.4 (2)	N2—N3—C9—C10	0.8 (2)
C2—C3—C4—C5	0.6 (2)	N2—N3—C9—C14	−174.84 (12)
C3—C4—C5—C6	0.0 (2)	N3—C9—C10—C11	−120.72 (16)
C4—C5—C6—C1	−0.8 (2)	C14—C9—C10—C11	54.96 (16)
C2—C1—C6—C5	1.0 (2)	C9—C10—C11—C12	−52.49 (16)
C7—C1—C6—C5	−176.31 (13)	C10—C11—C12—C13	55.00 (17)
C8—N1—C7—C1	−102.88 (15)	C11—C12—C13—C14	−56.90 (17)
C6—C1—C7—N1	−138.48 (13)	N3—C9—C14—C13	119.63 (14)
C2—C1—C7—N1	44.22 (17)	C10—C9—C14—C13	−56.62 (17)
C7—N1—C8—N2	179.85 (12)	C12—C13—C14—C9	56.04 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.91	2.14	2.5713 (17)	108
N2—H2A···S1i	0.91	2.55	3.4577 (12)	172
C10—H10B···S1i	0.99	2.61	3.4847 (14)	147
C7—H7A···S1ii	0.99	2.85	3.8413 (15)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N3	0.91	2.14	2.5713 (17)	108
N2—H2A⋯S1i	0.91	2.55	3.4577 (12)	172
C10—H10B⋯S1i	0.99	2.61	3.4847 (14)	147
C7—H7A⋯S1ii	0.99	2.85	3.8413 (15)	175

Symmetry codes: (i) ; (ii) .