8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5 H
-1-oxa-2,4-diazaacenaphthylene

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya, Jean-Marie Coustard

► To cite this version:

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya, Jean-Marie Coustard. 8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5 H -1-oxa-2,4-diazaacenaphthylene. 2021, pp.x210674. 10.1107/s241431462100674x. hal-04417478

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Distributed under a Creative Commons Attribution 4.0 International License
8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5 H
-1-oxa-2,4-diazaacenaphthylene

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya, Jean-Marie Coustard

► To cite this version:

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya, Jean-Marie Coustard. 8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5 H -1-oxa-2,4-diazaacenaphthylene. 2021, pp.x210674. 10.1107/s241431462100674x. hal-04417478

HAL Id: hal-04417478

https://hal.science/hal-04417478v1

Submitted on 4 Jun 2024

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
<figure><img src="image_2.png" /></figure>

IUCrData

<figure><img src="image_3.png" /></figure>

IUCrData

ISSN 2414-3146

Received 21 June 2021

Accepted 28 June 2021

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China

‡ Deceased August 2013.

Keywords: crystal structure; diazadihydroacenaphthylene derivative; hydrogen bonding and C—H···π interactions.

CCDC reference: 2089097

Structural data: full structural data are available
from iucrdata.iucr.org

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Akoun Abou,<sup>a,*</sup> Fanté Bamba,<sup>b</sup> Jérôme Marrot,<sup>c</sup> Soro Yaya<sup>d</sup> and Jean-Marie Coustard<sup>e,‡</sup>

<sup>a</sup>Department of Training and Research in Electrical and Electronic Engineering, Research Team: Instrumentation, Image and Spectroscopy, Félix Houphouët-Boigny National Polytechnic Institute, BP 1093 Yamoussoukro, Côte d'Ivoire,
<sup>b</sup>Laboratoire de Constitution et Réaction de la Matière, UFR SSMT, Université Félix Houphouët-Boigny, 22 BP 582 Abidjan 22, Côte d'Ivoire, <sup>c</sup>Laboratoire ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, <sup>d</sup>Laboratoire des Procédés Industriels de Synthèse et d'Environnement, Institut National Polytechnique Félix Houphouët-Boigny, BP 991 Yamoussoukro, Côte d'Ivoire, and <sup>e</sup>Laboratoire IC2MP-UMR 7285 CNRS, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France. *Correspondence e-mail: abouakoun@gmail.com

In the tricyclic title compound, C₁₁H₁₂N₂OS, the 2,3,4,5-tetrahydropyridine ring adopts a half-chair conformation. This ring makes dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring is oriented at an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. In the crystal, molecules associate *via* C—H···N hydrogen bonds and C—H···π interactions, forming a three-dimensional network.

<figure><img src="image_4.png" /><figcaption>Chemical scheme</figcaption></figure>

<figure><img src="image_5.png" /></figure>

Structure description

Diazadihydroacenaphthylene derivatives contain an isoxazoline scaffold and constitute an important class of heterocyclic compounds whose chemical properties have been investigated over the years (Jäger & Buss, 1980; Jäger *et al.*, 1980). This scaffold is used in the synthesis of several complex natural products (Saha & Bhattacharjya, 1997; Copp *et al.*, 1992) and is a pharmacophore of numerous medicinal chemistry compounds (Brandi *et al.*, 2003; King *et al.*, 1982; Bacher *et al.*, 1997; You *et al.*, 1995). It has also been reported that this scaffold has a multiple range of biological activities, covering the agricultural field (Liu & Howe, 1983), medicinal properties such as anticancer, antibiotic (Habeeb *et al.*, 2001; Mallesha *et al.*, 2001), antiviral and anti-HIV (Ichiba *et al.*, 1993) agents.

We report herein the synthesis and crystal structure of the title compound (Fig. 1). The 2,3,4,5-tetrahydro-pyridine ring adopts a half-chair conformation with puckering para-

<figure><img src="image_6.png" /></figure>

OPEN ACCESS
<figure><img src="image_2.png" /></figure>

IUCrData

<figure><img src="image_3.png" /></figure>

IUCrData

ISSN 2414-3146

Received 21 June 2021

Accepted 28 June 2021

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China

‡ Deceased August 2013.

