# Synthesis and crystal structure of (E)-2-(2-[aza-niumylidene(methylsultanyl)methyl]hydrazinyl-idenemethl)benzene-1,4-diol hydrogen suitate

Oussama Nehar, Samira Louhibi, Thierry Roisnel

► To cite this version:

Oussama Nehar, Samira Louhibi, Thierry Roisnel. Synthesis and crystal structure of (E)-2-(2-[aza-niumylidene(methylsultanyl)methyl]hydrazinyl-idenemethl)benzene-1,4-diol hydrogen suitate. Acta crystallographica Section E: Crystallographic communications [2015-..], 2019, 75 (11), pp.1738-+. 10.1107/S2056989019014233. hal-02391899

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Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

# Synthesis and crystal structure of (E)-2-({2-[azaniumylidene(methylsulfanyl)methyl]hydrazinylidene}methyl)benzene-1,4-diol hydrogen sulfate

Oussama Nehar,<sup>a*</sup> Samira Louhibi<sup>a</sup> and Thierry Roisnel<sup>b</sup>

Received 26 September 2019

Accepted 17 October 2019

Edited by A. J. Lough, University of Toronto,
Canada

**Keywords:** crystal structure; thiosemicarbazone; hydrogen bonding; organic salt.

CCDC reference: 1960006

**Supporting information:** this article has
supporting information at journals.iucr.org/e

The title molecular salt, C₉H₁₂N₃O₂S⁺·HSO₄⁻, was obtained through the protonation of the azomethine N atom in a sulfuric acid medium. The crystal comprises two entities, a thiosemicarbazide cation and a hydrogen sulfate anion. The cation is essentially planar and is further stabilized by a strong intramolecular O-H···N hydrogen bond. In the crystal, a three-dimensional network is established through O-H···O and N-H···O hydrogen bonds. A weak intermolecular C-H···O hydrogen bond is also observed. The hydrogen sulfate anion exhibits disorder over two sets of sites and was modelled with refined occupancies of 0.501 (6) and 0.499 (6).

## 1. Chemical context

Thiosemicarbazones and their complexes are well known for their pharmacological properties, as antimicrobial (Plech et al., 2011; Pandeya et al., 1999; Küçükgüzel et al., 2006), anti-inflammatory (Palaska et al., 2002) and antiumoural (de Oliveira et al., 2015) agents. Complexes of thiosemicarbazones are studied in the literature as drug candidates, biomarkers and biocatalysts (Hayne et al., 2014; Lim et al., 2010). It is believed that the biological activity of these compounds has a strong relationship with the nature of the aldehydes and ketones from which those thiosemicarbazones were obtained (Teoh et al., 1999), and also on the substituents attached at the +NH₂ N atom (Beraldo & Gambino, 2004). An interesting attribute of thiosemicarbazones is their ability to exhibit thione-thiol tautomerism and they can also exist as *E* and *Z* isomers. Thiosemicarbazones have an excellent capacity to complex transition metals, acting as chelating agents; this process usually takes place via dissociation of the acidic proton (Pal et al., 2002). The crystal structure of the title molecular salt was determined in order to investigate its biological and catalytic activities.

## 2. Structural commentary

The molecular structure of the title molecular salt is illustrated in Fig. 1. It comprises two entities, i.e. a thiosemicarbazone cation and a hydrogen sulfate anion. The cation is essentially planar and shows an *E* conformation with regard to the C6-N5 bond, the maximum deviation from the mean plane through the 15 non-H atoms being 0.1 (2) Å for atom C6. This planarity is due to electron delocalization along the cation backbone, which is further stabilized by an intramolecular O13-H13···N5 hydrogen bond (Zhu *et al.*, 2004). The bond

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OPEN

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ACCESS

<footnote><sup>a</sup>Laboratoire de Chimie Inorganique et Environnement, Université de Tlemcen, BP 119, 13000 Tlemcen, Algeria, and</footnote>

