2-[(E)-(2S,5R)-2-Isopropyl-5-methyl­cyclo­hexyl­idene]-N-methylhydrazine-1-carbo­thio­amide

Oliveira, A.B. de; Beck, J.; Daniels, J.; Farias, R.L. de

doi:10.1107/S2414314616004594

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160459

doi:10.1107/S2414314616004594

Open

access

2-[(E)-(2S,5R)-2-Isopropyl-5-methylcyclohexylidene]-N-methylhydrazine-1-carbothioamide

Adriano Bof de Oliveira,^a ^* Johannes Beck,^b Jörg Daniels ^b and Renan Lira de Farias ^c

^aDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, 49100-000 São Cristóvão-SE, Brazil, ^bInstitut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany, and ^cInstituto de Química, Universidade Estadual Paulista, Rua Francisco Degni s/n, 14801-970 Araraquara-SP, Brazil
^*Correspondence e-mail: adriano@daad-alumni.de

Edited by I. Brito, University of Antofagasta, Chile (Received 8 March 2016; accepted 16 March 2016; online 31 March 2016)

There are two molecules in the asymmetric unit of the title compound, C₁₂H₂₃N₃S, which are linked by two strong N—H⋯S hydrogen bonds, building a non-centrosymmetric dimer with graph-set motif R₂²(8). The molecules are further connected by N—H⋯S interactions into a two-dimensional hydrogen-bonded polymeric structure along the [001] direction. The absolute structure is based on the refinement of the Flack parameter.

Keywords: crystal structure; chiral thiosemicarbazone; hydrogen-bonded polymer; non-centrosymmetric dimer.

CCDC reference: 1469055

3D view (loading...)

Chemical scheme

Structure description

As part of our ongoing research on the synthesis and chemical structure of thiosemicarbazone derivatives from natural products, we report herein the crystal structure of a (−)-menthone-thiosemicarbazone compound.

In the crystal structure of the title compound, there are two discrete molecules in general positions in the asymmetric unit. As enantiopure (−)-menthone was used in the chemical reaction, both of the crystallographically independent molecules have the same chirality. The atoms C3, C6, C15 and C18 are chiral centres and maintain the chirality of the employed reagent and the obtained product emerges as enantiopure crystals in the non-centrosymmetric space group P2₁. The molecules are connected by mutual N—H⋯S interactions, building a non-centrosymmetric dimer with an $[R_{2}^{2}]$ (8) ring. The thiosemicarbazone entities are not planar and the torsion angles N1—N2—C11—N3 and N4—N5—C23—N6 are 2.4 (3) and 12.5 (3)°, respectively. For the N1—N2 and N4—N5 bonds, the E conformation is observed. The cyclohexane rings of the menthone units are in a chair conformation (Fig. 1). Both of these conformations are also observed for the (−)-menthone-3-thiosemicarbazone derivative (Oliveira et al., 2014 ).

Figure 1
The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines; see Table 1

for details.

In the crystal, the molecules are also connected by symmetry-generated N—H⋯S hydrogen bonds into a one-dimensional polymer along the b-axis (Fig. 2 and Table 1). In addition, other hydrogen bonds of the same type, with bridging sulfur atoms, connect the molecules into a two-dimensional polymeric chain along [001].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S2	0.88	2.79	3.671 (2)	174
N3—H3A⋯S1ⁱ	0.88	2.61	3.378 (2)	147
N5—H5⋯S1	0.88	2.61	3.356 (2)	143
N6—H6A⋯S2ⁱⁱ	0.88	2.79	3.445 (2)	132
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Partial view of the of the crystal structure of the title compound along the a axis, showing the non non-centrosymmetric dimer and the extended N—H⋯S interactions along the b axis. The complete two-dimensional hydrogen-bonded polymeric structure is not shown for clarity. Hydrogen bonds are shown as dashed lines; see Table 1

for details.

