N-Methyl-2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclo­pent-2-en-1-yl­idene}hydrazinecarbo­thio­amide

Oliveira, A.B. de; Bresolin, L.; Beck, J.; Daniels, J.

doi:10.1107/S2414314624000130

organic compounds

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ISSN: 2414-3146

Volume 9| Part 1| January 2024| x240013

https://doi.org/10.1107/S2414314624000130

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N-Methyl-2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclopent-2-en-1-ylidene}hydrazinecarbothioamide

Adriano Bof de Oliveira,^a ^* Leandro Bresolin,^b Johannes Beck ^c and Jörg Daniels ^c

^aDepartamento de Química, Universidade Federal de Sergipe, Av. Marcelo Deda Chagas s/n, Campus Universitário, 49107-230 São Cristóvão-SE, Brazil, ^bEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil, and ^cInstitut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany
^*Correspondence e-mail: adriano@daad-alumni.de

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 3 January 2024; accepted 4 January 2024; online 9 January 2024)

The equimolar and hydrochloric acid-catalysed reaction between cis-jasmone and 4-methylthiosemicarbazide in ethanolic solution yields the title compound, C₁₃H₂₁N₃S (common name: cis-jasmone 4-methylthiosemicarbazone). Two molecules with all atoms in general positions are present in the asymmetric unit. In one of them, the carbon chain is disordered [site occupancy ratio = 0.821 (3):0.179 (3)]. The thiosemicarbazone entities [N—N—C(=S)—N] are approximately planar, with the maximum deviation from the mean plane through the selected atoms being −0.0115 (16) Å (r.m.s.d. = 0.0078 Å) for the non-disordered molecule and 0.0052 (14) Å (r.m.s.d. = 0.0031 Å) for the disordered one. The molecules are not planar, since the jasmone groups have a chain with sp³-hybridized carbon atoms and, in addition, the thiosemicarbazone fragments are attached to the respective carbon five-membered rings and the dihedral angles between them for each molecule amount to 8.9 (1) and 6.3 (1)°. In the crystal, the molecules are connected through pairs of N—H⋯S and C—H⋯S interactions into crystallographically independent centrosymmetric dimers, in which rings of graph-set motifs R₂²(8) and R₂¹(7) are observed. A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are from H⋯H (70.6%), H⋯S/S⋯H (16.7%), H⋯C/C⋯H (7.5%) and H⋯N/N⋯H (4.9%) interactions [considering the two crystallographically independent molecules and only the disordered atoms with the highest s.o.f. for the evaluation].

Keywords: thiosemicarbazone; cis-jasmone; methylthiosemicarbazone derivative; centrosymmetric dimers; crystal structure; Hirshfeld analysis.

CCDC reference: 2304272

Structure description

To the best of our knowledge, the first crystal structure of cis-jasmone thiosemicarbazone was reported recently and it was pointed out that this derivative based on non-substituted cis-jasmone shows antifungal activity (Orsoni et al., 2020 ; Jamiołkowska et al., 2022 ).

As part of our interest in thiosemicarbazones attached to natural product derivatives and on the influence of the substituent groups at the terminal N atom on the supramolecular arrangement, we report here the synthesis, crystal structure and Hirshfeld analysis of cis-jasmone 4-methylthiosemicarbazone. It is important to highlight that the substituents at the terminal N atom are relevant not only to the crystal packing, but also to the biological properties of the thiosemicarbazone derivatives. For example, a small chemical library of 4-methylthiosemicarbazones has been studied for the treatment of Parkinson's disease (Mathew et al., 2021 ) and for microbial growth inhibition (D'Agostino et al., 2022 ). In addition, for a review article on coordination compounds with 4-methylthiosemicarbazone derivatives including biological applications and catalytic activity, see: Monsur Showkot Hossain et al. (2023 ).

The asymmetric unit of the title compound comprises two molecules with all atoms in general positions, with one of them showing disorder over the carbon chain [site occupancy ratio = 0.821 (3):0.179 (3)]. The molecules are not planar due to the chain with sp³-hybridized carbon atoms in the jasmone fragment and the dihedral angles between the thiosemicarbazone fragment and the respective carbon five-membered ring, which amount to 8.9 (1)° for the non-disordered molecule and 6.3 (1)° for the disordered one (Fig. 1). To simplify the structure description, the non-disordered molecule, with atoms C1–C13/N–N3/S1, will be designated as JMTSC-1, while the disordered one, with the atoms C14–C23A/C23B/N4–N6/S2, will be designated as JMTSC-2. To get a stable refinement, the C20, C21, C22 and C23 atoms were split into two positions and A-labelled for the higher s.o.f and B-labelled for the lower. Atom C19, which is itself not disordered, is bound to C20A and C20B, and to achieve the best orientations for the C19—H bonds, the H19A and H19B atoms were also split, into two positions. Thus, the H19A and H19B atoms have a s.o.f. of 0.821 (3) and the H19C and H19D atoms have a s.o.f. of 0.179 (3). Selected geometric parameters for the structural description of JMTSC-1 and JMTSC-2 are given in Table 1; these are in agreement with literature data (Oliveira et al., 2016 ; Rocha et al., 2014 ).

Table 1
Selected geometric parameters (Å, °) for the two crystallographically independent cis-jasmone 4-methylthiosemicarbazone molecules, JMTSC-1 and JMTSC-2

Compound	Atom chain	Torsion angle	Atom chain	Torsion angle
JMTSC-1	N1/N2/C11/N3	−1.2 (3)	C5/C6/C7/C8	114.6 (3)
JMTSC-1	N1/N2/C11/S1	178.55 (17)	C7/C8/C9/C10	128.0 (4)
JMTSC-2	N4/N5/C25/N6	0.8 (3)	C18/C19/C20A/C21A	139.9 (4)
JMTSC-2	N4/N5/C25/S2	−179.57 (16)	C18/C19/C20B/C21B	−117.6 (13)
			C20A/C21A/C22A/C23A	121.9 (4)
			C20B/C21B/C22B/C23B	−95 (4)