<footnote><sup>b</sup>Centre de Diffractometrie X, UMR 6226 CNRS, Unit Sciences Chimiques de Rennes, Universite de Rennes I, 263 Avenue du General Leclerc, 35042 Rennes, France. *Correspondence e-mail: oussamanehar@gmail.com</footnote>
<table><caption>**Table 1**
Hydrogen-bond geometry (Å, °).</caption><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>C10–H10···O12A<sup>i</sup></td><td>0.95</td><td>2.60</td><td>3.541 (10)</td><td>170</td></tr><tr><td>N3–H3A···O12A<sup>ii</sup></td><td>0.89 (2)</td><td>1.85 (2)</td><td>2.738 (12)</td><td>178 (3)</td></tr><tr><td>N3–H3A···O12B<sup>ii</sup></td><td>0.89 (2)</td><td>1.98 (2)</td><td>2.841 (11)</td><td>163 (3)</td></tr><tr><td>N3–H3B···O14<sup>iii</sup></td><td>0.86 (2)</td><td>2.05 (2)</td><td>2.874 (3)</td><td>160 (3)</td></tr><tr><td>N4–H4···O13A<sup>ii</sup></td><td>0.86 (3)</td><td>2.00 (3)</td><td>2.849 (5)</td><td>167 (3)</td></tr><tr><td>N4–H4···O13B<sup>ii</sup></td><td>0.86 (3)</td><td>2.00 (3)</td><td>2.841 (5)</td><td>164 (3)</td></tr><tr><td>O13–H13···N5</td><td>0.78 (3)</td><td>2.03 (3)</td><td>2.685 (3)</td><td>142 (3)</td></tr><tr><td>O14–H14···O11A<sup>iv</sup></td><td>0.83 (4)</td><td>1.90 (4)</td><td>2.716 (16)</td><td>167 (3)</td></tr><tr><td>O14–H14···O11B<sup>iv</sup></td><td>0.83 (4)</td><td>1.82 (4)</td><td>2.62 (2)</td><td>162 (3)</td></tr><tr><td>O14A–H14A···O11A<sup>iv</sup></td><td>0.84</td><td>2.28</td><td>3.123 (17)</td><td>180</td></tr><tr><td>O14B–H14B···S2B<sup>ii</sup></td><td>0.84</td><td>2.73</td><td>3.490 (9)</td><td>152</td></tr><tr><td>O14B–H14B···O13B<sup>ii</sup></td><td>0.84</td><td>1.73</td><td>2.567 (7)</td><td>180</td></tr></tbody></table>

Symmetry codes: (i) $-x + \frac{1}{2}, y - \frac{1}{2}, -z + \frac{1}{2}$; (ii) $-x + 2, -y + 1, -z + 1$; (iii) $x + \frac{1}{2}, -y + \frac{1}{2}, z - \frac{1}{2}$; (iv) $x - 1, y, z$.

lengths and angles resemble those observed for similar thiosemicarbazone derivatives (Gangadharan *et al.*, 2015; Joseph *et al.*, 2004; Nehar *et al.*, 2016; Houari *et al.*, 2013). The anion (hydrogen sulfate) is disordered, split over two sets of sites with relative occupancies of 0.501 (6) and 0.499 (6), and labelled with A and B suffixes.

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### 3. Supramolecular features

In the crystal, the three-dimensional structure is established through an extensive network of O–H···O and N–H···O hydrogen bonds. Also within this network exists a weak C–H···O intermolecular hydrogen bond (Table 1 and Fig. 2). The crystal packing is shown in Fig. 2.

### 4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.4, May 2019 update; Groom *et al.*, 2016) for the S-methyl-(methylidene)thiosemicarbazidium cation yielded three results, viz. S-methyl-N-(pyrrolyl-2-methylene)isothiosemicarbazidium iodide monohydrate (CSD refcode JIHZUV; Bourosh *et al.*, 1990), 8-quinolinealdehyde S-methylthiosemicarbazone hydrochloride dihydrate (RUJXOK; Botoshansky *et al.*, 2009) and ((E)-[2-[(E)-(4-hydroxynaphthalen-1-yl)methylidene]hydrazin-1-yl}(methylsulfanyl)methylidene)azanium hydrogen sulfate monohydrate. The three-dimensional coordinates for the first structure are unavailable. A comparison of the structures reveals that the cation in the RUJXOK structure is less planar than the cation in ESOTIR, the latter being more similar to the cation of the title compound. However, for structures RUJXOK and ESOTIR, the

<figure><img src="image_7.png" /><figcaption>**Figure 1**
The molecular structure of the title molecular salt, showing the labelling and with displacement ellipsoids drawn at the 50% probability level. The disordered hydrogen sulfate anion is shown.</figcaption></figure>

bond lengths and angles are similar to those of the title molecular salt.

### 5. Synthesis and crystallization

An equimolar amount of thiosemicarbazide (10 mmol, 0.91 g) and 2,5-dihydroxybenzaldehyde (10 mmol, 1.38 g) were dissolved in a methanol-water solution in the presence of sulfuric acid. The mixture was then refluxed for 3 h. The solution was filtered and left to evaporate at room temperature. After slow evaporation, brown crystals suitable for X-ray diffraction analysis were obtained.

<figure><img src="image_8.png" /><figcaption>**Figure 2**
Projection along the *a* axis of the crystal packing of the title molecular salt. Hydrogen bonds are shown as dashed lines.</figcaption></figure>
## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen sulfate anion is disordered and had to be modelled as two conformations A and B, with relative occupancies of 0.501 (6) and 0.499 (6), respectively. H atoms were located in difference Fourier maps, but were subsequently included in calculated positions and treated as riding on their parent atoms with constrained thermal parameters: $U_{iso}(H) = 1.5U_{eq}(C)$ and $C-H = 0.98 Å$ for methyl H atoms, and $U_{iso}(H) = 1.2U_{eq}(C,N)$ and $C-H = 0.95 Å$ or $N-H = 0.88 Å$ otherwise.

## Acknowledgements

The authors are grateful for the support provided by the Algerian Ministry for Education and Research.