Synthesis and crystallization

The synthesis of the title compound was adapted from a previously reported procedure (Freund & Schander, 1902 ). In a hydrochloric acid-catalysed reaction, a mixture of (−)-menthone (10 mmol) and 4-methyl-3-thiosemicarbazide (10 mmol) in ethanol (80 mL) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Colourless plates were obtained by slow evaporation of a solution in the solvent DMSO.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The correct assignment of the absolute configuration was assured by the Flack parameter of 0.00 (7).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₂₃N₃S
M_r	241.39
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	123
a, b, c (Å)	11.5579 (5), 9.9279 (4), 12.5271 (5)
β (°)	95.030 (2)
V (Å³)	1431.90 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.21
Crystal size (mm)	0.77 × 0.30 × 0.08

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Analytical (Alcock, 1970 )
T_min, T_max	0.857, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	23116, 6380, 5069
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.104, 1.06
No. of reflections	6380
No. of parameters	297
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.37
Absolute structure	Flack x determined using 1954 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.00 (7)
Computer programs: COLLECT (Nonius, 1998 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Structural data

CCDC reference: 1469055

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616004594/bx4002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004594/bx4002Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616004594/bx4002Isup3.cml

checkCIF report

Experimental top

The synthesis of the title compound was adapted from a previously reported procedure (Freund & Schander, 1902). In a hydrochloric acid-catalysed reaction, a mixture of (-)-menthone (10 mmol) and 4-methyl-3-thiosemicarbazide (10 mmol) in ethanol (80 ml) was refluxed for 5 h. After cooling and filtering, the title compound was obtained. Colourless plates were obtained by slow evaporation of a solution in the solvent DMSO.

Structure description top

As part of our ongoing research on the synthesis and chemical structure of thiosemicarbazone derivatives from natural products, we report herein the crystal structure of a (-)-menthone-thiosemicarbazone compound.

In the crystal structure of the title compound, there are two discrete molecules in general positions in the asymmetric unit. As enantiopure (-)-menthone was used in the chemical reaction, both of the crystallographically independent molecules have the same chirality. The atoms C3, C6, C15 and C18 are chiral centres and maintain the chirality of the employed reagent and the obtained product emerges as enantiopure crystals in the non-centrosymmetric space group P2₁. The molecules are connected by mutual N—H···S interactions, building a non-centrosymmetric dimer with an R₂²(8) ring. The thiosemicarbazone entities are not planar and the torsion angles N1—N2—C11—N3 and N4—N5—C23—N6 are 2.4 (3) and 12.5 (3)°, respectively. For the N1—N2 and N4—N5 bonds, the E conformation is observed. The cyclohexane rings of the menthone units are in a chair conformation (Fig. 1). Both of these conformations are also observed for the (-)-menthone-3-thiosemicarbazone derivative (Oliveira et al., 2014).

In the crystal, the molecules are also connected by symmetry-generated N—H···S hydrogen bonds into a one-dimensional polymer along the b-axis (Fig. 2 and Table 1). In addition, other hydrogen bonds of the same type, with bridging sulfur atoms, connect the molecules into a two-dimensional polymeric structure along [001].

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Partial view of the of the crystal structure of the title compound along the a axis, showing the non non-centrosymmetric dimer and the extended N—H···S interactions along the b axis. The complete two-dimensional hydrogen-bonded polymeric structure is not shown for clarity. Hydrogen bonds are shown as dashed lines; see Table 1 for details.

2-[(E)-(2S,5R)-2-Isopropyl-5-methylcyclohexylidene]-N-methylhydrazine-1-carbothioamide top

Crystal data top

C₁₂H₂₃N₃S	F(000) = 528
M_r = 241.39	D_x = 1.120 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 80422 reflections
a = 11.5579 (5) Å	θ = 2.9–27.5°
b = 9.9279 (4) Å	µ = 0.21 mm⁻¹
c = 12.5271 (5) Å	T = 123 K
β = 95.030 (2)°	Plate, colourless
V = 1431.90 (10) Å³	0.77 × 0.30 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	6380 independent reflections
Radiation source: fine-focus sealed tube, Nonius KappaCCD	5069 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.075
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD scans	h = −15→14
Absorption correction: analytical (Alcock, 1970)	k = −12→12
T_min = 0.857, T_max = 0.984	l = −16→16
23116 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0456P)² + 0.1712P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6380 reflections	Δρ_max = 0.24 e Å⁻³
297 parameters	Δρ_min = −0.36 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1954 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