	Fragment	Max. deviation^a	r.m.s.d.	Angle^b
JMTSC-1	N1/N2/C11/S1/N3	−0.0115 (16) [N2]	0.0078
JMTSC-1	C1—C5 ring	0.0130 (16) [C4]	0.0089	8.9 (1)
JMTSC-2	N4/N5/C25/S2/N6	0.0052 (14) [N5]	0.0031
JMTSC-2	C14—C18 ring	0.0078 (16) [C17]	0.0054	6.3 (1)

	Bond lengths^c	N—N	N—C	C=S
JMTSC-1		1.392 (3)	1.351 (3)	1.680 (2)
JMTSC-2		1.394 (2)	1.357 (3)	1.678 (2)
Notes: (a) The maximum deviation from the mean plane through the selected atoms; (b) angle to previous plane; (c) bond lengths for the N1/N2/C11/S1 and N4/N5/C25/S2 entities.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 40% probability level for the two crystallographically independent molecules. Disordered atoms are drawn with 40% transparency and labelled C20A, C21A, C22A, C23A, H19A and H19B [s.o.f. = 0.821 (3)] and C20B, C21B, C22B, C23B, H19C and H19D [s.o.f. = 0.179 (3)]. The remaining H atoms were omitted for clarity.

For the supramolecular arrangement and Hirshfeld analysis, for clarity only the disordered atoms with the highest s.o.f. value were considered. In the crystal, the molecules are connected through pairs of N—H⋯S and C—H⋯S interactions into centrosymmetric dimers with graph-set motifs R₂²(8) and R₂¹(7) (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯S1ⁱ	0.81 (3)	2.80 (3)	3.591 (2)	167 (2)
C2—H5B⋯S1ⁱ	0.97 (3)	2.90 (3)	3.457 (2)	117.4 (18)
N5—H3⋯S2ⁱⁱ	0.84 (3)	2.75 (3)	3.585 (2)	172 (2)
C15—H18A⋯S2ⁱⁱ	0.93 (2)	2.98 (2)	3.472 (2)	115.0 (17)
Symmetry codes: (i) ; (ii) .

With the coordinates that were used for the refinement, the crystallographically independent dimers of the JMTSC-1 molecules have the gravity centre located in the cell vertices (Fig. 2), and in the centre of the ac planes for the JMTSC-2 molecules (Fig. 3). In addition, the molecules are stacked along [100] and only weak intermolecular interactions, e.g., London dispersion forces can be presumed in this direction (Fig. 4).

Figure 2
Crystal structure section of the title compound for the JMTSC-1 molecule, showing the hydrogen-bond intermolecular interactions as dashed lines. The molecules are linked into centrosymmetric dimers via pairs of N—H⋯S and C—H⋯S interactions with graph-set motifs R₂²(8) and R₂¹(7). [Symmetry code: (i) −x, −y, −z + 2.]

Figure 3
Crystal structure section of the title compound for the JMTSC-2 molecule, showing the hydrogen-bonded intermolecular interactions drawn as dashed lines. Disorder is not shown for clarity. The molecules are linked into centrosymmetric dimers via pairs of N—H⋯S and C—H⋯S interactions with graph-set motifs R₂²(8) and R₂¹(7). [Symmetry code: (ii) −x + 1, −y, −z + 1.]

Figure 4
Selected crystal section of the title compound viewed along [010] showing the JMTSC-1 and JMTSC-2 molecules stacked along [100]. Only the non-H atoms of the thiosemicarbazone entities are labelled and disorder is not shown for clarity. [Symmetry code: (iii) x + 1, y, z.]

The Hirshfeld surface analysis (Hirshfeld, 1977 ), the graphical representations and the two-dimensional Hirshfeld surface fingerprints (HSFP) were evaluated with the Crystal Explorer software (Wolff et al., 2012 ). The Hirshfeld surface analysis of the title compound, considering the JMTSC-1 and the JMTSC-2 molecules, suggests that the most relevant intermolecular interactions for the crystal packing are H⋯H (70.6%), H⋯S/S⋯H (16.7%), H⋯C/C⋯H (7.5%) and H⋯N/N⋯H (4.9%). A graphical representation of the Hirshfeld surface (d_norm) is shown in Fig. 5 with the locations of the strongest intermolecular contacts, i.e, the regions around the atoms H1, H3, S1 and S2, indicated in red. These atoms are those involved in the H⋯S interactions showed in the previous figures (Figs. 2 and 3). The contributions to the crystal cohesion are shown as two-dimensional Hirshfeld surface fingerprint plots (HSFP) with cyan dots (Fig. 6).

Figure 5
Hirshfeld surface graphical representation (d_norm) for the two crystallographically independent molecules of the title compound. The surface is drawn with transparency, and the disorder is not shown for clarity. The regions with strongest intermolecular interactions are shown in red (d_norm range: −0.216 to 1.522 a.u.).

Figure 6
The Hirshfeld surface two-dimensional fingerprint plot for the title compound, showing the contacts in detail (cyan dots). The major contributions of the interactions to the crystal cohesion amount to (a) H⋯H (70.6%), (b) H⋯S/S⋯H (16.7%), (c) H⋯C/C⋯H (7.5%) and (d) H⋯N/N⋯H (4.9%). The d_i (x-axis) and the d_e (y-axis) values are the closest internal and external distances from given points on the Hirshfeld surface contacts (in Å). Regarding the disorder, only the atoms with the highest s.o.f. were considered.

The crystalline supramolecular arrangement of thiosemicarbazones depends on the template effect of the crystallization solvent, the presence of solvate molecules and on the crystallization methods. In addition, the steric effect of the substituents in the R₁R₂N—N(H)—C(=S)—NR₃R₄ fragment is of prime importance for the crystal packing. In the title compound, two structural features lead to the building of dimers. The first one is the terminal methyl group, N(H)CH₃, which decreases the possibility for N—H⋯S intermolecular interactions and enhances the formation of hydrogen-bonded supramolecular structures. On the other side of the molecule, the second feature is the cis-jasmone entity, which, through steric hindrance, precludes intermolecular interactions, e.g., N—H⋯S or N—H⋯N (Figs. 2 and 3); thus, four methyl-substituted thiosemicarbazone derivatives were selected for structural comparison with the title compound.