Keywords: crystal structure; diazadihydroacenaphthylene derivative; hydrogen bonding and C—H···π interactions.

CCDC reference: 2089097

Structural data: full structural data are available
from iucrdata.iucr.org

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Akoun Abou,<sup>a*</sup> Fanté Bamba,<sup>b</sup> Jérôme Marrot,<sup>c</sup> Soro Yaya<sup>d</sup> and Jean-Marie Coustard<sup>e‡</sup>

<sup>a</sup>Department of Training and Research in Electrical and Electronic Engineering, Research Team: Instrumentation, Image and Spectroscopy, Félix Houphouët-Boigny National Polytechnic Institute, BP 1093 Yamoussoukro, Côte d'Ivoire,
<sup>b</sup>Laboratoire de Constitution et Réaction de la Matière, UFR SSMT, Université Félix Houphouët-Boigny, 22 BP 582 Abidjan 22, Côte d'Ivoire, <sup>c</sup>Laboratoire ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, <sup>d</sup>Laboratoire des Procédés Industriels de Synthèse et d'Environnement, Institut National Polytechnique Félix Houphouët-Boigny, BP 991 Yamoussoukro, Côte d'Ivoire, and <sup>e</sup>Laboratoire IC2MP-UMR 7285 CNRS, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France. *Correspondence e-mail: abouakoun@gmail.com

In the tricyclic title compound, C₁₁H₁₂N₂OS, the 2,3,4,5-tetrahydropyridine ring adopts a half-chair conformation. This ring makes dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring is oriented at an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. In the crystal, molecules associate *via* C—H···N hydrogen bonds and C—H···π interactions, forming a three-dimensional network.

<figure><img src="image_4.png" /><figcaption>Chemical scheme</figcaption></figure>

<figure><img src="image_5.png" /></figure>

Structure description

Diazadihydroacenaphthylene derivatives contain an isoxazoline scaffold and constitute an important class of heterocyclic compounds whose chemical properties have been investigated over the years (Jäger & Buss, 1980; Jäger *et al.*, 1980). This scaffold is used in the synthesis of several complex natural products (Saha & Bhattacharjya, 1997; Copp *et al.*, 1992) and is a pharmacophore of numerous medicinal chemistry compounds (Brandi *et al.*, 2003; King *et al.*, 1982; Bacher *et al.*, 1997; You *et al.*, 1995). It has also been reported that this scaffold has a multiple range of biological activities, covering the agricultural field (Liu & Howe, 1983), medicinal properties such as anticancer, antibiotic (Habeeb *et al.*, 2001; Mallesha *et al.*, 2001), antiviral and anti-HIV (Ichiba *et al.*, 1993) agents.

We report herein the synthesis and crystal structure of the title compound (Fig. 1). The 2,3,4,5-tetrahydro-pyridine ring adopts a half-chair conformation with puckering para-

<figure><img src="image_6.png" /></figure>

OPEN ACCESS
<caption>**Table 1**
Hydrogen-bond geometry (Å, °).</caption>

Cg is the centroid of the cyclohexa-1,3-diene ring.

<table><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>C1-H1···N12<sup>i</sup></td><td>0.98</td><td>2.64</td><td>3.4173 (16)</td><td>136</td></tr><tr><td>C5-H5B···Cg3<sup>ii</sup></td><td>0.97</td><td>2.80</td><td>3.6158 (17)</td><td>142</td></tr></tbody></table>

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

meters (Cremer & Pople, 1975) $Q_T = 0.4779 (15) Å$, $\theta = 129.65 (18)°$, $\phi = 29.0 (2)°$ and is oriented at dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring makes an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. These dihedral angles show that this tricycle compound is not planar, as confirmed by the total puckering amplitude $Q_T$ of 1.4727 (15) Å.

In the crystal, C1-H1···N12($x - \frac{1}{2}$, $-y + \frac{1}{2}$, $-z + 2$) hydrogen bonds (Table 1) link the molecules along the [010] direction (Fig. 2) and C5-H5B···Cg3($-x$, $-y + 1$, $-z$) interactions, where Cg3 is the centroid of the cyclohexa-1,3-diene ring (Fig. 3) are observed.