## References

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<table><caption>Table 2
Experimental details.</caption><tr><td colspan="2">Crystal data</td></tr><tr><td>Chemical formula</td><td>C<sub>9</sub>H<sub>12</sub>N<sub>3</sub>O<sub>2</sub>S<sup>+</sup>·HSO<sub>4</sub><sup>−</sup></td></tr><tr><td>M<sub>r</sub></td><td>323.34</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, <i>P</i>2<sub>1</sub>/<i>n</i></td></tr><tr><td>Temperature (K)</td><td>150</td></tr><tr><td><i>a</i>, <i>b</i>, <i>c</i> (Å)</td><td>4.9411 (8), 16.139 (2), 16.426 (3)</td></tr><tr><td>β (°)</td><td>100.440 (7)</td></tr><tr><td><i>V</i> (Å<sup>3</sup>)</td><td>1288.2 (3)</td></tr><tr><td><i>Z</i></td><td>4</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>−1</sup>)</td><td>0.44</td></tr><tr><td>Crystal size (mm)</td><td>0.38 × 0.15 × 0.12</td></tr><tr><td colspan="2">Data collection</td></tr><tr><td>Diffractometer</td><td>Bruker APEXII</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Bruker, 2015)</td></tr><tr><td><i>T</i><sub>min</sub>, <i>T</i><sub>max</sub></td><td>0.838, 0.948</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>7962, 2846, 2014</td></tr><tr><td><i>R</i><sub>int</sub></td><td>0.045</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>−1</sup>)</td><td>0.644</td></tr><tr><td colspan="2">Refinement</td></tr><tr><td><i>R</i>[<i>F</i><sup>2</sup> > 2σ(<i>F</i><sup>2</sup>)], <i>wR</i>(<i>F</i><sup>2</sup>), <i>S</i></td><td>0.050, 0.147, 1.03</td></tr><tr><td>No. of reflections</td><td>2846</td></tr><tr><td>No. of parameters</td><td>243</td></tr><tr><td>No. of restraints</td><td>8</td></tr><tr><td>H-atom treatment</td><td>H atoms treated by a mixture of independent and constrained refinement</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>−3</sup>)</td><td>0.36, −0.46</td></tr></table>

Computer programs: *APEX2* (Bruker, 2015), *SAINT* (Bruker, 2015), *SHELXT* (Sheldrick, 2015a), *SHELXL2018* (Sheldrick, 2015b), *SXGRAPH* (Farrugia, 1999), *Mercury* (Macrae *et al.*, 2008) and *CRYSCALC* (T. Roisnel, local program).

* R., Neves, J. L., Ruiz, A. L., Ernesto de Carvalho, J. & Alves de Lima, M. C. (2015). *Eur. J. Med. Chem.* **104**, 148–156.

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* Palaska, E., Şahin, G., Kelicen, P., Durlu, N. T. & Altinok, G. (2002). *Farmaco*, **57**, 101–107.

* Pandeya, S. N., Sriram, D., Nath, G. & DeClercq, E. (1999). *Eur. J. Pharm. Sci.* **9**, 25–31.

* Plech, T., Wujec, M., Siwek, A., Kosikowska, U. & Malm, A. (2011). *Eur. J. Med. Chem.* **46**, 241–248.

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* Sheldrick, G. M. (2015b). *Acta Cryst.* **C71**, 3–8.

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supporting information

*Acta Cryst.* (2019). **E75**, 1738-1740 [https://doi.org/10.1107/S2056989019014233]

# Synthesis and crystal structure of (E)-2-({2-[azaniumylidene(methylsulfanyl)methyl]hydrazinylidene}methyl)benzene-1,4-diol hydrogen sulfate

Oussama Nehar, Samira Louhibi and Thierry Roisnel

## Computing details

Data collection: *APEX2* (Bruker, 2014); cell refinement: *APEX2* (Bruker, 2014); data reduction: *APEX2* (Bruker, 2014); program(s) used to solve structure: *SHELXT* (Sheldrick, 2015a); program(s) used to refine structure: *SHELXL2018* (Sheldrick, 2015b); molecular graphics: SXGRAPH (Farrugia, 1999) and *Mercury* (Macrae *et al.*, 2008); software used to prepare material for publication: CRYSCALC (T. Roisnel, local program, 2019).

## (E)-2-({2-[Azaniumylidene(methylsulfanyl)methyl]hydrazinylidene}methyl)benzene-1,4-diol sulfate

### Crystal data

$C_9H_{12}N_3O_2S^{+}.HSO_4^-$

$M_r = 323.34$

Monoclinic, $P2_1/n$

$a = 4.9411 (8) Å$

$b = 16.139 (2) Å$

$c = 16.426 (3) Å$

$\beta = 100.440 (7)°$

$V = 1288.2 (3) Å^3$

$Z = 4$

$F(000) = 672$

$D_x = 1.667 \text{ Mg m}^{-3}$

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 2859 reflections

$\theta = 2.5-27.0°$

$\mu = 0.44 \text{ mm}^{-1}$

$T = 150$ K

Prism, colourless

$0.38 \times 0.15 \times 0.12 \text{ mm}$

### Data collection

Bruker APEXII

diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

CCD rotation images, thin slices scans

Absorption correction: multi-scan
(SADABS; Sheldrick, 2014)