The first example is the crystal structure of benzylideneacetone 4-methylthiosemicarbazone (Rocha et al., 2014). As a result of the steric effect of two methyl groups, one on the terminal N atom and other on the C atom attached to the thiosemicarbazone entity, dimer formation was favoured. The remaining N—H bond is involved in the N—H⋯N intramolecular interaction, with graph-set motif S(5). Thus, the molecules are linked by N—H⋯S interactions, with graph-set motif R₂²(8), into centrosymmetric dimers. For the graphical representation of the dimeric unit, see Fig. 7(a).

Figure 7
(a) Dimeric structure of the benzylideneacetone 4-methylthiosemicarbazone compound (Rocha et al., 2014

). The molecules are connected via pairs of centrosymmetric N—H⋯S interactions, with graph-set R₂²(8). [Symmetry code: (i) −x + 1, −y, −z.] and (b) section of the molecular arrangement of the vanilline 4-methylthiosemicarbazone structure (Oliveira, Beck et al., 2015

). The molecules are connected by pairs of centrosymmetric N—H⋯S interactions, with graph-set R₂²(8). The dimers are linked further by O—H⋯S and N—H⋯O interactions into a tape-like structure. Only the subunit of the supramolecular arrangement is shown for clarity. [Symmetry codes: (i) x + 1, y-1, z;; (ii) −x − 2, −y, −z; (iii) -x-1, y + $[{1\over 2}]$ , −z − $[{1\over 2}]$ .]

The second selected molecule is the vanilline 4-methylthiosemicarbazone derivative (Oliveira, Beck et al., 2015 ) in which the thiosemicarbazone entities are connected by N—H⋯S interactions, with graph-set motif R₂²(8), into centrosymmetric dimers. The dimers are further linked through N—H⋯S and O—H⋯S interactions and can be considered subunits of a hydrogen-bonded tape-like supramolecular arrangement. This is only possible because of the O atoms in the vanilline structure, see Fig. 7(b).

A further example is 3′,4′-(methylenedioxy)acetophenone 4-methylthiosemicarbazone (Oliveira, Näther et al., 2015 ). As mentioned above, the terminal methyl group decreases the dimensionality of the molecular arrangement and the thiosemicarbazone entities are connected by pairs of centrosymmetric N—H⋯S interactions, with graph-set motifs R₂²(8). A feature of the structural arrangement of this compound is that every thiosemicarbazone fragment bridges two other molecules through N—H⋯S interactions in opposite directions, see Fig. 8(a).

Figure 8
(a) Section of the molecular arrangement of the 3′,4′-(methylenedioxy)acetophenone 4-methylthiosemicarbazone structure (Oliveira, Näther et al., 2015

). The molecules are connected by pairs of centrosymmetric N—H⋯S interactions, with graph-set R₂²(8), and further linked by additional N—H⋯S interactions into a tape-like structure. H atoms were omitted for clarity and only the subunit of the supramolecular arrangement is shown [Symmetry codes: (i) −x + 1, −y + 1, −z + 2; (ii) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .] and (b) section of the molecular arrangement of the (–)-menthone 4-methylthiosemicarbazone structure (Oliveira et al., 2016

). The molecules are connected by pairs of N—H⋯S interactions, with graph-set R₂²(8), into non-centrosymmetric dimers and further linked by additional N—H⋯S interactions, forming a tape-like structure. Only the subunit of the supramolecular arrangement is shown for clarity [Symmetry codes: (i) −x + 1, y − $[{1\over 2}]$ , −z + 1; (ii) −x + 2, y + $[{1\over 2}]$ , −z + 1.]

Finally, the structure of (–)-menthone 4-methylthiosemicarbazone (Oliveira et al., 2016) shows a non-centrosymmetric dimer, with the molecules connected by pairs of N—H⋯S interactions, also with graph-set motif R₂²(8). A difference in this structure is the linking of the terminal N—H bonds between the molecules through N—H⋯S interactions into a tape-like structure. For the dimeric subunit of the supramolecular arrangement, see Fig. 8(b).

As observed for the title compound, pairs of N—H⋯S intermolecular interactions with graph-set motif R₂²(8) are a remarkable feature for the crystal structure of thiosemicarbazone derivatives. The supramolecular arrangement of the compounds depends on the structure of the substituents on the terminal N atom, as well as on the fragment attached to the first N atom.

Synthesis and crystallization

The starting materials are commercially available and were used without further purification. The synthesis of the cis-jasmone 4-methylthiosemicarbazone derivative was adapted from previously reported procedures (Oliveira, Beck et al., 2015; Orsoni et al., 2020). A mixture of ethanolic solutions of cis-jasmone (8 mmol in 50 ml) and 4-methylthiosemicarbazide (8 mmol in 50 ml) was catalysed with HCl and refluxed for 8 h. After cooling, the precipitated product was filtered off and washed with cold ethanol. Colourless single crystals suitable for X-ray diffraction were obtained from tetrahydrofuran by slow evaporation of the solvent at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. There are two crystallographically independent molecules in the asymmetric unit of the title compound and one of them, JMTSC-2, shows disorder over the chain of the cis-jasmone fragment, namely the C20, C21, C22, C23, H19C and H19D atoms (Fig. 1). These atoms were split over two positions, with the carbon atoms being A-labelled for the higher s.o.f. value positions and B-labelled for the lower [site-occupancy ratio = 0.821 (3):0.179 (3)]. The atom C19 is itself not disordered, but it is bound to C20A and C20B, and to get the best orientations for the C19—H bonds, the hydrogen atoms were disordered. Thus, H19A and H19B have the positions with higher s.o.f., while H19C and H19D have the positions with the lower. The EADP command was used to constrain the displacement parameters of the disordered carbon atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₃H₂₁N₃S
M_r	251.39
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	223
a, b, c (Å)	7.9583 (2), 11.2703 (2), 16.0080 (5)
α, β, γ (°)	83.0428 (18), 86.9392 (13), 76.5236 (18)
V (Å³)	1385.51 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.22
Crystal size (mm)	0.28 × 0.13 × 0.12

Data collection
Diffractometer	Enraf–Nonius FR590 Kappa CCD
Absorption correction	Analytical (Alcock, 1970 )
T_min, T_max	0.945, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	23118, 6319, 3700
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.140, 1.03
No. of reflections	6319
No. of parameters	432
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Computer programs: COLLECT (Nonius, 1998 ), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SIR92 (Altomare et al., 1994 ), SHELXL2018/3 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 2006 ), Crystal Explorer 3.1 (Wolff et al., 2012), WinGX (Farrugia, 2012 ), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

The H atoms were treated by a mixture of constrained and independent refinement. The constrained H atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined using a riding model. For the C13H₃, C23AH₃, C23BH₃ and C26H₃ groups, the methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density, with U_iso(H) = 1.5 U_eq(C), and the C—H bonds were set to 0.96 Å. In an analogous manner, with U_iso(H) = 1.2 U_eq(C), for the C22AH₂ and C22BH₂ groups the C—H bond lengths were set to 0.97 Å and for the C20AH, C20BH, C21AH and C21BH, were set to 0.93 Å. In addition, the C19—H bonds were set to 0.97 Å. The remaining H atoms were refined freely.