Crystal data top

C₁₂H₂₃N₃S	V = 1431.90 (10) Å³
M_r = 241.39	Z = 4
Monoclinic, P2₁	Mo Kα radiation
a = 11.5579 (5) Å	µ = 0.21 mm⁻¹
b = 9.9279 (4) Å	T = 123 K
c = 12.5271 (5) Å	0.77 × 0.30 × 0.08 mm
β = 95.030 (2)°

Data collection top

Nonius KappaCCD diffractometer	6380 independent reflections
Absorption correction: analytical (Alcock, 1970)	5069 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.984	R_int = 0.075
23116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	H-atom parameters constrained
wR(F²) = 0.104	Δρ_max = 0.24 e Å⁻³
S = 1.06	Δρ_min = −0.36 e Å⁻³
6380 reflections	Absolute structure: Flack x determined using 1954 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
297 parameters	Absolute structure parameter: 0.00 (7)
1 restraint

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
C1	0.73525 (19)	0.1924 (3)	0.71879 (19)	0.0293 (5)
C2	0.71388 (19)	0.0693 (3)	0.78399 (18)	0.0302 (5)
H2A	0.6428	0.0234	0.7526	0.036*
H2B	0.7005	0.0970	0.8578	0.036*
C3	0.81593 (19)	−0.0294 (3)	0.78822 (19)	0.0365 (5)
H3	0.8226	−0.0636	0.7139	0.044*
C4	0.9285 (2)	0.0439 (3)	0.8247 (2)	0.0420 (7)
H4A	0.9947	−0.0193	0.8238	0.050*
H4B	0.9251	0.0763	0.8991	0.050*
C5	0.9473 (2)	0.1634 (3)	0.7512 (2)	0.0424 (7)
H5A	0.9547	0.1297	0.6778	0.051*
H5B	1.0210	0.2087	0.7763	0.051*
C6	0.84778 (19)	0.2668 (3)	0.74798 (19)	0.0330 (5)
H6	0.8592	0.3319	0.6889	0.040*
C7	0.8407 (2)	0.3491 (3)	0.8524 (2)	0.0451 (7)
H7	0.8211	0.2855	0.9101	0.054*
C8	0.7447 (3)	0.4539 (3)	0.8378 (2)	0.0536 (8)
H8A	0.7419	0.5055	0.9042	0.080*
H8B	0.6700	0.4087	0.8205	0.080*
H8C	0.7602	0.5149	0.7793	0.080*
C9	0.9558 (3)	0.4164 (4)	0.8886 (3)	0.0687 (10)
H9A	0.9843	0.4656	0.8284	0.103*
H9B	1.0126	0.3476	0.9137	0.103*
H9C	0.9446	0.4793	0.9471	0.103*
C10	0.7951 (2)	−0.1501 (3)	0.8595 (2)	0.0463 (7)
H10A	0.8580	−0.2155	0.8555	0.069*
H10B	0.7208	−0.1925	0.8351	0.069*
H10C	0.7929	−0.1198	0.9338	0.069*
C11	0.58527 (19)	0.3497 (2)	0.49598 (19)	0.0272 (5)
C12	0.3993 (2)	0.2741 (3)	0.4070 (2)	0.0376 (6)
H12A	0.3523	0.3538	0.4193	0.056*
H12B	0.3512	0.1931	0.4095	0.056*
H12C	0.4296	0.2808	0.3366	0.056*
N1	0.65657 (16)	0.2190 (2)	0.64304 (16)	0.0293 (5)