$T_{\text{min}} = 0.838, T_{\text{max}} = 0.948$

7962 measured reflections

2846 independent reflections

2014 reflections with $I > 2\sigma(I)$

$R_{\text{int}} = 0.045$

$\theta_{\text{max}} = 27.3°, \theta_{\text{min}} = 3.6°$

$h = -6 \rightarrow 4$

$k = -19 \rightarrow 20$

$l = -21 \rightarrow 19$

### Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.050$

$wR(F^2) = 0.147$

$S = 1.03$

2846 reflections

243 parameters

8 restraints

Primary atom site location: dual

Secondary atom site location: difference Fourier map

Hydrogen site location: mixed

H atoms treated by a mixture of independent and constrained refinement

$w = 1/[\sigma^2(F_o^2) + (0.086P)^2]$ where $P = (F_o^2 + 2F_c^2)/3$

($\Delta/\sigma)_{\text{max}} < 0.001$

$\Delta\rho_{\text{max}} = 0.36 \text{ e Å}^{-3}$

$\Delta\rho_{\text{min}} = -0.46 \text{ e Å}^{-3}$
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.

**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 > 2sigma(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.

<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th><th>Occ. (&lt;1)</th></tr></thead><tbody><tr><td>S1</td><td>0.99180 (14)</td><td>0.09724 (4)</td><td>0.39012 (4)</td><td>0.0247 (2)</td><td></td></tr><tr><td>C1</td><td>1.1843 (6)</td><td>0.05832 (18)</td><td>0.31564 (19)</td><td>0.0283 (7)</td><td></td></tr><tr><td>H1A</td><td>1.103765</td><td>0.079127</td><td>0.260512</td><td>0.042*</td><td></td></tr><tr><td>H1B</td><td>1.178644</td><td>-0.002377</td><td>0.315474</td><td>0.042*</td><td></td></tr><tr><td>H1C</td><td>1.375761</td><td>0.076956</td><td>0.330229</td><td>0.042*</td><td></td></tr><tr><td>C2</td><td>1.0137 (5)</td><td>0.20289 (18)</td><td>0.37549 (16)</td><td>0.0196 (6)</td><td></td></tr><tr><td>N3</td><td>1.1584 (4)</td><td>0.23722 (15)</td><td>0.32555 (15)</td><td>0.0212 (5)</td><td></td></tr><tr><td>H3A</td><td>1.163 (6)</td><td>0.2922 (11)</td><td>0.3217 (18)</td><td>0.025*</td><td></td></tr><tr><td>H3B</td><td>1.253 (5)</td><td>0.2090 (17)</td><td>0.2961 (16)</td><td>0.025*</td><td></td></tr><tr><td>N4</td><td>0.8734 (5)</td><td>0.25101 (15)</td><td>0.41903 (15)</td><td>0.0221 (5)</td><td></td></tr><tr><td>H4</td><td>0.897 (6)</td><td>0.304 (2)</td><td>0.4220 (19)</td><td>0.027*</td><td></td></tr><tr><td>N5</td><td>0.7288 (4)</td><td>0.21422 (15)</td><td>0.47329 (14)</td><td>0.0209 (5)</td><td></td></tr><tr><td>C6</td><td>0.6012 (5)</td><td>0.26348 (17)</td><td>0.51479 (17)</td><td>0.0207 (6)</td><td></td></tr><tr><td>H6</td><td>0.611234</td><td>0.321565</td><td>0.506437</td><td>0.025*</td><td></td></tr><tr><td>C7</td><td>0.4421 (5)</td><td>0.23214 (17)</td><td>0.57410 (16)</td><td>0.0179 (6)</td><td></td></tr><tr><td>C8</td><td>0.4293 (5)</td><td>0.14784 (17)</td><td>0.59347 (17)</td><td>0.0204 (6)</td><td></td></tr><tr><td>C9</td><td>0.2738 (5)</td><td>0.12280 (18)</td><td>0.65151 (18)</td><td>0.0239 (6)</td><td></td></tr><tr><td>H9</td><td>0.265269</td><td>0.065663</td><td>0.664710</td><td>0.029*</td><td></td></tr><tr><td>C10</td><td>0.1324 (5)</td><td>0.17925 (17)</td><td>0.69007 (17)</td><td>0.0225 (6)</td><td></td></tr><tr><td>H10</td><td>0.025988</td><td>0.161037</td><td>0.729373</td><td>0.027*</td><td></td></tr><tr><td>C11</td><td>0.1446 (5)</td><td>0.26363 (17)</td><td>0.67161 (17)</td><td>0.0199 (6)</td><td></td></tr><tr><td>C12</td><td>0.2983 (5)</td><td>0.28879 (17)</td><td>0.61429 (16)</td><td>0.0209 (6)</td><td></td></tr><tr><td>H12</td><td>0.306923</td><td>0.346085</td><td>0.601728</td><td>0.025*</td><td></td></tr><tr><td>O13</td><td>0.5640 (4)</td><td>0.08764 (12)</td><td>0.55849 (13)</td><td>0.0270 (5)</td><td></td></tr><tr><td>H13</td><td>0.648 (7)</td><td>0.106 (2)</td><td>0.527 (2)</td><td>0.032*</td><td></td></tr><tr><td>O14</td><td>0.0054 (4)</td><td>0.31741 (13)</td><td>0.71335 (13)</td><td>0.0279 (5)</td><td></td></tr><tr><td>H14</td><td>0.001 (6)</td><td>0.366 (2)</td><td>0.697 (2)</td><td>0.034*</td><td></td></tr><tr><td>S2A</td><td>0.8844 (12)</td><td>0.5353 (4)</td><td>0.6254 (4)</td><td>0.0254 (10)</td><td>0.501 (6)</td></tr><tr><td>O11A</td><td>1.081 (3)</td><td>0.4743 (10)</td><td>0.6620 (9)</td><td>0.031 (3)</td><td>0.501 (6)</td></tr><tr><td>O12A</td><td>0.810 (2)</td><td>0.5938 (7)</td><td>0.6848 (5)</td><td>0.030 (2)</td><td>0.501 (6)</td></tr><tr><td>O13A</td><td>0.9688 (11)</td><td>0.5797 (2)</td><td>0.5572 (3)</td><td>0.0297 (14)</td><td>0.501 (6)</td></tr><tr><td>O14A</td><td>0.6216 (9)</td><td>0.4839 (3)</td><td>0.5891 (3)</td><td>0.0302 (13)</td><td>0.501 (6)</td></tr><tr><td>H14A</td><td>0.476218</td><td>0.481337</td><td>0.608697</td><td>0.045*</td><td>0.501 (6)</td></tr><tr><td>S2B</td><td>0.9553 (12)</td><td>0.5327 (5)</td><td>0.6250 (5)</td><td>0.0292 (12)</td><td>0.499 (6)</td></tr><tr><td>O11B</td><td>1.084 (4)</td><td>0.4751 (12)</td><td>0.6870 (8)</td><td>0.038 (3)</td><td>0.499 (6)</td></tr></tbody></table>
<table><tr><td>O12B</td><td>0.767 (2)</td><td>0.5891 (7)</td><td>0.6534 (6)</td><td>0.038 (2)</td><td>0.499 (6)</td></tr><tr><td>O13B</td><td>1.1639 (10)</td><td>0.5733 (3)</td><td>0.5857 (3)</td><td>0.0294 (13)</td><td>0.499 (6)</td></tr><tr><td>O14B</td><td>0.7723 (10)</td><td>0.4819 (4)</td><td>0.5562 (3)</td><td>0.0506 (17)</td><td>0.499 (6)</td></tr><tr><td>H14B</td><td>0.793868</td><td>0.463761</td><td>0.509852</td><td>0.076*</td><td>0.499 (6)</td></tr></table>