Structural data

CCDC reference: 2304272

Crystal structure: contains datablocks I, publication_text. DOI: https://doi.org/10.1107/S2414314624000130/bt4146sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624000130/bt4146Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624000130/bt4146Isup3.cml

checkCIF report

Computing details top

N-Methyl-2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclopent-2-en-1-ylidene}hydrazinecarbothioamide top

Crystal data top

C₁₃H₂₁N₃S	Z = 4
M_r = 251.39	F(000) = 544
Triclinic, P1	D_x = 1.205 Mg m⁻³
a = 7.9583 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2703 (2) Å	Cell parameters from 22795 reflections
c = 16.0080 (5) Å	θ = 2.9–27.5°
α = 83.0428 (18)°	µ = 0.22 mm⁻¹
β = 86.9392 (13)°	T = 223 K
γ = 76.5236 (18)°	Prism, colourless
V = 1385.51 (6) Å³	0.28 × 0.13 × 0.12 mm

Data collection top

Enraf–Nonius FR590 Kappa CCD diffractometer	6319 independent reflections
Radiation source: sealed X-ray tube, Enraf Nonius FR590	3700 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.056
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD rotation images, thick slices, κ–goniostat scans	h = −10→10
Absorption correction: analytical (Alcock, 1970)	k = −14→14
T_min = 0.945, T_max = 0.978	l = −20→20
23118 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)] = 0.052	Hydrogen site location: mixed
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0556P)² + 0.4261P] where P = (F_o² + 2F_c²)/3
6319 reflections	(Δ/σ)_max = 0.001
432 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.0353 (3)	0.1677 (2)	0.75329 (13)	0.0349 (5)
C2	0.0002 (4)	0.0424 (2)	0.75249 (14)	0.0389 (5)
C3	0.0007 (4)	0.0248 (2)	0.65901 (15)	0.0417 (6)
C4	0.0398 (3)	0.1401 (2)	0.61351 (13)	0.0376 (5)
C5	0.0551 (3)	0.2205 (2)	0.66637 (13)	0.0364 (5)
C6	0.0898 (4)	0.3467 (2)	0.64395 (17)	0.0442 (6)
C7	−0.0620 (4)	0.4410 (2)	0.60830 (17)	0.0486 (6)
H7	−0.090 (3)	0.427 (3)	0.5551 (18)	0.067 (9)*
C8	−0.1493 (4)	0.5392 (3)	0.6422 (2)	0.0583 (7)
H8	−0.243 (3)	0.593 (2)	0.6108 (16)	0.055 (7)*
C9	−0.1227 (6)	0.5789 (3)	0.7249 (2)	0.0773 (10)
H9A	−0.009 (5)	0.516 (4)	0.750 (2)	0.124 (14)*
H9B	−0.226 (5)	0.571 (3)	0.762 (2)	0.110 (13)*
C10	−0.1051 (5)	0.7098 (3)	0.7187 (2)	0.0664 (9)
H10A	−0.003 (5)	0.725 (3)	0.684 (2)	0.090 (11)*
H10B	−0.095 (5)	0.735 (3)	0.771 (2)	0.103 (13)*
H10C	−0.203 (5)	0.764 (3)	0.692 (2)	0.102 (12)*
C11	0.0650 (3)	0.2114 (2)	0.96479 (14)	0.0410 (6)
C12	0.0594 (4)	0.1544 (3)	0.52013 (16)	0.0502 (7)
C13	0.1722 (4)	0.3754 (3)	1.01676 (17)	0.0605 (8)
H13A	0.078825	0.394161	1.057058	0.091*
H13B	0.202888	0.449897	0.992591	0.091*
H13C	0.270256	0.321649	1.044276	0.091*
H1	0.000 (3)	0.099 (3)	0.9014 (16)	0.055 (9)*
H2	0.136 (4)	0.342 (3)	0.9011 (18)	0.062 (9)*
H4A	−0.107 (3)	0.012 (2)	0.6423 (14)	0.043 (7)*
H4B	0.087 (3)	−0.043 (2)	0.6446 (14)	0.041 (6)*
H5A	−0.111 (4)	0.036 (2)	0.7836 (16)	0.062 (8)*
H5B	0.083 (3)	−0.023 (2)	0.7831 (16)	0.055 (7)*
H6A	0.132 (3)	0.375 (2)	0.6918 (14)	0.037 (6)*
H6B	0.178 (4)	0.344 (2)	0.6043 (17)	0.058 (8)*
H11A	−0.050 (4)	0.144 (3)	0.4942 (19)	0.078 (10)*
H11B	0.151 (4)	0.097 (3)	0.5017 (18)	0.070 (9)*
H11C	0.082 (4)	0.233 (3)	0.4981 (18)	0.078 (10)*
N1	0.0527 (2)	0.22380 (17)	0.81644 (11)	0.0402 (5)
N2	0.0324 (3)	0.1628 (2)	0.89595 (12)	0.0443 (5)
N3	0.1185 (3)	0.3154 (2)	0.95063 (14)	0.0503 (6)
S1	0.03760 (10)	0.14256 (6)	1.06201 (4)	0.0555 (2)
C14	0.5379 (3)	0.16267 (19)	0.71740 (13)	0.0329 (5)
C15	0.5078 (4)	0.0367 (2)	0.74221 (14)	0.0370 (5)
C16	0.5116 (4)	0.0211 (2)	0.83872 (14)	0.0412 (6)
C17	0.5457 (3)	0.1391 (2)	0.86107 (13)	0.0375 (5)
C18	0.5580 (3)	0.21881 (19)	0.79294 (13)	0.0347 (5)
C19	0.5811 (3)	0.3483 (2)	0.78856 (15)	0.0448 (6)
H19A	0.643811	0.356753	0.837003	0.054*	0.821 (3)
H19B	0.647894	0.366698	0.738193	0.054*	0.821 (3)
H19C	0.685443	0.350346	0.754772	0.054*	0.179 (3)
H19D	0.486229	0.399219	0.755824	0.054*	0.179 (3)
C20A	0.4087 (5)	0.4364 (3)	0.7871 (2)	0.0532 (8)	0.821 (3)
H20A	0.329480	0.415962	0.754005	0.064*	0.821 (3)
C21A	0.3451 (5)	0.5388 (3)	0.8238 (2)	0.0569 (9)	0.821 (3)
H21A	0.229448	0.576497	0.815022	0.068*	0.821 (3)
C22A	0.4385 (6)	0.5964 (3)	0.8758 (2)	0.0621 (10)	0.821 (3)
H22A	0.557592	0.550356	0.879680	0.075*	0.821 (3)
H22B	0.387225	0.595899	0.932190	0.075*	0.821 (3)
C23A	0.4333 (6)	0.7287 (3)	0.8386 (3)	0.0612 (11)	0.821 (3)
H23A	0.474681	0.729616	0.781112	0.092*	0.821 (3)
H23B	0.505314	0.763050	0.870457	0.092*	0.821 (3)
H23C	0.316591	0.776477	0.840756	0.092*	0.821 (3)