## Synthesis and crystallization

1-[(4-Methylbenzyl)amino]-1-methylthio-2-nitroethylene (236 mg; 1 mmol) was dissolved in 4.4 ml (50 mmol) of triflic acid at a temperature within the range -26 to -15°C under a nitrogen atmosphere. The reaction was monitored as follows: one or two drops of the reacting medium were quenched over ice (about 1 g) and extracted with CH₂Cl₂ (0.5 ml). The organic extract was dried over Na₂CO₃ and was purified by flash chromatography on a silica column (eluent: petroleum ether/ethyl acetate: (85:15, v/v)) to afford the title compound (97 mg; 0.441 mmol) as a colourless powder. The powder was dissolved in a minimum of dichloromethane by heating under agitation. To this hot mixture, petroleum ether was added until the formation of a new precipitate started, which dissolved in the resulting mixture upon heating. Upon cooling, colourless

<figure><img src="image_7.png" /><figcaption>**Figure 1**
The molecular structure of the title compound and the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>**Figure 2**
Part of the crystal packing of the title compound showing the formation of intermolecular C1-H1···N12 hydrogen bonds along the **b** axis. Dashed lines indicate hydrogen bond contacts. H atoms not involved in hydrogen bond interactions have been omitted for clarity.</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>**Figure 3**
A view of the crystal packing, showing the π-ring interactions (dashed lines). The yellow dots are centroids of rings. H atoms not involved in these interactions have been omitted for clarity.</figcaption></figure>
<caption>**Table 1**
Hydrogen-bond geometry (Å, °).</caption>

Cg is the centroid of the cyclohexa-1,3-diene ring.

<table><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>C1-H1···N12<sup>i</sup></td><td>0.98</td><td>2.64</td><td>3.4173 (16)</td><td>136</td></tr><tr><td>C5-H5B···Cg3<sup>ii</sup></td><td>0.97</td><td>2.80</td><td>3.6158 (17)</td><td>142</td></tr></tbody></table>

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

meters (Cremer & Pople, 1975) $Q_T = 0.4779 (15) Å$, $\theta = 129.65 (18)°$, $\phi = 29.0 (2)°$ and is oriented at dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring makes an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. These dihedral angles show that this tricycle compound is not planar, as confirmed by the total puckering amplitude $Q_T$ of 1.4727 (15) Å.

In the crystal, C1-H1···N12($x - \frac{1}{2}, -y + \frac{1}{2}, -z + 2$) hydrogen bonds (Table 1) link the molecules along the [010] direction (Fig. 2) and C5-H5B···Cg3($-x, -y + 1, -z$) interactions, where Cg3 is the centroid of the cyclohexa-1,3-diene ring (Fig. 3) are observed.

## Synthesis and crystallization

1-[(4-Methylbenzyl)amino]-1-methylthio-2-nitroethylene (236 mg; 1 mmol) was dissolved in 4.4 ml (50 mmol) of triflic acid at a temperature within the range -26 to -15°C under a nitrogen atmosphere. The reaction was monitored as follows: one or two drops of the reacting medium were quenched over ice (about 1 g) and extracted with CH₂Cl₂ (0.5 ml). The organic extract was dried over Na₂CO₃ and was purified by flash chromatography on a silica column (eluent: petroleum ether/ethyl acetate: (85:15, v/v)) to afford the title compound (97 mg; 0.441 mmol) as a colourless powder. The powder was dissolved in a minimum of dichloromethane by heating under agitation. To this hot mixture, petroleum ether was added until the formation of a new precipitate started, which dissolved in the resulting mixture upon heating. Upon cooling, colourless

<figure><img src="image_7.png" /><figcaption>**Figure 1**
The molecular structure of the title compound and the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>**Figure 2**
Part of the crystal packing of the title compound showing the formation of intermolecular C1-H1···N12 hydrogen bonds along the **b** axis. Dashed lines indicate hydrogen bond contacts. H atoms not involved in hydrogen bond interactions have been omitted for clarity.</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>**Figure 3**
A view of the crystal packing, showing the π-ring interactions (dashed lines). The yellow dots are centroids of rings. H atoms not involved in these interactions have been omitted for clarity.</figcaption></figure>
crystals suitable for single-crystal X-ray diffraction analysis were obtained, m.p. 120.1°C.