Atomic displacement parameters (Å²)

<table><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>S1</td><td>0.0307 (4)</td><td>0.0178 (4)</td><td>0.0285 (4)</td><td>-0.0005 (3)</td><td>0.0136 (3)</td><td>0.0018 (3)</td></tr><tr><td>C1</td><td>0.0313 (14)</td><td>0.0220 (15)</td><td>0.0354 (18)</td><td>0.0012 (12)</td><td>0.0162 (13)</td><td>0.0003 (13)</td></tr><tr><td>C2</td><td>0.0205 (11)</td><td>0.0207 (14)</td><td>0.0172 (14)</td><td>-0.0001 (11)</td><td>0.0027 (11)</td><td>-0.0014 (11)</td></tr><tr><td>N3</td><td>0.0252 (11)</td><td>0.0175 (12)</td><td>0.0236 (13)</td><td>0.0011 (10)</td><td>0.0114 (10)</td><td>0.0049 (10)</td></tr><tr><td>N4</td><td>0.0285 (11)</td><td>0.0178 (12)</td><td>0.0228 (13)</td><td>-0.0013 (10)</td><td>0.0121 (10)</td><td>0.0013 (10)</td></tr><tr><td>N5</td><td>0.0226 (10)</td><td>0.0229 (12)</td><td>0.0188 (12)</td><td>-0.0018 (9)</td><td>0.0079 (9)</td><td>0.0010 (10)</td></tr><tr><td>C6</td><td>0.0230 (11)</td><td>0.0178 (14)</td><td>0.0220 (15)</td><td>-0.0004 (11)</td><td>0.0057 (11)</td><td>0.0001 (11)</td></tr><tr><td>C7</td><td>0.0197 (11)</td><td>0.0182 (13)</td><td>0.0162 (14)</td><td>-0.0007 (10)</td><td>0.0040 (10)</td><td>-0.0011 (11)</td></tr><tr><td>C8</td><td>0.0214 (11)</td><td>0.0185 (14)</td><td>0.0211 (15)</td><td>-0.0003 (10)</td><td>0.0035 (11)</td><td>-0.0024 (11)</td></tr><tr><td>C9</td><td>0.0285 (13)</td><td>0.0185 (14)</td><td>0.0252 (15)</td><td>-0.0032 (12)</td><td>0.0063 (12)</td><td>0.0006 (12)</td></tr><tr><td>C10</td><td>0.0249 (12)</td><td>0.0238 (15)</td><td>0.0201 (15)</td><td>-0.0030 (11)</td><td>0.0075 (11)</td><td>0.0009 (12)</td></tr><tr><td>C11</td><td>0.0214 (11)</td><td>0.0191 (14)</td><td>0.0202 (14)</td><td>0.0002 (11)</td><td>0.0064 (11)</td><td>-0.0040 (11)</td></tr><tr><td>C12</td><td>0.0244 (12)</td><td>0.0172 (14)</td><td>0.0213 (15)</td><td>-0.0008 (11)</td><td>0.0043 (11)</td><td>0.0002 (11)</td></tr><tr><td>O13</td><td>0.0342 (11)</td><td>0.0182 (10)</td><td>0.0329 (13)</td><td>0.0024 (9)</td><td>0.0175 (9)</td><td>-0.0009 (9)</td></tr><tr><td>O14</td><td>0.0363 (10)</td><td>0.0186 (10)</td><td>0.0336 (12)</td><td>0.0014 (9)</td><td>0.0186 (9)</td><td>-0.0015 (9)</td></tr><tr><td>S2A</td><td>0.038 (3)</td><td>0.0164 (14)</td><td>0.0231 (13)</td><td>-0.0028 (16)</td><td>0.0076 (16)</td><td>0.0061 (9)</td></tr><tr><td>O11A</td><td>0.028 (3)</td><td>0.020 (3)</td><td>0.043 (8)</td><td>0.003 (3)</td><td>0.007 (5)</td><td>0.010 (5)</td></tr><tr><td>O12A</td><td>0.040 (4)</td><td>0.026 (3)</td><td>0.026 (4)</td><td>-0.010 (3)</td><td>0.009 (3)</td><td>-0.005 (3)</td></tr><tr><td>O13A</td><td>0.050 (3)</td><td>0.018 (2)</td><td>0.026 (3)</td><td>-0.004 (2)</td><td>0.021 (2)</td><td>0.0035 (18)</td></tr><tr><td>O14A</td><td>0.031 (2)</td><td>0.025 (2)</td><td>0.038 (3)</td><td>-0.0049 (18)</td><td>0.016 (2)</td><td>-0.0021 (19)</td></tr><tr><td>S2B</td><td>0.037 (3)</td><td>0.0182 (14)</td><td>0.0338 (15)</td><td>-0.0054 (16)</td><td>0.0117 (17)</td><td>-0.0075 (10)</td></tr><tr><td>O11B</td><td>0.051 (4)</td><td>0.030 (4)</td><td>0.035 (7)</td><td>-0.001 (3)</td><td>0.014 (5)</td><td>0.007 (5)</td></tr><tr><td>O12B</td><td>0.038 (4)</td><td>0.017 (3)</td><td>0.062 (7)</td><td>0.005 (3)</td><td>0.021 (5)</td><td>-0.011 (5)</td></tr><tr><td>O13B</td><td>0.030 (3)</td><td>0.025 (2)</td><td>0.036 (3)</td><td>0.0028 (19)</td><td>0.014 (2)</td><td>0.008 (2)</td></tr><tr><td>O14B</td><td>0.042 (3)</td><td>0.068 (4)</td><td>0.044 (3)</td><td>-0.018 (3)</td><td>0.012 (3)</td><td>-0.029 (3)</td></tr></tbody></table>

Geometric parameters (Å, °)

