Synthesis, crystal structure and Hirshfeld analysis of N-ethyl-2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclo­pent-2-en-1-yl­­idene}hydrazinecarbo­thio­amide

The title compound (C₁₄H₂₃N₃S, common name: cis-jasmone 4-ethyl­thio­semicarbazone) was synthesized by the equimolar reaction of cis-jasmone and 4-ethyl­thio­semicarbazide in ethanol facilitated by acid catalysis. There is one crystallographically independent mol­ecule in the asymmetric unit, which shows disorder of the terminal ethyl group of the jasmone carbon chain [site-occupancy ratio = 0.911 (5):0.089 (5)]. The thio­semicarbazone entity [N—N—C(=S)—N] is approximately planar, with the maximum deviation of the mean plane through the N/N/C/S/N atoms being 0.0331 (8) Å, while the maximum deviation of the mean plane through the five-membered ring of the jasmone fragment amounts to −0.0337 (8) Å. The dihedral angle between the two planes is 4.98 (7)°. The mol­ecule is not planar due to this structural feature and the sp³-hybridized atoms of the jasmone carbon chain. Additionally, one H⋯N intra­molecular inter­action is observed, with graph-set motif S(5). In the crystal, the mol­ecules are connected through pairs of H⋯S inter­actions with R₂²(8) and R₂¹(7) graph-set motifs into centrosymmetric dimers. The dimers are further connected by H⋯N inter­actions with graph-set motif R₂²(12), which are related by an inversion centre, forming a mono-periodic hydrogen-bonded ribbon parallel to the b-axis. The crystal structure and the supra­molecular assembly of the title compound are compared with four known cis-jasmone thio­semicarbazone derivatives (two crystalline modifications of the non-substituted form, the 4-methyl and the 4-phenyl derivatives). A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are from H⋯H (70.7%), H⋯S/S⋯H (13.5%), H⋯C/C⋯H (8.8%), and H⋯N/N⋯H (6.6%) inter­faces (only the disordered atoms with the highest s.o.f. were considered for the evaluation).

1. Chemical context

Thio­semicarbazones [R₁R₂C=N—N(H)C(=S)NR₃R₄] can be readily prepared through a well-known condensation reaction between a ketone or an aldehyde (R₁R₂C=O) and a thio­semicarbazide derivative [H₂N—N(H)C(=S)NR₃R₄] (Freund & Schander, 1902). Due to the structural diversity of the educts, a huge number of thio­semicarbazone derivatives (TSC) can be synthesized for numerous applications across a wide range of scientific disciplines, such as coordination chemistry, medicinal chemistry and materials science. These three main approaches are inter­connected, as demonstrated by Farias et al. (2021) in a report concerning the synthesis, in vitro and in silico evaluations of the anti­tumor activities of two thio­semicarbazone Ni^II complexes, which were considered materials with biological properties. The coordination chemistry of thio­semicarbazone derivatives was addressed in a review by Lobana et al. (2009), illustrating the chemical bonding of TSCs with metal centres of different Lewis acidity, the coordination modes and geometries, and some biological and analytical applications.

Several thio­semicarbazone derivatives have biological properties either as metal complexes or as non-coordinated mol­ecules. For examples of thio­semicarbazone complexes with biological activity, see: Gupta et al. (2022); Khan et al. (2022); Monsur Showkot Hossain et al. (2023); Parrilha et al. (2022), which covers compounds for chemotherapy and medical diagnostic imaging combined, also referred to as theranostics, and Singh et al. (2023). For a review of TSC complexes in the inhibition of topoisomerases, which are biological targets of prime importance in cancer research, see: Jiang et al. (2023). For examples of the biological activity of non-coordinated thio­semicarbazone derivatives, see: Fatondji et al. (2013), which shows a small chemical library with 35 derivatives with trypanocidal activity against the Trypanosoma brucei brucei parasite, and for a review on tyrosinase inhibitory activity, which is another important biological target, see: Hałdys & Latajka (2019). The non-coordinated TSCs are also mentioned in a review on tyrosinase inhibition by Zolghadri et al. (2019). In addition, thio­semicarbazone derivatives have been studied for the treatment of Parkinson's disease (Mathew et al., 2021), microbial growth inhibition (D'Agostino et al., 2022), anti-inflammatory pathologies (Kanso et al., 2021) and anti­fungal activity (Bajaj et al., 2021). Specifically, in the context of this work, the parent cis-jasmone thio­semicarbazone derivative has shown fungistatic biological activity as a free mol­ecule (Jamiołkowska et al., 2022) and also as a Cu^II complex (Orsoni et al., 2020).

