A second crystalline modification of 2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclopent-2-en-1-ylidene}hydrazinecarbothioamide

The crystal structure and Hirshfeld analysis of a second crystalline modification of the cis-jasmone thiosemicarbazone is reported. The molecular structure matches the asymmetric unit and the molecules are linked into mono-periodic hydrogen-bonded ribbons along [010].


Structure description
The first references to the synthesis of thiosemicarbazone derivatives [R 1 R 2 N-N(H)-C( S)-NR 3 R 4 ] can be traced back to the beginning of the 1900s (Freund & Schander, 1902) and since the report of Domagk et al. (1946) on the tuberculostatic effect of some compounds with this functional group, the biological activity of these molecules has been intensively studied, being one of the major approaches for this chemistry (for some examples, see: Acharya et al., 2021;Bajaj et al., 2021;Kanso et al., 2021;Siqueira et al., 2019).Concerning the cisjasmone thiosemicarbazone, it has been pointed out that this compound has antifungal activity (Orsoni et al., 2020;Jamiołkowska et al., 2022).As part of our studies on the thiosemicarbazone derivatives of natural products, the crystal structure and the Hirshfeld analysis of a new crystalline modification of the cis-jasmone thiosemicarbazone is reported herein.
For the title compound, the �-crystalline modification of the cis-jasmone thiosemicarbazone, there is one molecule with all atoms in general positions in the asymmetric unit, which shows disorder in the cis-jasmone chain [s.o.f.= 0.590 (14): 0.410 ( 14)].The atoms with the higher s.o.f. are A-labelled and those with the lower, B-labelled (Fig. 1).The thiosemicarbazone (TSC) entity is approximately planar, with the maximum deviation from the mean plane through the N1/N2/ C12/S1/N3 atoms being 0.0463 (14) A ˚for N2 (r.m.s.d.= 0.0324 A ˚).The TSC entity is attached to the C1-C5 fivemembered ring of the jasmone fragment, which is also almost planar, with the maximum deviation from the mean plane through the C atoms being 0.0465 (15) A ˚for C2 (r.m.sd.= 0.0338 A ˚).The molecule is not planar due the dihedral angle between these two entities, 8.93 (1) � , and due to the sp 3hybridized carbon atoms in the jasmone fragment.In addition, the torsion angles for the N1/N2/C12/S1 and N1/N2/C12/N3 chains are 174.04(15) and À 4.8 (3) � , respectively.
In the crystal, the molecules are connected by pairs of N-H� � �S interactions, forming rings with R 2 2 (8) graph-set motif, and by pairs of N-H� � �S/C-H� � �S interactions, where rings of graph-set motif R 1 2 (7) are observed (Fig. 2, Table 1).The N1, N3 and C2 atoms act as hydrogen-bond donors and the S1 atoms act as hydrogen-bond acceptors, connecting the molecules into mono-periodic hydrogen-bonded ribbons along [010] (Fig. 3).No other strong intermolecular interactions are observed for the title compound, possibly due to the non-polar organic periphery of the cis-jasmone fragment, and only weak interactions, i.e., London dispersion forces can be suggested.
In the Hirshfeld surface analysis (Hirshfeld, 1977), the graphical representations and the two-dimensional Hirshfeld surface fingerprint (HSFP) were evaluated with Crystal Explorer (Wolff et al., 2012).The Hirshfeld surface analysis of the title compound considering the A-labelled atoms [s.o.f.= 0.590 ( 14 Since no considerable differences between the values were observed, the evaluations and graphics were performed for the structure with the A-labelled atoms only.The graphical representation of the Hirshfeld surface (d norm ) is drawn in a figure with two separate opposite side-views of the molecule with transparency and using a ball-and-stick model.The locations of the strongest intermolecular contacts, i.e, the regions around the H1, H3 and S1 atoms (Fig. 4) are indicated in red.These atoms are those involved in the H� � �S interactions shown in the previous figures (Figs. 2 and 3).The contributions to the crystal packing are shown as two-dimensional Hirshfeld surface fingerprint plots (HSFP) with cyan dots (Fig. 5).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 (in A ˚).
The crystal structure of the �-crystalline modification of the cis-jasmone thiosemicarbazone was reported recently (Orsoni et al., 2020).As already mentioned above, the �-modification has three crystallographically independent molecules in the asymmetric unit, namely �-JATSC(A), �-JATSC(B) and �-JATSC(C).In the crystal, the molecules are connected by pairs of N-H� � �S interactions, with graph-set motif R 2 2 (8), into mono-periodic hydrogen-bonded ribbons along [100]  (Fig. 6).The �-modification contains two crystallographically different strands.Within one of the strands, inversion centres are located at the centroids of every eight-membered C 2 H 2 N 2 S 2 ring, while the other strand has no internal symmetry.The �-modification has only one independent strand that has no internal symmetry.For a comparison of selected geometric parameters of the �-and �-modifications of cis-jasmone thiosemicarbazone, see Table 2.The crystal structures of non-substituted thiosemicarbazones attached to non-polar organic groups have been studied by our group, such as the structures of the (À )-menthone (Oliveira et al., 2014) and the tetralone thiosemicarbazone derivatives (Oliveira et al., 2012(Oliveira et al., , 2017)).In the structure of the (À )-menthone thiosemicarbazone, the molecules are linked by N-H� � �S intermolecular interactions, forming rings with graph-set motif R 2 2 (8), into mono-periodic hydrogen-bonded ribbons along [100].For the structure of the tetralone thiossemicarbazone, the molecules are connected by N-H� � �S and C-H� � �S intermolecular interactions along [110], where rings of graph-set motifs R 2 2 (8) and R 1 2 (7) are observed.The same supramolecular arrangement was observed for both structures, forming a structural pattern for these entities (Fig. 7).This packing pattern is common for non-substituted thiosemicarbazones attached to non-polar organic entities, as observed in this work (Fig. 3).Selected geometric parameters (A ˚, � ) of the TSC entities for the �-and �-crystalline modifications of the cis-jasmone thiosemicarbazone.