<table><tr><td>S1—C2</td><td>1.728 (3)</td><td>C9—H9</td><td>0.9500</td></tr><tr><td>S1—C1</td><td>1.794 (3)</td><td>C10—C11</td><td>1.399 (4)</td></tr><tr><td>C1—H1A</td><td>0.9800</td><td>C10—H10</td><td>0.9500</td></tr><tr><td>C1—H1B</td><td>0.9800</td><td>C11—O14</td><td>1.367 (3)</td></tr><tr><td>C1—H1C</td><td>0.9800</td><td>C11—C12</td><td>1.374 (3)</td></tr><tr><td>C2—N3</td><td>1.305 (3)</td><td>C12—H12</td><td>0.9500</td></tr><tr><td>C2—N4</td><td>1.332 (3)</td><td>O13—H13</td><td>0.78 (3)</td></tr><tr><td>N3—H3A</td><td>0.890 (18)</td><td>O14—H14</td><td>0.83 (4)</td></tr><tr><td>N3—H3B</td><td>0.861 (17)</td><td>S2A—O11A</td><td>1.435 (8)</td></tr><tr><td>N4—N5</td><td>1.374 (3)</td><td>S2A—O12A</td><td>1.452 (7)</td></tr><tr><td>N4—H4</td><td>0.86 (3)</td><td>S2A—O13A</td><td>1.453 (6)</td></tr><tr><td>N5—C6</td><td>1.285 (3)</td><td>S2A—O14A</td><td>1.564 (8)</td></tr></table>
<table>
  <tbody>
    <tr>
      <td>C6—C7</td>
      <td>1.449 (3)</td>
      <td>O14A—H14A</td>
      <td>0.8399</td>
    </tr>
    <tr>
      <td>C6—H6</td>
      <td>0.9500</td>
      <td>S2B—O12B</td>
      <td>1.437 (7)</td>
    </tr>
    <tr>
      <td>C7—C12</td>
      <td>1.395 (4)</td>
      <td>S2B—O11B</td>
      <td>1.439 (8)</td>
    </tr>
    <tr>
      <td>C7—C8</td>
      <td>1.401 (4)</td>
      <td>S2B—O13B</td>
      <td>1.467 (6)</td>
    </tr>
    <tr>
      <td>C8—O13</td>
      <td>1.362 (3)</td>
      <td>S2B—O14B</td>
      <td>1.549 (9)</td>
    </tr>
    <tr>
      <td>C8—C9</td>
      <td>1.388 (4)</td>
      <td>O14B—H14B</td>
      <td>0.8401</td>
    </tr>
    <tr>
      <td>C9—C10</td>
      <td>1.371 (4)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>C2—S1—C1</td>
      <td>101.32 (13)</td>
      <td>C10—C9—H9</td>
      <td>119.5</td>
    </tr>
    <tr>
      <td>S1—C1—H1A</td>
      <td>109.5</td>
      <td>C8—C9—H9</td>
      <td>119.5</td>
    </tr>
    <tr>
      <td>S1—C1—H1B</td>
      <td>109.5</td>
      <td>C9—C10—C11</td>
      <td>120.1 (2)</td>
    </tr>
    <tr>
      <td>H1A—C1—H1B</td>
      <td>109.5</td>
      <td>C9—C10—H10</td>
      <td>120.0</td>
    </tr>
    <tr>
      <td>S1—C1—H1C</td>
      <td>109.5</td>
      <td>C11—C10—H10</td>
      <td>120.0</td>
    </tr>
    <tr>
      <td>H1A—C1—H1C</td>
      <td>109.5</td>
      <td>O14—C11—C12</td>
      <td>123.2 (3)</td>
    </tr>
    <tr>
      <td>H1B—C1—H1C</td>
      <td>109.5</td>
      <td>O14—C11—C10</td>
      <td>117.6 (2)</td>
    </tr>
    <tr>
      <td>N3—C2—N4</td>
      <td>119.2 (3)</td>
      <td>C12—C11—C10</td>
      <td>119.2 (2)</td>
    </tr>
    <tr>
      <td>N3—C2—S1</td>
      <td>124.2 (2)</td>
      <td>C11—C12—C7</td>
      <td>121.5 (3)</td>
    </tr>
    <tr>
      <td>N4—C2—S1</td>
      <td>116.7 (2)</td>
      <td>C11—C12—H12</td>
      <td>119.2</td>
    </tr>
    <tr>
      <td>C2—N3—H3A</td>
      <td>119.5 (19)</td>
      <td>C7—C12—H12</td>
      <td>119.2</td>
    </tr>
    <tr>
      <td>C2—N3—H3B</td>
      <td>123 (2)</td>
      <td>C8—O13—H13</td>
      <td>112 (2)</td>
    </tr>
    <tr>
      <td>H3A—N3—H3B</td>
      <td>118 (3)</td>
      <td>C11—O14—H14</td>
      <td>115 (2)</td>
    </tr>
    <tr>
      <td>C2—N4—N5</td>
      <td>118.6 (2)</td>
      <td>O11A—S2A—O12A</td>
      <td>113.5 (9)</td>
    </tr>
    <tr>
      <td>C2—N4—H4</td>
      <td>122 (2)</td>
      <td>O11A—S2A—O13A</td>
      <td>113.2 (7)</td>
    </tr>
    <tr>
      <td>N5—N4—H4</td>
      <td>118 (2)</td>
      <td>O12A—S2A—O13A</td>
      <td>109.8 (7)</td>
    </tr>
    <tr>
      <td>C6—N5—N4</td>
      <td>116.1 (2)</td>
      <td>O11A—S2A—O14A</td>
      <td>104.4 (10)</td>
    </tr>
    <tr>
      <td>N5—C6—C7</td>
      <td>121.3 (3)</td>
      <td>O12A—S2A—O14A</td>
      <td>107.9 (5)</td>
    </tr>
    <tr>
      <td>N5—C6—H6</td>
      <td>119.4</td>