In materials science, thio­semicarbazone complexes are employed as single-source educts for the synthesis of nanostructured materials, e.g., CdS nanocrystals (Masikane et al., 2019) and nanostructured CuFeS₂, which is being used as an electrode material for supercapacitors (Ansari et al., 2022). Non-coordinated thio­semicarbazones have been used to functionalize metal–organic frameworks (MOFs), such as zeolitic imidazolate frameworks (mainly, ZIF-8), for the removal of Hg^II from aqueous solutions at room temperature and neutral pH (Jaafar et al., 2021). TSC derivatives have also been studied as corrosion inhibitors for metals and alloys. For the respective theoretical approach, see: Silva & Martínez-Huitle (2021). Additionally, thio­semicarbazone derivatives have turned out to be useful in several fields of analytical chemistry, including calorimetry, fluorimetry and electrochemical sensors, e.g., in the detection of anions and metallic cations (Özbek & Berkel, 2023).

In this context and as a contribution to the TSC chemistry, we report here the synthesis, crystal structure and Hirshfeld analysis of cis-jasmone 4-ethyl­thio­semicarbazone.

2. Structural commentary

For the title compound, cis-jasmone 4-ethyl­thio­semicarbazone (JETSC), the asymmetric unit consists of one mol­ecule with all atoms in general positions, which shows disorder over the jasmone carbon chain [s.o.f. = 0.911 (5):0.089 (5)]. The disordered atoms with higher s.o.f. are A-labelled and the atoms with lower s.o.f. are B-labelled (Fig. 1). The thio­semicarbazone entity is approximately planar, with the maximum deviation of the mean plane through the N1/N2/C12/S1 atoms being 0.0331 (8) Å for N2 (r.m.s.d. = 0.0215 Å). For the five-membered ring of the jasmone fragment, the maximum deviation of the mean plane through the selected atoms amounts to −0.0337 (8) Å for C2 (r.m.s.d. = 0.0256 Å) and the dihedral angle between the two planes is 4.98 (7)°. The mol­ecule is not planar due to this angle and to the sp³-hybridized atoms of the jasmone carbon chain, with the torsion angles for the C5—C6—C7—C8, C7—C8—C9A—C10A and C7—C8— C9B—C10B fragments being −138.74 (16), −106.5 (2) and 132.7 (10)°. Finally, an intra­molecular hydrogen-bond inter­action is observed, N3—H3⋯N1, which forms a ring of graph-set motif S(5) (Fig. 1 and Table 1). For a review addressing hydrogen bonding in the solid state, see: Steiner (2002).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S1^i	0.873 (18)	2.608 (18)	3.4808 (12)	177.6 (15)
N3—H3⋯N1	0.828 (16)	2.187 (15)	2.6008 (15)	111.0 (13)
C2—H2A⋯S1^i	1.003 (16)	2.822 (15)	3.3535 (13)	113.7 (10)
C13—H13B⋯N1^ii	0.966 (15)	2.655 (15)	3.5466 (17)	153.5 (12)
Symmetry codes: (i) ; (ii) .

Figure 1 The mol­ecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 40% probability level. Disordered atoms are drawn with 40% transparency and labelled C9A/C10A [s.o.f. = 0.911 (5)] and C9B/C10B [s.o.f. = 0.089 (5)]. For the N3—H3⋯N1 intra­molecular inter­action, a ring with graph-set motif S(5) is observed.

3. Supra­molecular features

In the crystal, the mol­ecules are connected through H⋯S and H⋯N inter­actions, forming rings of graph-set motifs R₂²(8), R₂¹(7) and R₂²(12) for the C₂H₂N₂S₂, C₂H₂N₂S and C₄H₂N₆ entities, respectively (Fig. 2). The S1 and N1 atoms act as double hydrogen-bond acceptors, where the N1 atoms play an important role in the supra­molecular arrangement of the mol­ecules. Firstly, the mol­ecules are connected into centrosymmetric dimers through C2—H2A⋯S1ⁱ and N2—H2⋯S1ⁱ inter­molecular inter­actions [symmetry code: (i) −x + 1, −y, −z + 1], as has also been observed in other cis-jasmone thio­semicarbazone derivatives (Oliveira et al., 2023a, 2024). These centrosymmetric dimers, in which rings of graph-set motif R₂²(8) and R₂¹(7) are present, have their centres of gravity located in the centre of the ac planes. In addition, the dimers are further connected by C13—H13B⋯N1ⁱⁱ inter­molecular inter­actions [symmetry code: (ii) −x + 1, −y + 1, −z + 1], where rings of graph-set motif R₂²(12) are observed (Fig. 2, Table 1). The centre of gravity of the centrosymmetric C₄H₂N₆ ring lies at an inversion centre of the cell and thus, the mol­ecules are linked into a mono-periodic hydrogen-bonded ribbon parallel to the b-axis. (Fig. 3).