C20B	0.592 (2)	0.4084 (12)	0.8561 (9)	0.0532 (8)	0.179 (3)
H20B	0.682753	0.377545	0.892534	0.064*	0.179 (3)
C21B	0.479 (2)	0.5069 (15)	0.8714 (11)	0.0569 (9)	0.179 (3)
H21B	0.516842	0.521502	0.922436	0.068*	0.179 (3)
C22B	0.319 (3)	0.6156 (17)	0.8557 (11)	0.0621 (10)	0.179 (3)
H22C	0.239982	0.592198	0.820463	0.075*	0.179 (3)
H22D	0.260444	0.632136	0.909131	0.075*	0.179 (3)
C23B	0.366 (3)	0.728 (2)	0.8152 (14)	0.0612 (11)	0.179 (3)
H23D	0.363076	0.783573	0.856476	0.092*	0.179 (3)
H23E	0.284292	0.766305	0.772294	0.092*	0.179 (3)
H23F	0.479632	0.707879	0.790243	0.092*	0.179 (3)
C24	0.5633 (5)	0.1554 (3)	0.95104 (15)	0.0526 (7)
C25	0.5613 (3)	0.2125 (2)	0.49665 (13)	0.0354 (5)
C26	0.6433 (4)	0.3925 (2)	0.41676 (15)	0.0529 (7)
H26A	0.739134	0.344372	0.387775	0.079*
H26B	0.673244	0.465559	0.430318	0.079*
H26C	0.544756	0.414694	0.381308	0.079*
H3	0.508 (3)	0.089 (3)	0.5819 (16)	0.052 (8)*
H4	0.611 (3)	0.348 (2)	0.5401 (16)	0.048 (7)*
H17A	0.599 (3)	−0.050 (2)	0.8611 (15)	0.053 (7)*
H17B	0.401 (3)	0.004 (2)	0.8647 (15)	0.050 (7)*
H18A	0.590 (3)	−0.023 (2)	0.7182 (14)	0.044 (7)*
H18B	0.398 (3)	0.032 (2)	0.7211 (15)	0.048 (7)*
H24A	0.573 (4)	0.238 (3)	0.960 (2)	0.095 (11)*
H24B	0.459 (4)	0.138 (3)	0.9862 (18)	0.070 (9)*
H24C	0.662 (4)	0.096 (3)	0.9751 (19)	0.078 (10)*
N4	0.5513 (2)	0.22004 (16)	0.64328 (11)	0.0370 (4)
N5	0.5353 (3)	0.15779 (19)	0.57504 (11)	0.0384 (5)
N6	0.6022 (3)	0.32130 (18)	0.49376 (13)	0.0453 (5)
S2	0.54338 (9)	0.14458 (6)	0.41094 (3)	0.04489 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0328 (13)	0.0353 (12)	0.0357 (12)	−0.0050 (10)	−0.0016 (9)	−0.0056 (9)
C2	0.0442 (15)	0.0375 (13)	0.0337 (12)	−0.0094 (11)	0.0011 (11)	−0.0002 (10)
C3	0.0490 (16)	0.0385 (14)	0.0375 (13)	−0.0090 (12)	0.0019 (11)	−0.0076 (10)
C4	0.0383 (13)	0.0390 (13)	0.0335 (12)	−0.0059 (10)	0.0031 (10)	−0.0035 (9)
C5	0.0373 (13)	0.0366 (13)	0.0340 (12)	−0.0063 (10)	−0.0003 (9)	−0.0028 (9)
C6	0.0495 (16)	0.0426 (14)	0.0425 (15)	−0.0161 (12)	−0.0001 (13)	−0.0023 (11)
C7	0.0600 (18)	0.0396 (15)	0.0477 (16)	−0.0185 (13)	−0.0049 (13)	0.0053 (11)
C8	0.0541 (18)	0.0418 (16)	0.075 (2)	−0.0109 (13)	−0.0013 (15)	0.0083 (14)
C9	0.111 (3)	0.0500 (19)	0.064 (2)	−0.0098 (19)	0.033 (2)	−0.0092 (15)
C10	0.078 (2)	0.0518 (19)	0.067 (2)	−0.0093 (17)	0.0050 (19)	−0.0087 (15)
C11	0.0462 (15)	0.0418 (14)	0.0355 (13)	−0.0086 (11)	−0.0052 (10)	−0.0072 (10)
C12	0.063 (2)	0.0497 (17)	0.0366 (14)	−0.0105 (15)	0.0044 (13)	−0.0067 (12)
C13	0.083 (2)	0.0542 (17)	0.0518 (16)	−0.0235 (15)	−0.0136 (14)	−0.0132 (13)
N1	0.0460 (12)	0.0425 (11)	0.0324 (10)	−0.0114 (9)	−0.0009 (8)	−0.0029 (8)
N2	0.0604 (14)	0.0447 (13)	0.0321 (11)	−0.0210 (11)	−0.0027 (9)	−0.0035 (9)
N3	0.0715 (16)	0.0471 (13)	0.0372 (13)	−0.0233 (11)	−0.0059 (11)	−0.0036 (10)
S1	0.0842 (5)	0.0544 (4)	0.0327 (3)	−0.0261 (4)	−0.0033 (3)	−0.0034 (3)
C14	0.0371 (13)	0.0325 (12)	0.0292 (11)	−0.0085 (10)	0.0009 (9)	−0.0039 (9)
C15	0.0450 (15)	0.0325 (13)	0.0335 (12)	−0.0087 (11)	0.0003 (11)	−0.0045 (9)
C16	0.0585 (17)	0.0331 (13)	0.0319 (12)	−0.0119 (12)	0.0020 (12)	−0.0014 (9)
C17	0.0463 (14)	0.0353 (12)	0.0307 (12)	−0.0085 (10)	0.0020 (10)	−0.0064 (9)
C18	0.0404 (13)	0.0338 (12)	0.0315 (11)	−0.0110 (10)	0.0006 (9)	−0.0057 (9)
C19	0.0614 (17)	0.0410 (14)	0.0381 (13)	−0.0233 (12)	−0.0009 (11)	−0.0059 (10)
C20A	0.071 (2)	0.0345 (16)	0.0559 (19)	−0.0156 (15)	−0.0056 (16)	−0.0041 (13)
C21A	0.054 (2)	0.0441 (19)	0.072 (2)	−0.0135 (16)	−0.0031 (16)	−0.0019 (16)
C22A	0.089 (3)	0.052 (2)	0.049 (2)	−0.024 (2)	−0.004 (2)	−0.0035 (15)
C23A	0.092 (4)	0.0384 (17)	0.057 (3)	−0.023 (2)	−0.008 (2)	−0.0053 (17)
C20B	0.071 (2)	0.0345 (16)	0.0559 (19)	−0.0156 (15)	−0.0056 (16)	−0.0041 (13)
C21B	0.054 (2)	0.0441 (19)	0.072 (2)	−0.0135 (16)	−0.0031 (16)	−0.0019 (16)
C22B	0.089 (3)	0.052 (2)	0.049 (2)	−0.024 (2)	−0.004 (2)	−0.0035 (15)
C23B	0.092 (4)	0.0384 (17)	0.057 (3)	−0.023 (2)	−0.008 (2)	−0.0053 (17)
C24	0.079 (2)	0.0511 (18)	0.0284 (13)	−0.0152 (16)	−0.0032 (14)	−0.0050 (11)
C25	0.0385 (13)	0.0341 (12)	0.0324 (12)	−0.0075 (10)	0.0000 (9)	−0.0013 (9)
C26	0.0690 (18)	0.0466 (15)	0.0443 (14)	−0.0222 (13)	0.0037 (13)	0.0056 (11)
N4	0.0457 (12)	0.0375 (11)	0.0302 (10)	−0.0129 (9)	−0.0012 (8)	−0.0067 (8)
N5	0.0550 (13)	0.0338 (11)	0.0287 (10)	−0.0147 (10)	0.0006 (8)	−0.0044 (8)
N6	0.0667 (15)	0.0414 (12)	0.0314 (11)	−0.0209 (10)	0.0021 (10)	−0.0027 (9)
S2	0.0637 (4)	0.0434 (4)	0.0286 (3)	−0.0142 (3)	−0.0008 (3)	−0.0043 (2)