Synthesis and crystallization
The starting materials are commercially available and were used without further purification.The synthesis of cis-jasmone thiosemicarbazone was adapted from previously reported procedures (Freund & Schander, 1902;Oliveira et al., 2017;Orsoni et al., 2020).The mixture of ethanolic solutions of cisjasmone (8 mmol in 50 ml) and thiosemicarbazide (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 solution by slow evaporation of the solvent at room temperature.The template effect of the crystallization solvent and the temperature can be suggested as factors for the formation of the new crystalline modification of the cis-jasmone thiosemicarbazone, since the �-crystalline modification was crystallized from ethanol solution at 273 K (Orsoni et al., 2020).

Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3.The molecule of title compound shows disorder over the chain of the cis-jasmone fragment, namely the H8, C9 and C10 atoms (Fig. 1), which are Alabelled for the atoms with the higher s.o.f.value and Blabelled for the lower [site-occupancy ratio = 0.590 (14):0.410( 14)].H atoms attached to the C2, C3, C6, C7, C11, N2 and N3 atoms were located in the difference Fourier map.The one bonded to N2 was refined freely, and those bonded to C2, C3, C6, C7, C11, and N3 were refined freely using the same isotropic displacement parameter for the atoms bonded to the same parent atom.The remaining hydrogen atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined isotropically using a riding model (HFIX command).Methyl H atoms were allowed to rotate but not to tip to best fit the experimental electron density.Thus, for the C10AH 3 and C10BH 3 fragments, with U iso (H) = 1.5 U eq (C), the C-H bond lengths were set to 0.96 A ˚.For the H atoms attached to the C8 atom and to the C9A and C9B atoms, with U iso (H) = 1.2 U eq (C), the C-H bond lengths were set to 0.93 and 0.97 A ˚, respectively.(Nonius, 1998), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL2018/3 (Sheldrick, 2015), DIAMOND (Brandenburg, 2006), CrystalExplorer (Wolff et al., 2012), WinGX (Farrugia, 2012), publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).
Figure 3 Graphical representation of the N-H� � �S and C-H� � �S intermolecular interactions in the title compound viewed along [100].The interactions are drawn as dashed lines and connect the molecules along [010] with graph-set motifs of R 2 2 (8) and R 1 2 (7), forming a mono-periodic hydrogenbonded ribbon.Disorder is not shown for clarity.

Figure 4 Figure 5
Figure 4 Two opposite side-views in separate figures of the Hirshfeld surface graphical representation (d norm ) for the title compound.The surface is drawn with transparency, the molecule is drawn in ball and stick mode and the disorder is not shown for clarity.The regions with strongest intermolecular interactions are shown in red.(d norm range: À 0.404 to 1.518.) viewed along [001].Selected atoms of the TSC entities are labelled to indicate the three crystallographically independent molecules [�-JATSC(A); �-JATSC(B); �-JATSC(C)].The N-H� � �S intermolecular interactions, forming rings with graph-set motif R 2 2 (8), are drawn as dashed lines and connect the molecules into mono-periodic H-bonded ribbons along [100].

Figure 7 (
Figure7(a) (À )-Menthone thiosemicarbazone(Oliveira et al., 2014) and (b) tetralone thiosemicarbazone(Oliveira et al., 2012) graphical representations of the mono-periodic hydrogen-bonded ribbons structures along [100] and[110], respectively.The molecules are connected by H� � �S intermolecular interactions drawn as dashed lines.The atoms of the TSC entities and one C-H donor in general positions are labelled.This packing pattern is common for non-substituted thiosemicarbazones attached to non-polar organic entities.

Table 3
Experimental details.
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