Figure 2 Crystal structure section of the title compound showing the inter­molecular hydrogen-bonding inter­actions as dashed lines. The mol­ecules are linked via pairs of C2—H2A⋯S1^i, N—H2⋯S1^i and C13—H13B—N1^ii inter­actions with graph-set motifs R2^2(8), R2^1(7) and R2^2(12). [Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) −x + 1, −y + 1, −z + 1.]

Figure 3 Crystal structure section of the title compound, showing the inter­molecular hydrogen-bonded inter­actions as dashed lines. Disorder is not shown for clarity. The mol­ecules are linked into mono-periodic hydrogen-bonded ribbons parallel to the b-axis via pairs of N—H⋯S, C—H⋯S and C—H⋯N inter­actions with graph-set motifs R2^2(8), R2^1(7) and R2^2(12).

The Hirshfeld surface analysis (Hirshfeld, 1977), the graphical representations and the two-dimensional Hirshfeld surface fingerprint plots (HSFP) were calculated with the Crystal Explorer software (Wolff et al., 2012) and only the atoms with the higher s.o.f. were taken into account. The Hirshfeld surface analysis of the title compound suggests that the most relevant inter­molecular inter­actions for the crystal packing are H⋯H (70.7%), H⋯S/S⋯H (13.5%), H⋯C/C⋯H (8.8%) and H ⋯N/N⋯H (6.4%). The graphical representation of the Hirshfeld surface (d_norm) is given in a figure with transparency and using the ball-and-stick model. Locations of the strongest inter­molecular contacts, i.e, the regions around the H2, H2A and S1 atoms are indicated in red (Fig. 4). These atoms are those involved in the H⋯S inter­actions shown in previous figures (Figs. 2 and 3). The contributions to the crystal cohesion are represented as two-dimensional Hirshfeld surface fingerprint plots (HSFP) with coloured 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 contacts (in Å).

Figure 4 Hirshfeld surface graphical representation (dnorm) for the title compound. The surface is drawn with transparency, the mol­ecules are drawn in ball and stick model and the disorder is not shown for clarity. The regions with strongest inter­molecular inter­actions are shown in red.

Figure 5 The Hirshfeld surface two-dimensional fingerprint plot (HSFP) for the title compound, showing the contacts in detail (coloured). The major contributions of the inter­actions to the crystal cohesion amount to (a) H⋯H (70.7%), (b) H⋯S/S⋯H (13.5%), (c) H⋯C/C⋯H (8.8%) and (d) H⋯N/N⋯H (6.4%). The di (x-axis) and the de (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.

4. Database survey

To the best of our knowledge and from using database tools such as the Cambridge Structural Database (CSD, accessed via WebCSD on March 15, 2024; Groom et al., 2016), there are four crystal structures of cis-jasmone thio­semicarbazone derivatives reported in the literature: the α-crystalline modification of cis-jasmone thio­semicarbazone, α-JTSC (refcode ZAJRUB; Orsoni et al., 2020), the β-crystalline modification, β-JTSC (ZAJRUB01; Oliveira et al., 2023b), cis-jasmone 4-methyl­thio­semicarbazone, JMTSC (JOFYOW; Oliveira et al., 2024), cis-jasmone 4-phenyl­thio­semicarbazone, JPTSC (QIVYIH; Oliveira et al., 2023a), with cis-jasmone 4-ethyl­thio­semicarbazone, JETSC (this work) being the fifth. For the Hirshfeld analysis comparison, of the α-JTSC and the β-JTSC crystalline modifications, only β-JTSC was considered and will be designated in the following merely as JTSC. Fig. 6 provides the chemical structures of JTSC, JMTSC, JETSC and JPTSC. The Hirshfeld surface fingerprint signatures of the TSC derivatives are drawn as two-dimensional plots (HSFP) and the most relevant contribution for the crystal packing, the H⋯H inter­molecular inter­actions, are highlighted (coloured) (Fig. 7). Their contributions for the crystal cohesion are 67.8% for JTSC, 70.6% for JMTSC, 70.7% for the title compound, JETSC, and 65.3% for JPTSC. It might be argued that the methyl and ethyl derivatives show more C—H entities for H⋯H inter­molecular inter­actions in comparison to the non-substituted JTSC, and less steric hindrance than the phenyl derivative JPTSC. These structural features would explain the higher values of the H⋯H contributions to the crystal packing for JMTSC and JETSC, and the lower contributions for JTSC and JPTSC. In addition, the H⋯N/N⋯H contacts, which are important for the supra­molecular arrangement of JETSC (this work) are clearly represented in the HSFP signature of the crystal structure and do not appear in the same way in the signature of the related compounds (Fig. 8). Although the contributions of the H⋯N/N⋯H contacts to the crystal packing for all the jasmone thio­semicarbazone derivatives are very similar in value, within a range of 4.9% to 6.4%, the H⋯N inter­molecular inter­actions are of major importance for the mol­ecular assembly of JETSC, as shown in Figs. 2 and 3.