N2	0.66934 (17)	0.3292 (2)	0.57647 (17)	0.0309 (5)
H2	0.7296	0.3834	0.5863	0.037*
N3	0.49569 (16)	0.2660 (2)	0.48970 (16)	0.0306 (5)
H3A	0.4944	0.2019	0.5382	0.037*
S1	0.59813 (5)	0.47563 (6)	0.40686 (5)	0.03005 (15)
C13	0.75271 (18)	0.7836 (3)	0.26402 (18)	0.0284 (5)
C14	0.7259 (2)	0.6502 (3)	0.20902 (19)	0.0322 (5)
H14A	0.7458	0.5760	0.2602	0.039*
H14B	0.7746	0.6403	0.1483	0.039*
C15	0.5962 (2)	0.6393 (3)	0.16702 (19)	0.0333 (5)
H15	0.5489	0.6421	0.2301	0.040*
C16	0.5633 (2)	0.7605 (3)	0.0968 (2)	0.0412 (6)
H16A	0.4794	0.7564	0.0729	0.049*
H16B	0.6070	0.7577	0.0323	0.049*
C17	0.5897 (2)	0.8927 (3)	0.1569 (2)	0.0425 (6)
H17A	0.5428	0.8975	0.2192	0.051*
H17B	0.5670	0.9693	0.1089	0.051*
C18	0.7195 (2)	0.9054 (3)	0.1962 (2)	0.0337 (5)
H18	0.7634	0.8985	0.1310	0.040*
C19	0.7520 (2)	1.0418 (3)	0.2477 (2)	0.0380 (6)
H19	0.8317	1.0329	0.2850	0.046*
C20	0.6707 (2)	1.0854 (3)	0.3315 (2)	0.0486 (7)
H20A	0.5934	1.1043	0.2961	0.073*
H20B	0.7015	1.1668	0.3681	0.073*
H20C	0.6651	1.0131	0.3841	0.073*
C21	0.7570 (3)	1.1512 (3)	0.1618 (3)	0.0549 (8)
H21A	0.6799	1.1620	0.1234	0.082*
H21B	0.8129	1.1249	0.1112	0.082*
H21C	0.7813	1.2366	0.1960	0.082*
C22	0.5731 (2)	0.5053 (3)	0.1103 (2)	0.0441 (7)
H22A	0.4907	0.4990	0.0848	0.066*
H22B	0.5936	0.4314	0.1602	0.066*
H22C	0.6203	0.4992	0.0491	0.066*
C23	0.89897 (19)	0.7001 (2)	0.51244 (18)	0.0264 (5)
C24	1.0523 (2)	0.8330 (3)	0.6096 (2)	0.0418 (6)
H24A	1.0229	0.8081	0.6779	0.063*
H24B	1.0749	0.9282	0.6116	0.063*
H24C	1.1200	0.7774	0.5976	0.063*
N4	0.80179 (16)	0.8028 (2)	0.35901 (16)	0.0290 (4)
N5	0.82468 (16)	0.6882 (2)	0.42301 (16)	0.0284 (4)
H5	0.7916	0.6106	0.4055	0.034*
N6	0.96169 (16)	0.8114 (2)	0.52266 (16)	0.0326 (5)
H6A	0.9481	0.8756	0.4747	0.039*
S2	0.90891 (5)	0.57300 (6)	0.60289 (5)	0.03129 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0226 (11)	0.0391 (14)	0.0259 (12)	−0.0002 (10)	0.0012 (9)	0.0003 (10)
C2	0.0238 (11)	0.0398 (14)	0.0267 (12)	−0.0056 (11)	−0.0003 (9)	0.0046 (11)
C3	0.0321 (12)	0.0480 (15)	0.0286 (12)	0.0019 (12)	−0.0014 (9)	0.0066 (12)
C4	0.0287 (12)	0.0542 (18)	0.0420 (15)	0.0028 (12)	−0.0027 (10)	0.0173 (13)