Geometric parameters (Å, º) top

C1—N1	1.285 (3)	C16—H17A	0.98 (3)
C1—C5	1.461 (3)	C16—H17B	1.00 (3)
C1—C2	1.504 (3)	C17—C18	1.341 (3)
C2—C3	1.533 (3)	C17—C24	1.492 (3)
C2—H5A	1.00 (3)	C18—C19	1.506 (3)
C2—H5B	0.97 (3)	C19—C20B	1.359 (14)
C3—C4	1.500 (3)	C19—C20A	1.493 (4)
C3—H4A	0.96 (2)	C19—H19A	0.9700
C3—H4B	0.95 (2)	C19—H19B	0.9700
C4—C5	1.342 (3)	C19—H19C	0.9700
C4—C12	1.488 (3)	C19—H19D	0.9700
C5—C6	1.509 (3)	C20A—C21A	1.339 (5)
C6—C7	1.498 (4)	C20A—H20A	0.9300
C6—H6A	0.97 (2)	C21A—C22A	1.445 (5)
C6—H6B	0.92 (3)	C21A—H21A	0.9300
C7—C8	1.323 (4)	C22A—C23A	1.530 (5)
C7—H7	0.93 (3)	C22A—H22A	0.9700
C8—C9	1.488 (5)	C22A—H22B	0.9700
C8—H8	0.96 (3)	C23A—H23A	0.9600
C9—C10	1.505 (5)	C23A—H23B	0.9600
C9—H9A	1.07 (4)	C23A—H23C	0.9600
C9—H9B	1.00 (4)	C20B—C21B	1.29 (2)
C10—H10A	1.00 (4)	C20B—H20B	0.9300
C10—H10B	0.93 (4)	C21B—C22B	1.56 (3)
C10—H10C	0.96 (4)	C21B—H21B	0.9300
C11—N3	1.329 (3)	C22B—C23B	1.47 (3)
C11—N2	1.351 (3)	C22B—H22C	0.9700
C11—S1	1.680 (2)	C22B—H22D	0.9700
C12—H11A	1.02 (3)	C23B—H23D	0.9600
C12—H11B	0.91 (3)	C23B—H23E	0.9600
C12—H11C	0.96 (3)	C23B—H23F	0.9600
C13—N3	1.455 (3)	C24—H24A	0.97 (4)
C13—H13A	0.9600	C24—H24B	1.02 (3)
C13—H13B	0.9600	C24—H24C	0.97 (3)
C13—H13C	0.9600	C25—N6	1.335 (3)
N1—N2	1.392 (3)	C25—N5	1.357 (3)
N2—H1	0.81 (3)	C25—S2	1.678 (2)
N3—H2	0.83 (3)	C26—N6	1.453 (3)
C14—N4	1.292 (3)	C26—H26A	0.9600
C14—C18	1.463 (3)	C26—H26B	0.9600
C14—C15	1.498 (3)	C26—H26C	0.9600
C15—C16	1.535 (3)	N4—N5	1.394 (2)
C15—H18A	0.93 (2)	N5—H3	0.84 (3)
C15—H18B	0.97 (3)	N6—H4	0.85 (3)
C16—C17	1.505 (3)