      <td>O13A—S2A—O14A</td>
      <td>107.6 (5)</td>
    </tr>
    <tr>
      <td>C7—C6—H6</td>
      <td>119.4</td>
      <td>S2A—O14A—H14A</td>
      <td>126.1</td>
    </tr>
    <tr>
      <td>C12—C7—C8</td>
      <td>118.7 (2)</td>
      <td>O12B—S2B—O11B</td>
      <td>114.1 (9)</td>
    </tr>
    <tr>
      <td>C12—C7—C6</td>
      <td>118.3 (2)</td>
      <td>O12B—S2B—O13B</td>
      <td>114.0 (7)</td>
    </tr>
    <tr>
      <td>C8—C7—C6</td>
      <td>123.0 (2)</td>
      <td>O11B—S2B—O13B</td>
      <td>110.1 (9)</td>
    </tr>
    <tr>
      <td>O13—C8—C9</td>
      <td>117.1 (2)</td>
      <td>O12B—S2B—O14B</td>
      <td>104.2 (6)</td>
    </tr>
    <tr>
      <td>O13—C8—C7</td>
      <td>123.4 (2)</td>
      <td>O11B—S2B—O14B</td>
      <td>107.4 (11)</td>
    </tr>
    <tr>
      <td>C9—C8—C7</td>
      <td>119.5 (2)</td>
      <td>O13B—S2B—O14B</td>
      <td>106.2 (5)</td>
    </tr>
    <tr>
      <td>C10—C9—C8</td>
      <td>121.0 (3)</td>
      <td>S2B—O14B—H14B</td>
      <td>133.8</td>
    </tr>
    <tr>
      <td>C1—S1—C2—N3</td>
      <td>-4.6 (3)</td>
      <td>C6—C7—C8—C9</td>
      <td>179.5 (2)</td>
    </tr>
    <tr>
      <td>C1—S1—C2—N4</td>
      <td>175.8 (2)</td>
      <td>O13—C8—C9—C10</td>
      <td>179.7 (2)</td>
    </tr>
    <tr>
      <td>N3—C2—N4—N5</td>
      <td>-178.0 (2)</td>
      <td>C7—C8—C9—C10</td>
      <td>0.1 (4)</td>
    </tr>
    <tr>
      <td>S1—C2—N4—N5</td>
      <td>1.6 (3)</td>
      <td>C8—C9—C10—C11</td>
      <td>-0.4 (4)</td>
    </tr>
    <tr>
      <td>C2—N4—N5—C6</td>
      <td>178.8 (2)</td>
      <td>C9—C10—C11—O14</td>
      <td>-178.4 (2)</td>
    </tr>
    <tr>
      <td>N4—N5—C6—C7</td>
      <td>-179.8 (2)</td>
      <td>C9—C10—C11—C12</td>
      <td>0.3 (4)</td>
    </tr>
    <tr>
      <td>N5—C6—C7—C12</td>
      <td>-177.1 (2)</td>
      <td>O14—C11—C12—C7</td>
      <td>178.7 (2)</td>
    </tr>
    <tr>
      <td>N5—C6—C7—C8</td>
      <td>3.7 (4)</td>
      <td>C10—C11—C12—C7</td>
      <td>0.1 (4)</td>
    </tr>
    <tr>
      <td>C12—C7—C8—O13</td>
      <td>-179.3 (2)</td>
      <td>C8—C7—C12—C11</td>
      <td>-0.4 (4)</td>
    </tr>
    <tr>
      <td>C6—C7—C8—O13</td>
      <td>-0.1 (4)</td>
      <td>C6—C7—C12—C11</td>
      <td>-179.6 (2)</td>
    </tr>
    <tr>
      <td>C12—C7—C8—C9</td>
      <td>0.3 (4)</td>
      <td></td>
      <td></td>
    </tr>
  </tbody>
</table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>C10—H10···O12A<sup>i</sup></td><td>0.95</td><td>2.60</td><td>3.541 (10)</td><td>170</td></tr><tr><td>N3—H3A···O12A<sup>ii</sup></td><td>0.89 (2)</td><td>1.85 (2)</td><td>2.738 (12)</td><td>178 (3)</td></tr><tr><td>N3—H3A···O12B<sup>ii</sup></td><td>0.89 (2)</td><td>1.98 (2)</td><td>2.841 (11)</td><td>163 (3)</td></tr><tr><td>N3—H3B···O14<sup>iii</sup></td><td>0.86 (2)</td><td>2.05 (2)</td><td>2.874 (3)</td><td>160 (3)</td></tr><tr><td>N4—H4···O13A<sup>ii</sup></td><td>0.86 (3)</td><td>2.00 (3)</td><td>2.849 (5)</td><td>167 (3)</td></tr><tr><td>N4—H4···O13B<sup>ii</sup></td><td>0.86 (3)</td><td>2.00 (3)</td><td>2.841 (5)</td><td>164 (3)</td></tr><tr><td>O13—H13···N5</td><td>0.78 (3)</td><td>2.03 (3)</td><td>2.685 (3)</td><td>142 (3)</td></tr><tr><td>O14—H14···O11A<sup>iv</sup></td><td>0.83 (4)</td><td>1.90 (4)</td><td>2.716 (16)</td><td>167 (3)</td></tr><tr><td>O14—H14···O11B<sup>iv</sup></td><td>0.83 (4)</td><td>1.82 (4)</td><td>2.62 (2)</td><td>162 (3)</td></tr><tr><td>O14A—H14A···O11A<sup>iv</sup></td><td>0.84</td><td>2.28</td><td>3.123 (17)</td><td>180</td></tr><tr><td>O14B—H14B···S2B<sup>ii</sup></td><td>0.84</td><td>2.73</td><td>3.490 (9)</td><td>152</td></tr><tr><td>O14B—H14B···O13B<sup>ii</sup></td><td>0.84</td><td>1.73</td><td>2.567 (7)</td><td>180</td></tr></tbody></table>

Symmetry codes: (i) $-x+1/2, y-1/2, -z+3/2$; (ii) $-x+2, -y+1, -z+1$; (iii) $x+3/2, -y+1/2, z-1/2$; (iv) $x-1, y, z$.