Figure 6 Chemical structure formulae of (a) cis-jasmone thio­semicarbazone, JTSC, (b) cis-jasmone 4-methyl­thio­semicarbazone, JMTSC, (c) cis-jasmone 4-ethyl­thio­semicarbazone, JETSC, and (d) cis-jasmone 4-phenyl­thio­semicarbazone, JPTSC.

Figure 7 The Hirshfeld surface two-dimensional fingerprint plot (HSFP) signatures for (a) JTSC (Oliveira et al., 2023b), (b) JMTSC (Oliveira et al., 2024), (c) JETSC (this work) and (d) JPTSC (Oliveira et al., 2023a). The major contributions for the crystal cohesion in all structures are the H⋯H inter­molecular inter­actions, which amount to 67.8%, 70.6%, 70.7% and 65.3%, respectively, and are highlighted (coloured). The di (x-axis) and the de (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.

Figure 8 The Hirshfeld surface two-dimensional fingerprint plot (HSFP) signatures for (a) JTSC (Oliveira et al., 2023b), (b) JMTSC (Oliveira et al., 2024), (c) JETSC (this work) and (d) JPTSC (Oliveira et al., 2023a), with the H⋯N/N⋯H contacts highlighted (coloured). The di (x-axis) and the de (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 influence of the substituent at the terminal N atom on the supra­molecular assembly in the crystal structures of jasmone TSC derivatives is shown in Figs. 9 and 10. For the non-substituted α- and β-crystalline modifications of cis-jasmone thio­semicarbazone, α-JTSC (Orsoni et al., 2020) and β-JTSC (Oliveira et al., 2023b), the mol­ecules are connected via pairs of H⋯S inter­actions into mono-periodic hydrogen-bonded ribbons. The crystal structure of α-JTSC shows three crystallographically independent mol­ecules in the asymmetric unit. The mol­ecules are linked by H⋯S inter­actions with graph-set motif R₂²(8) along [100] into two independent one-dimensional hydrogen-bonded polymers (Fig. 9a). For β-JTSC, with one crystallographically independent mol­ecule in the asymmetric unit, the mol­ecules are connected by H⋯S inter­actions with graph-set motifs R₂²(8) and R₂¹(7) into mono-periodic hydrogen-bonded ribbons along [010] (Fig. 9b). For the supra­molecular assembly of cis-jasmone 4-methyl­thio­semicarbazone, JMTSC, (Oliveira et al., 2024) and of cis-jasmone 4-phenyl­thio­semicarbazone, JPTSC, (Oliveira et al., 2023a), a structural similarity can be observed. In the crystal, the mol­ecules are linked into centrosymmetric dimers by pairs of H⋯S inter­actions, in which rings of graph-set motifs R₂²(8) and R₂¹(7) are present. As a result of the steric hindrance of the methyl and phenyl groups, respectively, the dimers are assembled as discrete units and only weak inter­molecular inter­actions, viz., London dispersion forces can be assumed (Fig. 10a,b). The C—H⋯N inter­molecular inter­actions observed in the crystal structure of the title compound, which cause the increase of the supra­molecular dimensionality, are not observed in any of the four crystal structures of closely related mol­ecules mentioned above.

Figure 9 (a) Section of the mol­ecular arrangement of α-JTSC (Orsoni et al., 2020). The three crystallographically independent mol­ecules are A-, B-, and C-labelled. They are linked by pairs of N—H⋯S inter­actions, with rings of graph-set motif R2^2(8), into two independent mono-periodic hydrogen-bonded ribbons along [100]. [Symmetry codes: (i) x + 1, y, z; (ii) x − 1, y, z; (iii) −x + 1, −y, −z + 1; (iv) −x, −y, −z + 1.] (b) Section of the mol­ecular arrangement of β-JTSC (Oliveira et al., 2023b). The mol­ecules are connected by pairs of N—H⋯S and C—H⋯S inter­molecular inter­actions, with rings of graph-set motifs R2^2(8) and R2^1(7), into mono-periodic hydrogen-bonded ribbons along [010]. Disorder is not shown for clarity. [Symmetry codes: (i) −x + 1, y + , −z + ; (ii) −x + 1, y − , −z + .]

Figure 10 (a) Graphical representation of the JMTSC dimeric arrangement. The mol­ecules are connected by pairs of N—H⋯S and C—H⋯S inter­molecular inter­actions, with rings of graph-set motifs R2^2(8) and R2^1(7), into centrosymmetric dimers. Only the non-disordered JMTSC-1 dimer is drawn for clarity (Oliveira et al., 2024). [Symmetry code: (i) −x, −y, −z + 2]. (b) Graphical representation of the JPTSC dimeric arrangement (Oliveira et al., 2023a). The mol­ecules are linked also via pairs of N—H⋯S and C—H⋯S inter­molecular inter­actions, with rings of graph-set motifs R2^2(8) and R2^1(7), into centrosymmetric dimers. One N—H⋯N intra­molecular inter­action of graph-set S(5) is observed. [Symmetry code: (i) −x + 1, −y, −z.]