¹H NMR (CDCl₃): δ (p.p.m.) = 2.01 (s, 3 H, CH₃); 2.39 (s, 3H, SCH₃); 4.23 (d, J = 14.94 Hz, 1 H, H-8 b); 4.47 (s, 2 H, CH₂); 5.46 (d, J = 14.9 Hz, 1 H, H-8a); 5.81 (d, J = 7.1 Hz, 1 H, vinylic H); 5.84 (d, J = 7.1 Hz, 1 H, vinylic H).

¹³C NMR (CDCl₃): δ (p.p.m.) = 12.0 (SCH₃); 21.1 (CH₃); 48.0 (C-8a); 58.4 (CH₂); 82.0 (C-8 b); 117.8 (CH); 121.7 (CH); 124.8 (quaternary carbon); 130.4 (C-8); 152.6 (>C=N-O-); 155.4 (-S-C=N-).

MS (mass spectrometer, 70 eV); m/z (%): 220 [M⁺]. MS-HR(IE) m/z ([M⁺]) C₁₁H₁₂N₂OS: 220.0680.

## Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

## Acknowledgements

We thank the laboratory ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, for the use of the spectrometer and for the spectroscopic analysis.

## References

Bacher, E., Demnitz, F. W. J. & Hurni, T. (1997). *Tetrahedron*, **53**, 14317–14326.

Brandi, A., Cicchi, S., Cordero, F. M. & Goti, A. (2003). *Chem. Rev.* **103**, 1213–1270.

Bruker (2016). *SAINT*. Bruker AXS, Inc., Madison, Wisconsin, USA.

Bruker (2018). *APEX3*. Bruker AXS Inc., Madison, Wisconsin, USA.

Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). *J. Appl. Cryst.* **48**, 306–309.

Copp, B. R., Ireland, C. M. & Barrows, L. R. (1992). *J. Nat. Prod.* **55**, 822–823.

Cremer, D. & Pople, J. (1975). *J. Am. Chem. Soc.* **97**, 1354–1358.

Farrugia, L. J. (2012). *J. Appl. Cryst.* **45**, 849–854.

Habeeb, A. G., Praveen Rao, P. N. & Knaus, E. E. (2001). *J. Med. Chem.* **44**, 2921–2927.

Ichiba, T., Scheuer, P. J. & Kelly-Borges, M. (1993). *J. Org. Chem.* **58**, 4149–4150.

Jäger, V., Buss, V. & Schwab, W. (1980). *Liebigs Ann. Chem.* pp. 122–139.

<table><caption>Table 2</caption><caption>Experimental details.</caption><tbody><tr><td colspan="2"><strong>Crystal data</strong></td></tr><tr><td>Chemical formula</td><td>C<sub>11</sub>H<sub>12</sub>N<sub>2</sub>OS</td></tr><tr><td>M<sub>r</sub></td><td>220.29</td></tr><tr><td>Crystal system, space group</td><td>Orthorhombic, <i>Pbca</i></td></tr><tr><td>Temperature (K)</td><td>293</td></tr><tr><td>a, b, c (Å)</td><td>8.0175 (2), 14.4611 (3), 18.5612 (4)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>2152.02 (8)</td></tr><tr><td>Z</td><td>8</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.27</td></tr><tr><td>Crystal size (mm)</td><td>0.30 × 0.10 × 0.06</td></tr><tr><td colspan="2"><strong>Data collection</strong></td></tr><tr><td>Diffractometer</td><td>Bruker CCD area detector</td></tr><tr><td>Absorption correction</td><td>Multi-scan (<i>SADABS</i>; Krause <i>et al.</i>, 2015)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.922, 0.984</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>67637, 3155, 2560</td></tr><tr><td>R<sub>int</sub></td><td>0.032</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.705</td></tr><tr><td colspan="2"><strong>Refinement</strong></td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.041, 0.129, 1.08</td></tr><tr><td>No. of reflections</td><td>3155</td></tr><tr><td>No. of parameters</td><td>138</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.32, -0.19</td></tr></tbody></table>

Computer programs: *APEX3* (Bruker, 2018), *SAINT* (Bruker, 2016), *SIR2019* (Burla *et al.*, 2015), *PLATON* (Spek, 2020), *WinGX* (Farrugia, 2012), *SHELXL2018/3* (Sheldrick, 2015) and *publCIF* (Westrip, 2010).