C5	0.0241 (12)	0.0587 (18)	0.0440 (15)	−0.0019 (12)	0.0000 (10)	0.0178 (13)
C6	0.0253 (11)	0.0475 (15)	0.0251 (12)	−0.0060 (11)	−0.0038 (9)	0.0073 (11)
C7	0.0456 (15)	0.0631 (19)	0.0257 (13)	−0.0186 (14)	−0.0022 (11)	0.0035 (12)
C8	0.0587 (18)	0.060 (2)	0.0449 (17)	−0.0211 (16)	0.0193 (14)	−0.0158 (14)
C9	0.064 (2)	0.094 (3)	0.0449 (19)	−0.034 (2)	−0.0157 (15)	−0.0006 (18)
C10	0.0439 (15)	0.0507 (17)	0.0425 (16)	−0.0014 (13)	−0.0061 (12)	0.0131 (13)
C11	0.0218 (11)	0.0333 (14)	0.0264 (13)	0.0006 (10)	0.0023 (9)	−0.0010 (10)
C12	0.0234 (11)	0.0545 (16)	0.0332 (13)	−0.0072 (12)	−0.0067 (10)	0.0055 (12)
N1	0.0257 (10)	0.0340 (11)	0.0276 (11)	−0.0025 (8)	−0.0012 (8)	0.0034 (9)
N2	0.0253 (10)	0.0367 (11)	0.0296 (11)	−0.0056 (9)	−0.0042 (8)	0.0044 (9)
N3	0.0228 (9)	0.0401 (12)	0.0280 (10)	−0.0045 (9)	−0.0028 (7)	0.0062 (9)
S1	0.0250 (3)	0.0327 (3)	0.0315 (3)	−0.0010 (3)	−0.0026 (2)	0.0036 (3)
C13	0.0190 (10)	0.0412 (14)	0.0249 (12)	0.0031 (10)	0.0016 (9)	0.0014 (11)
C14	0.0268 (12)	0.0423 (14)	0.0275 (12)	0.0002 (11)	0.0021 (9)	−0.0057 (11)
C15	0.0255 (12)	0.0468 (15)	0.0273 (13)	−0.0028 (11)	0.0002 (9)	−0.0012 (11)
C16	0.0312 (12)	0.0596 (18)	0.0309 (13)	−0.0061 (13)	−0.0078 (10)	0.0042 (13)
C17	0.0320 (13)	0.0521 (17)	0.0407 (15)	−0.0039 (12)	−0.0116 (11)	0.0084 (13)
C18	0.0292 (12)	0.0405 (14)	0.0310 (13)	0.0028 (11)	−0.0004 (10)	0.0033 (11)
C19	0.0314 (12)	0.0396 (16)	0.0416 (15)	0.0002 (11)	−0.0048 (11)	0.0042 (12)
C20	0.0408 (14)	0.0474 (16)	0.0566 (18)	0.0070 (13)	−0.0018 (13)	−0.0115 (14)
C21	0.0588 (18)	0.0495 (18)	0.0535 (19)	−0.0042 (15)	−0.0122 (14)	0.0127 (15)
C22	0.0342 (13)	0.0651 (19)	0.0330 (14)	−0.0115 (13)	0.0023 (11)	−0.0111 (13)
C23	0.0221 (11)	0.0331 (13)	0.0239 (12)	0.0025 (10)	0.0011 (9)	−0.0002 (10)
C24	0.0366 (14)	0.0486 (16)	0.0377 (15)	−0.0136 (12)	−0.0115 (11)	0.0039 (12)
N4	0.0238 (9)	0.0333 (11)	0.0295 (11)	0.0037 (8)	0.0005 (8)	0.0013 (9)
N5	0.0252 (10)	0.0320 (11)	0.0270 (10)	−0.0022 (8)	−0.0026 (8)	0.0016 (8)
N6	0.0321 (11)	0.0357 (12)	0.0283 (11)	−0.0025 (9)	−0.0065 (8)	0.0040 (9)
S2	0.0281 (3)	0.0348 (4)	0.0302 (3)	−0.0015 (3)	−0.0020 (2)	0.0035 (3)