5. Synthesis and crystallization

The starting materials are commercially available and were used without further purification. The synthesis of the cis-jasmone 4-ethyl­thio­semicarbazone derivative was adapted from previously reported procedures (Freund & Schander, 1902; Oliveira et al., 2024; Orsoni et al., 2020). cis-Jasmone was dissolved in ethanol under magnetic stirring at room temperature (8 mmol, 1.3139 g, in 50 mL). A solution of 4-ethyl­thio­semicarbazide in ethanol (8 mmol, 0.9535 g, in 50 mL) was prepared under the same conditions. The solutions were combined, the HCl catalyst was added (1 mL, 1 M), and the final mixture was refluxed under magnetic stirring for 8 h. After cooling, the precipitated product was filtered off and washed with cold ethanol. Yield = 0.7431 g (35%). Colourless single crystals suitable for X-ray diffraction were obtained from tetra­hydro­furan by slow evaporation of the solvent at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. There is one crystallographically independent mol­ecule in the asymmetric unit of the title compound, which shows disorder over the chain of the cis-jasmone fragment, viz., the C9 and C10 atoms [Fig. 1; site-occupancy ratio = 0.911 (5):0.089 (5)]. The H atoms were refined freely, with exception of those bonded to C9B and C10B. These constrained H atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined isotropically using a riding model. For the H atoms attached to atom C9B with U_iso(H) = 1.2 U_eq(C), the C—H bonds were set to 0.97 Å. For the C10B atom, 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.

Table 2
Experimental details

Crystal data
Chemical formula	C14H23N3S
Mr	265.41
Crystal system, space group	Triclinic, P
Temperature (K)	123
a, b, c (Å)	7.4584 (2), 7.7429 (3), 13.2461 (3)
α, β, γ (°)	103.025 (2), 98.735 (2), 90.769 (2)
V (Å^3)	735.73 (4)
Z	2
Radiation type	Mo Kα
μ (mm^−1)	0.21
Crystal size (mm)	0.30 × 0.20 × 0.05
Data collection
Diffractometer	Enraf–Nonius FR590 Kappa CCD
Absorption correction	Analytical (using the de Meulenaer & Tompa algorithm; Alcock, 1970)
Tmin, Tmax	0.944, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	13116, 3325, 2810
Rint	0.047
(sin θ/λ)max (Å^−1)	0.650
Refinement
R[F^2 > 2σ(F^2)], wR(F^2), S	0.034, 0.085, 1.02
No. of reflections	3325
No. of parameters	275
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å^−3)	0.29, −0.21
Computer programs: COLLECT (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).

Supporting information

Computing details

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

Crystal data

C14H23N3S	Z = 2
Mr = 265.41	F(000) = 288
Triclinic, P1	Dx = 1.198 Mg m^−3
a = 7.4584 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7429 (3) Å	Cell parameters from 27549 reflections
c = 13.2461 (3) Å	θ = 2.9–27.5°
α = 103.025 (2)°	µ = 0.21 mm^−1
β = 98.735 (2)°	T = 123 K
γ = 90.769 (2)°	Fragment, colourless
V = 735.73 (4) Å^3	0.30 × 0.20 × 0.05 mm