N1—C1—C5	122.2 (2)	C17—C16—H17B	112.7 (14)
N1—C1—C2	129.2 (2)	C15—C16—H17B	111.6 (14)
C5—C1—C2	108.56 (18)	H17A—C16—H17B	104 (2)
C1—C2—C3	104.79 (19)	C18—C17—C24	127.8 (2)
C1—C2—H5A	111.1 (15)	C18—C17—C16	112.35 (19)
C3—C2—H5A	113.8 (15)	C24—C17—C16	119.8 (2)
C1—C2—H5B	114.0 (16)	C17—C18—C14	109.11 (19)
C3—C2—H5B	111.5 (15)	C17—C18—C19	128.8 (2)
H5A—C2—H5B	102 (2)	C14—C18—C19	122.04 (19)
C4—C3—C2	104.5 (2)	C20B—C19—C18	125.2 (6)
C4—C3—H4A	111.7 (14)	C20A—C19—C18	109.9 (2)
C2—C3—H4A	112.7 (14)	C20A—C19—H19A	109.7
C4—C3—H4B	108.8 (14)	C18—C19—H19A	109.7
C2—C3—H4B	112.6 (14)	C20A—C19—H19B	109.7
H4A—C3—H4B	107 (2)	C18—C19—H19B	109.7
C5—C4—C12	127.4 (2)	H19A—C19—H19B	108.2
C5—C4—C3	112.30 (19)	C20B—C19—H19C	106.0
C12—C4—C3	120.3 (2)	C18—C19—H19C	106.0
C4—C5—C1	109.8 (2)	C20B—C19—H19D	106.0
C4—C5—C6	127.5 (2)	C18—C19—H19D	106.0
C1—C5—C6	122.7 (2)	H19C—C19—H19D	106.3
C7—C6—C5	114.0 (2)	C21A—C20A—C19	133.1 (3)
C7—C6—H6A	110.1 (13)	C21A—C20A—H20A	113.5
C5—C6—H6A	111.0 (13)	C19—C20A—H20A	113.5
C7—C6—H6B	107.0 (16)	C20A—C21A—C22A	126.4 (4)
C5—C6—H6B	110.0 (17)	C20A—C21A—H21A	116.8
H6A—C6—H6B	104 (2)	C22A—C21A—H21A	116.8
C8—C7—C6	127.3 (3)	C21A—C22A—C23A	110.4 (3)
C8—C7—H7	119.7 (17)	C21A—C22A—H22A	109.6
C6—C7—H7	112.9 (17)	C23A—C22A—H22A	109.6
C7—C8—C9	128.0 (3)	C21A—C22A—H22B	109.6
C7—C8—H8	117.7 (16)	C23A—C22A—H22B	109.6
C9—C8—H8	114.3 (15)	H22A—C22A—H22B	108.1
C8—C9—C10	113.3 (3)	C22A—C23A—H23A	109.5
C8—C9—H9A	106 (2)	C22A—C23A—H23B	109.5
C10—C9—H9A	112 (2)	H23A—C23A—H23B	109.5
C8—C9—H9B	107 (2)	C22A—C23A—H23C	109.5
C10—C9—H9B	109 (2)	H23A—C23A—H23C	109.5
H9A—C9—H9B	110 (3)	H23B—C23A—H23C	109.5
C9—C10—H10A	113.2 (19)	C21B—C20B—C19	122.2 (14)
C9—C10—H10B	113 (2)	C21B—C20B—H20B	118.9
H10A—C10—H10B	107 (3)	C19—C20B—H20B	118.9
C9—C10—H10C	110 (2)	C20B—C21B—C22B	157.0 (17)
H10A—C10—H10C	105 (3)	C20B—C21B—H21B	101.5
H10B—C10—H10C	108 (3)	C22B—C21B—H21B	101.5
N3—C11—N2	116.2 (2)	C23B—C22B—C21B	112.7 (18)
N3—C11—S1	122.86 (18)	C23B—C22B—H22C	109.0
N2—C11—S1	120.97 (19)	C21B—C22B—H22C	109.0
C4—C12—H11A	109.5 (17)	C23B—C22B—H22D	109.0
C4—C12—H11B	111.9 (18)	C21B—C22B—H22D	109.0
H11A—C12—H11B	108 (2)	H22C—C22B—H22D	107.8
C4—C12—H11C	112.6 (18)	C22B—C23B—H23D	109.5
H11A—C12—H11C	110 (2)	C22B—C23B—H23E	109.5
H11B—C12—H11C	105 (3)	H23D—C23B—H23E	109.5
N3—C13—H13A	109.5	C22B—C23B—H23F	109.5
N3—C13—H13B	109.5	H23D—C23B—H23F	109.5
H13A—C13—H13B	109.5	H23E—C23B—H23F	109.5
N3—C13—H13C	109.5	C17—C24—H24A	114 (2)
H13A—C13—H13C	109.5	C17—C24—H24B	110.5 (16)
H13B—C13—H13C	109.5	H24A—C24—H24B	108 (3)
C1—N1—N2	116.5 (2)	C17—C24—H24C	110.6 (18)
C11—N2—N1	119.4 (2)	H24A—C24—H24C	109 (3)
C11—N2—H1	119.8 (19)	H24B—C24—H24C	105 (2)
N1—N2—H1	120.8 (19)	N6—C25—N5	115.3 (2)
C11—N3—C13	123.6 (2)	N6—C25—S2	123.71 (17)
C11—N3—H2	118 (2)	N5—C25—S2	120.96 (17)
C13—N3—H2	118 (2)	N6—C26—H26A	109.5
N4—C14—C18	120.8 (2)	N6—C26—H26B	109.5
N4—C14—C15	129.58 (19)	H26A—C26—H26B	109.5
C18—C14—C15	109.57 (18)	N6—C26—H26C	109.5
C14—C15—C16	104.14 (19)	H26A—C26—H26C	109.5
C14—C15—H18A	112.0 (15)	H26B—C26—H26C	109.5
C16—C15—H18A	112.9 (14)	C14—N4—N5	116.71 (18)
C14—C15—H18B	109.4 (14)	C25—N5—N4	117.8 (2)
C16—C15—H18B	112.9 (14)	C25—N5—H3	120.8 (17)
H18A—C15—H18B	106 (2)	N4—N5—H3	121.4 (17)
C17—C16—C15	104.81 (19)	C25—N6—C26	124.3 (2)
C17—C16—H17A	111.6 (15)	C25—N6—H4	117.6 (17)
C15—C16—H17A	112.8 (14)	C26—N6—H4	118.0 (18)