Geometric parameters (Å, º) top

C1—N1	1.283 (3)	C13—N4	1.287 (3)
C1—C2	1.502 (3)	C13—C18	1.508 (4)
C1—C6	1.513 (3)	C13—C14	1.512 (4)
C2—C3	1.531 (4)	C14—C15	1.549 (3)
C2—H2A	0.9900	C14—H14A	0.9900
C2—H2B	0.9900	C14—H14B	0.9900
C3—C4	1.525 (4)	C15—C16	1.519 (4)
C3—C10	1.526 (4)	C15—C22	1.520 (4)
C3—H3	1.0000	C15—H15	1.0000
C4—C5	1.529 (4)	C16—C17	1.531 (4)
C4—H4A	0.9900	C16—H16A	0.9900
C4—H4B	0.9900	C16—H16B	0.9900
C5—C6	1.539 (4)	C17—C18	1.543 (3)
C5—H5A	0.9900	C17—H17A	0.9900
C5—H5B	0.9900	C17—H17B	0.9900
C6—C7	1.550 (4)	C18—C19	1.532 (4)
C6—H6	1.0000	C18—H18	1.0000
C7—C8	1.521 (4)	C19—C20	1.532 (4)
C7—C9	1.522 (4)	C19—C21	1.533 (4)
C7—H7	1.0000	C19—H19	1.0000
C8—H8A	0.9800	C20—H20A	0.9800
C8—H8B	0.9800	C20—H20B	0.9800
C8—H8C	0.9800	C20—H20C	0.9800
C9—H9A	0.9800	C21—H21A	0.9800
C9—H9B	0.9800	C21—H21B	0.9800
C9—H9C	0.9800	C21—H21C	0.9800
C10—H10A	0.9800	C22—H22A	0.9800
C10—H10B	0.9800	C22—H22B	0.9800
C10—H10C	0.9800	C22—H22C	0.9800
C11—N3	1.325 (3)	C23—N6	1.322 (3)
C11—N2	1.353 (3)	C23—N5	1.356 (3)
C11—S1	1.691 (2)	C23—S2	1.693 (2)
C12—N3	1.455 (3)	C24—N6	1.459 (3)
C12—H12A	0.9800	C24—H24A	0.9800
C12—H12B	0.9800	C24—H24B	0.9800
C12—H12C	0.9800	C24—H24C	0.9800
N1—N2	1.392 (3)	N4—N5	1.403 (3)
N2—H2	0.8800	N5—H5	0.8800
N3—H3A	0.8800	N6—H6A	0.8800