Data collection

Enraf–Nonius FR590 Kappa CCD diffractometer	3325 independent reflections
Radiation source: sealed X-ray tube, Enraf Nonius FR590	2810 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.047
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
CCD rotation images, thick slices, κ–goniostat scans	h = −9→9
Absorption correction: analytical (using the de Meulenaer & Tompa algorithm; Alcock, 1970)	k = −10→10
Tmin = 0.944, Tmax = 0.990	l = −17→17
13116 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: mixed
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0336P)^2 + 0.2782P] where P = (Fo^2 + 2Fc^2)/3
3325 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.87223 (16)	0.34727 (16)	0.71554 (9)	0.0198 (3)
C2	0.95725 (17)	0.17051 (17)	0.68820 (10)	0.0224 (3)
C3	1.14804 (18)	0.20144 (18)	0.75527 (11)	0.0243 (3)
C4	1.16282 (17)	0.39689 (17)	0.80623 (10)	0.0217 (3)
C5	1.00677 (16)	0.47688 (17)	0.78541 (9)	0.0207 (3)
C6	0.96603 (18)	0.66839 (18)	0.82233 (11)	0.0246 (3)
C7	0.8584 (2)	0.69971 (19)	0.91194 (11)	0.0304 (3)
C8	0.7226 (2)	0.8050 (2)	0.92470 (12)	0.0328 (3)
C9A	0.6346 (2)	0.9092 (3)	0.84930 (14)	0.0342 (5)	0.911 (5)
C10A	0.6880 (4)	1.1062 (3)	0.8879 (2)	0.0465 (6)	0.911 (5)
H9A	0.500 (3)	0.894 (3)	0.8412 (16)	0.050 (6)*	0.911 (5)
H9B	0.666 (2)	0.859 (2)	0.7779 (15)	0.036 (5)*	0.911 (5)
H10A	0.823 (3)	1.124 (3)	0.8960 (16)	0.048 (6)*	0.911 (5)
H10B	0.625 (3)	1.173 (3)	0.837 (2)	0.065 (7)*	0.911 (5)
H10C	0.655 (3)	1.149 (3)	0.959 (2)	0.063 (7)*	0.911 (5)
C9B	0.778 (3)	1.006 (2)	0.9103 (13)	0.033 (5)	0.089 (5)
H9C	0.794526	1.092924	0.976673	0.039*	0.089 (5)
H9D	0.886258	1.005830	0.878229	0.039*	0.089 (5)
C10B	0.614 (3)	1.036 (3)	0.839 (2)	0.042 (6)	0.089 (5)
H10D	0.595042	0.941005	0.777614	0.064*	0.089 (5)
H10E	0.630332	1.146535	0.819865	0.064*	0.089 (5)
H10F	0.510340	1.040027	0.874748	0.064*	0.089 (5)
C11	1.33750 (18)	0.4800 (2)	0.87064 (12)	0.0284 (3)
C12	0.43231 (16)	0.31557 (17)	0.57148 (10)	0.0203 (3)
C13	0.22713 (17)	0.56201 (18)	0.56951 (11)	0.0226 (3)
C14	0.2314 (2)	0.75737 (19)	0.62214 (12)	0.0279 (3)
H2	0.627 (2)	0.157 (2)	0.5899 (13)	0.037 (5)*
H3	0.477 (2)	0.548 (2)	0.6476 (12)	0.026 (4)*
H2A	0.883 (2)	0.072 (2)	0.7024 (12)	0.029 (4)*
H2B	0.967 (2)	0.139 (2)	0.6138 (13)	0.028 (4)*
H3A	1.243 (2)	0.167 (2)	0.7122 (12)	0.030 (4)*