N1—C1—C2—C3	−177.8 (2)	C15—C16—C17—C18	1.3 (3)
C5—C1—C2—C3	0.0 (3)	C15—C16—C17—C24	−178.2 (2)
C1—C2—C3—C4	1.2 (3)	C24—C17—C18—C14	178.0 (2)
C2—C3—C4—C5	−2.2 (3)	C16—C17—C18—C14	−1.4 (3)
C2—C3—C4—C12	177.1 (2)	C24—C17—C18—C19	−4.4 (4)
C12—C4—C5—C1	−176.9 (2)	C16—C17—C18—C19	176.2 (2)
C3—C4—C5—C1	2.3 (3)	N4—C14—C18—C17	−177.4 (2)
C12—C4—C5—C6	2.3 (4)	C15—C14—C18—C17	0.9 (3)
C3—C4—C5—C6	−178.5 (2)	N4—C14—C18—C19	4.8 (3)
N1—C1—C5—C4	176.6 (2)	C15—C14—C18—C19	−176.9 (2)
C2—C1—C5—C4	−1.4 (3)	C17—C18—C19—C20B	−0.8 (9)
N1—C1—C5—C6	−2.7 (3)	C14—C18—C19—C20B	176.5 (9)
C2—C1—C5—C6	179.3 (2)	C17—C18—C19—C20A	−91.4 (3)
C4—C5—C6—C7	73.9 (3)	C14—C18—C19—C20A	85.9 (3)
C1—C5—C6—C7	−107.0 (3)	C18—C19—C20A—C21A	139.9 (4)
C5—C6—C7—C8	114.6 (3)	C19—C20A—C21A—C22A	2.8 (6)
C6—C7—C8—C9	−2.1 (5)	C20A—C21A—C22A—C23A	121.9 (4)
C7—C8—C9—C10	128.0 (4)	C18—C19—C20B—C21B	−117.6 (13)
C5—C1—N1—N2	−179.33 (19)	C19—C20B—C21B—C22B	−4 (5)
C2—C1—N1—N2	−1.8 (4)	C20B—C21B—C22B—C23B	−95 (4)
N3—C11—N2—N1	−1.2 (3)	C18—C14—N4—N5	178.16 (19)
S1—C11—N2—N1	178.55 (17)	C15—C14—N4—N5	0.2 (4)
C1—N1—N2—C11	173.8 (2)	N6—C25—N5—N4	0.8 (3)
N2—C11—N3—C13	−175.1 (2)	S2—C25—N5—N4	−179.57 (16)
S1—C11—N3—C13	5.1 (4)	C14—N4—N5—C25	−175.3 (2)
N4—C14—C15—C16	178.1 (2)	N5—C25—N6—C26	176.9 (2)
C18—C14—C15—C16	−0.1 (3)	S2—C25—N6—C26	−2.7 (4)
C14—C15—C16—C17	−0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···S1ⁱ	0.81 (3)	2.80 (3)	3.591 (2)	167 (2)
C2—H5B···S1ⁱ	0.97 (3)	2.90 (3)	3.457 (2)	117.4 (18)
N5—H3···S2ⁱⁱ	0.84 (3)	2.75 (3)	3.585 (2)	172 (2)
C15—H18A···S2ⁱⁱ	0.93 (2)	2.98 (2)	3.472 (2)	115.0 (17)

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

Selected geometric parameters (Å, °) for the two crystallographically independent cis-jasmone 4-methylthiosemicarbazone molecules, JMTSC-1 and JMTSC-2 top

Compound	Atom chain	Torsion angle	Atom chain	Torsion angle
JMTSC-1	N1/N2/C11/N3	-1.2 (3)	C5/C6/C7/C8	114.6 (3)
JMTSC-1	N1/N2/C11/S1	178.55 (17)	C7/C8/C9/C10	128.0 (4)
JMTSC-2	N4/N5/C25/N6	0.8 (3)	C18/C19/C20A/C21A	139.9 (4)
JMTSC-2	N4/N5/C25/S2	-179.57 (16)	C18/C19/C20B/C21B	-117.6 (13)
			C20A/C21A/C22A/C23A	121.9 (4)
			C20B/C21B/C22B/C23B	-95 (4)

	Fragment	Max. deviation^a	r.m.s.d.	Angle^b
JMTSC-1	N1/N2/C11/S1/N3	-0.0115 (16) [N2]	0.0078
JMTSC-1	C1-C5 ring	0.0130 (16) [C4]	0.0089	8.9 (1)
JMTSC-2	N4/N5/C25/S2/N6	0.0052 (14) [N5]	0.0031
JMTSC-2	C14-C18 ring	0.0078 (16) [C17]	0.0054	6.3 (1)

	Bond lengths^c	N—N	N—C	C=S
JMTSC-1		1.392 (3)	1.351 (3)	1.680 (2)
JMTSC-2		1.394 (2)	1.357 (3)	1.678 (2)

Notes: (a) The maximum deviation from the mean plane through the selected atoms; (b) angle to previous plane; (c) bond lengths for the N1/N2/C11/S1 and N4/N5/C25/S2 entities.

Acknowledgements

We gratefully acknowledge financial support by the State of North Rhine-Westphalia, Germany. ABO is a former DAAD scholarship holder and alumnus of the University of Bonn, Germany, and thanks both of the institutions for the long-time support.

Funding information

Funding for this research was provided by: Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brazil (CAPES) - Finance Code 001.

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