N1—C1—C2	115.5 (2)	N4—C13—C18	118.2 (2)
N1—C1—C6	128.1 (2)	N4—C13—C14	127.4 (2)
C2—C1—C6	116.4 (2)	C18—C13—C14	114.43 (19)
C1—C2—C3	112.13 (19)	C13—C14—C15	111.7 (2)
C1—C2—H2A	109.2	C13—C14—H14A	109.3
C3—C2—H2A	109.2	C15—C14—H14A	109.3
C1—C2—H2B	109.2	C13—C14—H14B	109.3
C3—C2—H2B	109.2	C15—C14—H14B	109.3
H2A—C2—H2B	107.9	H14A—C14—H14B	107.9
C4—C3—C10	111.9 (2)	C16—C15—C22	113.4 (2)
C4—C3—C2	109.8 (2)	C16—C15—C14	109.1 (2)
C10—C3—C2	111.2 (2)	C22—C15—C14	110.2 (2)
C4—C3—H3	107.9	C16—C15—H15	108.0
C10—C3—H3	107.9	C22—C15—H15	108.0
C2—C3—H3	107.9	C14—C15—H15	108.0
C3—C4—C5	110.6 (2)	C15—C16—C17	111.4 (2)
C3—C4—H4A	109.5	C15—C16—H16A	109.3
C5—C4—H4A	109.5	C17—C16—H16A	109.3
C3—C4—H4B	109.5	C15—C16—H16B	109.3
C5—C4—H4B	109.5	C17—C16—H16B	109.3
H4A—C4—H4B	108.1	H16A—C16—H16B	108.0
C4—C5—C6	112.8 (2)	C16—C17—C18	111.9 (2)
C4—C5—H5A	109.0	C16—C17—H17A	109.2
C6—C5—H5A	109.0	C18—C17—H17A	109.2
C4—C5—H5B	109.0	C16—C17—H17B	109.2
C6—C5—H5B	109.0	C18—C17—H17B	109.2
H5A—C5—H5B	107.8	H17A—C17—H17B	107.9
C1—C6—C5	107.8 (2)	C13—C18—C19	115.48 (19)
C1—C6—C7	110.70 (19)	C13—C18—C17	107.8 (2)
C5—C6—C7	115.1 (2)	C19—C18—C17	113.7 (2)
C1—C6—H6	107.7	C13—C18—H18	106.4
C5—C6—H6	107.7	C19—C18—H18	106.4
C7—C6—H6	107.7	C17—C18—H18	106.4
C8—C7—C9	110.2 (3)	C20—C19—C18	113.4 (2)
C8—C7—C6	110.5 (2)	C20—C19—C21	110.1 (2)
C9—C7—C6	111.9 (2)	C18—C19—C21	110.7 (2)
C8—C7—H7	108.0	C20—C19—H19	107.5
C9—C7—H7	108.0	C18—C19—H19	107.5
C6—C7—H7	108.0	C21—C19—H19	107.5
C7—C8—H8A	109.5	C19—C20—H20A	109.5
C7—C8—H8B	109.5	C19—C20—H20B	109.5
H8A—C8—H8B	109.5	H20A—C20—H20B	109.5
C7—C8—H8C	109.5	C19—C20—H20C	109.5
H8A—C8—H8C	109.5	H20A—C20—H20C	109.5
H8B—C8—H8C	109.5	H20B—C20—H20C	109.5
C7—C9—H9A	109.5	C19—C21—H21A	109.5
C7—C9—H9B	109.5	C19—C21—H21B	109.5
H9A—C9—H9B	109.5	H21A—C21—H21B	109.5
C7—C9—H9C	109.5	C19—C21—H21C	109.5
H9A—C9—H9C	109.5	H21A—C21—H21C	109.5
H9B—C9—H9C	109.5	H21B—C21—H21C	109.5
C3—C10—H10A	109.5	C15—C22—H22A	109.5
C3—C10—H10B	109.5	C15—C22—H22B	109.5
H10A—C10—H10B	109.5	H22A—C22—H22B	109.5
C3—C10—H10C	109.5	C15—C22—H22C	109.5
H10A—C10—H10C	109.5	H22A—C22—H22C	109.5
H10B—C10—H10C	109.5	H22B—C22—H22C	109.5
N3—C11—N2	117.1 (2)	N6—C23—N5	117.0 (2)
N3—C11—S1	122.56 (18)	N6—C23—S2	123.64 (17)
N2—C11—S1	120.29 (18)	N5—C23—S2	119.31 (18)
N3—C12—H12A	109.5	N6—C24—H24A	109.5
N3—C12—H12B	109.5	N6—C24—H24B	109.5
H12A—C12—H12B	109.5	H24A—C24—H24B	109.5
N3—C12—H12C	109.5	N6—C24—H24C	109.5
H12A—C12—H12C	109.5	H24A—C24—H24C	109.5
H12B—C12—H12C	109.5	H24B—C24—H24C	109.5
C1—N1—N2	119.97 (19)	C13—N4—N5	117.0 (2)
C11—N2—N1	117.26 (19)	C23—N5—N4	118.4 (2)
C11—N2—H2	121.4	C23—N5—H5	120.8
N1—N2—H2	121.4	N4—N5—H5	120.8
C11—N3—C12	123.6 (2)	C23—N6—C24	123.2 (2)
C11—N3—H3A	118.2	C23—N6—H6A	118.4
C12—N3—H3A	118.2	C24—N6—H6A	118.4