H3B	1.163 (2)	0.132 (2)	0.8094 (12)	0.029 (4)*
H6A	0.900 (2)	0.712 (2)	0.7621 (12)	0.028 (4)*
H6B	1.081 (2)	0.739 (2)	0.8457 (12)	0.033 (4)*
H7	0.899 (3)	0.636 (3)	0.9680 (15)	0.054 (5)*
H8	0.670 (2)	0.817 (2)	0.9901 (14)	0.040 (5)*
H11A	1.438 (3)	0.449 (2)	0.8318 (14)	0.045 (5)*
H11B	1.335 (2)	0.609 (3)	0.8935 (14)	0.046 (5)*
H11C	1.366 (3)	0.434 (3)	0.9314 (15)	0.051 (5)*
H13A	0.127 (2)	0.4975 (19)	0.5857 (11)	0.021 (3)*
H13B	0.211 (2)	0.5436 (19)	0.4940 (12)	0.024 (4)*
H14A	0.244 (2)	0.775 (2)	0.6981 (13)	0.032 (4)*
H14B	0.332 (2)	0.821 (2)	0.6068 (13)	0.035 (4)*
H14C	0.118 (2)	0.805 (2)	0.5956 (13)	0.038 (4)*
N1	0.71169 (14)	0.39345 (14)	0.68391 (8)	0.0214 (2)
N2	0.59457 (14)	0.26386 (15)	0.61441 (9)	0.0222 (2)
N3	0.39593 (14)	0.48485 (15)	0.60530 (9)	0.0217 (2)
S1	0.28777 (4)	0.16924 (4)	0.48084 (3)	0.02554 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0176 (6)	0.0227 (6)	0.0190 (6)	−0.0003 (5)	0.0017 (5)	0.0055 (5)
C2	0.0184 (6)	0.0233 (6)	0.0231 (7)	−0.0006 (5)	−0.0009 (5)	0.0031 (5)
C3	0.0187 (6)	0.0257 (7)	0.0261 (7)	0.0019 (5)	−0.0009 (5)	0.0039 (5)
C4	0.0192 (6)	0.0255 (6)	0.0196 (6)	−0.0020 (5)	0.0005 (5)	0.0052 (5)
C5	0.0199 (6)	0.0226 (6)	0.0189 (6)	−0.0021 (5)	0.0019 (5)	0.0047 (5)
C6	0.0225 (6)	0.0222 (6)	0.0277 (7)	−0.0017 (5)	0.0010 (5)	0.0048 (5)
C7	0.0354 (8)	0.0288 (7)	0.0275 (7)	0.0040 (6)	0.0050 (6)	0.0075 (6)
C8	0.0354 (8)	0.0311 (8)	0.0325 (8)	0.0031 (6)	0.0095 (6)	0.0058 (6)
C9A	0.0276 (9)	0.0372 (12)	0.0351 (10)	0.0066 (7)	0.0011 (7)	0.0050 (8)
C10A	0.0618 (16)	0.0311 (12)	0.0514 (15)	0.0110 (11)	0.0225 (12)	0.0099 (10)
C9B	0.046 (10)	0.017 (8)	0.032 (9)	0.012 (7)	0.010 (7)	−0.003 (6)
C10B	0.048 (13)	0.037 (14)	0.054 (14)	0.011 (11)	0.043 (12)	0.010 (11)
C11	0.0203 (7)	0.0318 (8)	0.0291 (8)	−0.0025 (6)	−0.0040 (6)	0.0041 (6)
C12	0.0163 (6)	0.0234 (6)	0.0217 (6)	−0.0009 (5)	0.0021 (5)	0.0068 (5)
C13	0.0173 (6)	0.0263 (7)	0.0236 (7)	0.0016 (5)	−0.0003 (5)	0.0070 (5)
C14	0.0239 (7)	0.0276 (7)	0.0306 (8)	0.0051 (6)	0.0024 (6)	0.0043 (6)
N1	0.0184 (5)	0.0227 (5)	0.0212 (5)	−0.0025 (4)	−0.0009 (4)	0.0042 (4)
N2	0.0169 (5)	0.0204 (6)	0.0258 (6)	−0.0002 (4)	−0.0027 (4)	0.0023 (4)
N3	0.0161 (5)	0.0222 (5)	0.0234 (6)	−0.0003 (4)	−0.0028 (4)	0.0021 (4)
S1	0.01824 (16)	0.02307 (18)	0.03029 (19)	−0.00124 (12)	−0.00422 (12)	0.00120 (13)