N1—C1—C2—C3	125.8 (2)	N4—C13—C14—C15	126.1 (2)
C6—C1—C2—C3	−52.4 (3)	C18—C13—C14—C15	−55.5 (3)
C1—C2—C3—C4	52.6 (3)	C13—C14—C15—C16	53.7 (3)
C1—C2—C3—C10	177.1 (2)	C13—C14—C15—C22	178.8 (2)
C10—C3—C4—C5	179.6 (2)	C22—C15—C16—C17	−179.2 (2)
C2—C3—C4—C5	−56.4 (3)	C14—C15—C16—C17	−56.0 (3)
C3—C4—C5—C6	59.1 (3)	C15—C16—C17—C18	59.1 (3)
N1—C1—C6—C5	−126.7 (3)	N4—C13—C18—C19	1.8 (3)
C2—C1—C6—C5	51.2 (3)	C14—C13—C18—C19	−176.7 (2)
N1—C1—C6—C7	106.7 (3)	N4—C13—C18—C17	−126.6 (2)
C2—C1—C6—C7	−75.4 (3)	C14—C13—C18—C17	54.9 (3)
C4—C5—C6—C1	−53.9 (3)	C16—C17—C18—C13	−55.9 (3)
C4—C5—C6—C7	70.1 (3)	C16—C17—C18—C19	174.7 (2)
C1—C6—C7—C8	−61.2 (3)	C13—C18—C19—C20	−76.8 (3)
C5—C6—C7—C8	176.3 (2)	C17—C18—C19—C20	48.6 (3)
C1—C6—C7—C9	175.6 (2)	C13—C18—C19—C21	158.9 (2)
C5—C6—C7—C9	53.1 (3)	C17—C18—C19—C21	−75.6 (3)
C2—C1—N1—N2	−178.62 (19)	C18—C13—N4—N5	175.85 (18)
C6—C1—N1—N2	−0.7 (4)	C14—C13—N4—N5	−5.9 (3)
N3—C11—N2—N1	2.4 (3)	N6—C23—N5—N4	−12.5 (3)
S1—C11—N2—N1	−176.24 (16)	S2—C23—N5—N4	168.60 (15)
C1—N1—N2—C11	178.0 (2)	C13—N4—N5—C23	165.0 (2)
N2—C11—N3—C12	−179.2 (2)	N5—C23—N6—C24	−174.4 (2)
S1—C11—N3—C12	−0.6 (3)	S2—C23—N6—C24	4.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2	0.88	2.79	3.671 (2)	174
N3—H3A···S1ⁱ	0.88	2.61	3.378 (2)	147
N5—H5···S1	0.88	2.61	3.356 (2)	143
N6—H6A···S2ⁱⁱ	0.88	2.79	3.445 (2)	132

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2	0.88	2.79	3.671 (2)	174.2
N3—H3A···S1ⁱ	0.88	2.61	3.378 (2)	146.8
N5—H5···S1	0.88	2.61	3.356 (2)	143.4
N6—H6A···S2ⁱⁱ	0.88	2.79	3.445 (2)	132.1

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

Experimental details

Crystal data
Chemical formula	C₁₂H₂₃N₃S
M_r	241.39
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	123
a, b, c (Å)	11.5579 (5), 9.9279 (4), 12.5271 (5)
β (°)	95.030 (2)
V (Å³)	1431.90 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.77 × 0.30 × 0.08

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Analytical (Alcock, 1970)
T_min, T_max	0.857, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	23116, 6380, 5069
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.104, 1.06
No. of reflections	6380
No. of parameters	297
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.36
Absolute structure	Flack x determined using 1954 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	0.00 (7)

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

Acknowledgements

We gratefully acknowledge financial support by the State of North Rhine-Westphalia, Germany. ABO is an associate researcher in the project `Dinitrosyl complexes containing thiol and/or thiosemicarbazone: synthesis, characterization and treatment against cancer`, founded by FAPESP, Proc. 2015/12098–0, and acknowledges Professor José Clayston Melo Pereira (UNESP, Brazil) for his support in this work.

References

Alcock, N. W. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, p. 271. Copenhagen: Munksgaard. Google Scholar
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Freund, M. & Schander, A. (1902). Chem. Ber. 35, 2602–2606. CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Oliveira, A. B. de, Beck, J., Daniels, J., de Farias, R. L. & de Godoy Netto, A. V. (2014). Acta Cryst. E70, o903–o904. CrossRef IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press, United States. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.