Geometric parameters (Å, º)

C1—N1	1.2899 (16)	C10A—H10B	1.01 (3)
C1—C5	1.4639 (17)	C10A—H10C	0.99 (2)
C1—C2	1.5086 (18)	C9B—C10B	1.48 (3)
C2—C3	1.5436 (17)	C9B—H9C	0.9700
C2—H2A	1.003 (16)	C9B—H9D	0.9700
C2—H2B	0.974 (16)	C10B—H10D	0.9600
C3—C4	1.5068 (18)	C10B—H10E	0.9600
C3—H3A	0.977 (16)	C10B—H10F	0.9600
C3—H3B	0.980 (16)	C11—H11A	0.973 (19)
C4—C5	1.3465 (17)	C11—H11B	0.98 (2)
C4—C11	1.4939 (18)	C11—H11C	0.95 (2)
C5—C6	1.5035 (18)	C12—N3	1.3319 (17)
C6—C7	1.509 (2)	C12—N2	1.3620 (16)
C6—H6A	0.998 (16)	C12—S1	1.6877 (13)
C6—H6B	0.980 (17)	C13—N3	1.4606 (16)
C7—C8	1.316 (2)	C13—C14	1.5139 (19)
C7—H7	0.99 (2)	C13—H13A	0.971 (15)
C8—C9A	1.502 (2)	C13—H13B	0.966 (15)
C8—C9B	1.661 (17)	C14—H14A	0.975 (17)
C8—H8	0.992 (18)	C14—H14B	0.963 (17)
C9A—C10A	1.522 (3)	C14—H14C	0.973 (18)
C9A—H9A	0.99 (2)	N1—N2	1.3904 (15)
C9A—H9B	1.00 (2)	N2—H2	0.873 (18)
C10A—H10A	1.00 (2)	N3—H3	0.828 (16)
N1—C1—C5	120.80 (11)	C9A—C10A—H10C	109.0 (14)
N1—C1—C2	129.87 (11)	H10A—C10A—H10C	106.4 (18)
C5—C1—C2	109.28 (10)	H10B—C10A—H10C	111 (2)
C1—C2—C3	103.99 (10)	C10B—C9B—C8	100.0 (14)
C1—C2—H2A	111.9 (9)	C10B—C9B—H9C	111.8
C3—C2—H2A	113.2 (9)	C8—C9B—H9C	111.8
C1—C2—H2B	110.7 (9)	C10B—C9B—H9D	111.8
C3—C2—H2B	110.4 (9)	C8—C9B—H9D	111.8
H2A—C2—H2B	106.7 (12)	H9C—C9B—H9D	109.5
C4—C3—C2	104.68 (10)	C9B—C10B—H10D	109.5
C4—C3—H3A	112.1 (9)	C9B—C10B—H10E	109.5
C2—C3—H3A	111.3 (9)	H10D—C10B—H10E	109.5
C4—C3—H3B	109.8 (9)	C9B—C10B—H10F	109.5
C2—C3—H3B	112.2 (9)	H10D—C10B—H10F	109.5
H3A—C3—H3B	106.8 (13)	H10E—C10B—H10F	109.5
C5—C4—C11	127.60 (12)	C4—C11—H11A	110.2 (11)
C5—C4—C3	112.28 (11)	C4—C11—H11B	112.8 (11)
C11—C4—C3	120.11 (11)	H11A—C11—H11B	110.0 (15)
C4—C5—C1	109.42 (11)	C4—C11—H11C	110.6 (12)
C4—C5—C6	128.51 (12)	H11A—C11—H11C	105.0 (15)
C1—C5—C6	122.06 (11)	H11B—C11—H11C	107.9 (15)
C5—C6—C7	113.14 (11)	N3—C12—N2	116.44 (11)
C5—C6—H6A	109.4 (9)	N3—C12—S1	122.95 (10)
C7—C6—H6A	110.4 (9)	N2—C12—S1	120.61 (10)
C5—C6—H6B	108.9 (9)	N3—C13—C14	110.15 (11)
C7—C6—H6B	108.3 (9)	N3—C13—H13A	108.2 (8)
H6A—C6—H6B	106.6 (13)	C14—C13—H13A	111.2 (9)
C8—C7—C6	127.15 (14)	N3—C13—H13B	109.0 (9)
C8—C7—H7	117.6 (11)	C14—C13—H13B	111.4 (9)
C6—C7—H7	115.2 (11)	H13A—C13—H13B	106.7 (12)
C7—C8—C9A	126.93 (15)	C13—C14—H14A	111.1 (9)
C7—C8—C9B	110.7 (6)	C13—C14—H14B	111.1 (10)
C7—C8—H8	117.8 (10)	H14A—C14—H14B	107.7 (14)
C9A—C8—H8	115.3 (10)	C13—C14—H14C	108.0 (10)
C9B—C8—H8	109.2 (11)	H14A—C14—H14C	109.8 (14)
C8—C9A—C10A	111.28 (16)	H14B—C14—H14C	109.1 (14)
C8—C9A—H9A	110.1 (12)	C1—N1—N2	117.11 (11)
C10A—C9A—H9A	108.3 (13)	C12—N2—N1	117.59 (11)
C8—C9A—H9B	109.3 (11)	C12—N2—H2	118.7 (11)
C10A—C9A—H9B	112.1 (11)	N1—N2—H2	122.9 (11)
H9A—C9A—H9B	105.6 (16)	C12—N3—C13	123.81 (11)
C9A—C10A—H10A	109.6 (13)	C12—N3—H3	116.1 (11)
C9A—C10A—H10B	109.5 (16)	C13—N3—H3	120.0 (11)
H10A—C10A—H10B	111 (2)
N1—C1—C2—C3	−177.86 (13)	C1—C5—C6—C7	79.84 (15)
C5—C1—C2—C3	4.82 (14)	C5—C6—C7—C8	−138.74 (16)
C1—C2—C3—C4	−5.70 (13)	C6—C7—C8—C9A	4.5 (3)
C2—C3—C4—C5	5.04 (15)	C6—C7—C8—C9B	−50.1 (6)
C2—C3—C4—C11	−174.65 (12)	C7—C8—C9A—C10A	−106.5 (2)
C11—C4—C5—C1	177.60 (13)	C7—C8—C9B—C10B	132.7 (10)
C3—C4—C5—C1	−2.06 (15)	C5—C1—N1—N2	177.52 (10)
C11—C4—C5—C6	−1.1 (2)	C2—C1—N1—N2	0.47 (19)
C3—C4—C5—C6	179.29 (12)	N3—C12—N2—N1	−4.03 (17)
N1—C1—C5—C4	−179.51 (11)	S1—C12—N2—N1	176.25 (9)
C2—C1—C5—C4	−1.91 (14)	C1—N1—N2—C12	−172.87 (11)
N1—C1—C5—C6	−0.76 (18)	N2—C12—N3—C13	−178.66 (11)
C2—C1—C5—C6	176.84 (11)	S1—C12—N3—C13	1.04 (18)
C4—C5—C6—C7	−101.67 (16)	C14—C13—N3—C12	−179.07 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1^i	0.873 (18)	2.608 (18)	3.4808 (12)	177.6 (15)
N3—H3···N1	0.828 (16)	2.187 (15)	2.6008 (15)	111.0 (13)
C2—H2A···S1^i	1.003 (16)	2.822 (15)	3.3535 (13)	113.7 (10)
C13—H13B···N1^ii	0.966 (15)	2.655 (15)	3.5466 (17)	153.5 (12)

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