Jäger, V. & Buss, V. (1980). *Liebigs Ann. Chem.* pp. 101–121.

King, S. W., Riordan, J. M., Holt, E. M. & Stammer, C. H. (1982). *J. Org. Chem.* **47**, 3270–3273.

Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). *J. Appl. Cryst.* **48**, 3–10.

Liu, K. C. & Howe, R. K. (1983). *J. Org. Chem.* **48**, 4590–4592.

Mallesha, H., Ravi kumar, K. R., Mantelingu, K. & Rangappa, K. S. (2001). *Synthesis*, **10**, 1459–1461.

Saha, A. & Bhattacharjya, A. (1997). *Chem. Commun.* pp. 495–496.

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

Spek, A. L. (2020). *Acta Cryst.* **E76**, 1–11.

Westrip, S. P. (2010). *J. Appl. Cryst.* **43**, 920–925.

You, Z., Khalil, M. A., Ko, D. & Lee, H. J. (1995). *Tetrahedron Lett.* **36**, 3303–3306.
crystals suitable for single-crystal X-ray diffraction analysis
were obtained, m.p. 120.1°C.

¹H NMR (CDCl₃): δ (p.p.m.) = 2.01 (s, 3 H, CH₃); 2.39 (s, 3H, SCH₃); 4.23 (d, J = 14.94 Hz, 1 H, H-8 b); 4.47 (s, 2 H, CH₂); 5.46 (d, J = 14.9 Hz, 1 H, H-8a); 5.81 (d, J = 7.1 Hz, 1 H, vinylic H); 5.84 (d, J = 7.1 Hz, 1 H, vinylic H).

¹³C NMR (CDCl₃): δ (p.p.m.) = 12.0 (SCH₃); 21.1 (CH₃); 48.0 (C-8a); 58.4 (CH₂); 82.0 (C-8 b); 117.8 (CH); 121.7 (CH); 124.8 (quaternary carbon); 130.4 (C-8); 152.6 (>C≡N–O–); 155.4 (–S–C≡N–).

MS (mass spectrometer, 70 eV); m/z (%): 220 [M⁺]. MS–HR(IE) m/z ([M⁺]) C₁₁H₁₂N₂OS: 220.0680.

## Refinement

Crystal data, data collection and structure refinement details
are summarized in Table 2.

## Acknowledgements

We thank the laboratory ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, for the use of the spectrometer and for the spectroscopic analysis.

## References

Bacher, E., Demnitz, F. W. J. & Hurni, T. (1997). *Tetrahedron*, **53**, 14317–14326.

Brandi, A., Cicchi, S., Cordero, F. M. & Goti, A. (2003). *Chem. Rev.* **103**, 1213–1270.

Bruker (2016). *SAINT*. Bruker AXS, Inc., Madison, Wisconsin, USA.

Bruker (2018). *APEX3*. Bruker AXS Inc., Madison, Wisconsin, USA.

Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). *J. Appl. Cryst.* **48**, 306–309.

Copp, B. R., Ireland, C. M. & Barrows, L. R. (1992). *J. Nat. Prod.* **55**, 822–823.

Cremer, D. & Pople, J. (1975). *J. Am. Chem. Soc.* **97**, 1354–1358.

Farrugia, L. J. (2012). *J. Appl. Cryst.* **45**, 849–854.

Habeeb, A. G., Praveen Rao, P. N. & Knaus, E. E. (2001). *J. Med. Chem.* **44**, 2921–2927.

Ichiba, T., Scheuer, P. J. & Kelly-Borges, M. (1993). *J. Org. Chem.* **58**, 4149–4150.

Jäger, V., Buss, V. & Schwab, W. (1980). *Liebigs Ann. Chem.* pp. 122–139.

<table><caption>Table 2</caption><caption>Experimental details.</caption><tbody><tr><td colspan="2"><strong>Crystal data</strong></td></tr><tr><td>Chemical formula</td><td>C<sub>11</sub>H<sub>12</sub>N<sub>2</sub>OS</td></tr><tr><td>M<sub>r</sub></td><td>220.29</td></tr><tr><td>Crystal system, space group</td><td>Orthorhombic, <i>Pbca</i></td></tr><tr><td>Temperature (K)</td><td>293</td></tr><tr><td>a, b, c (Å)</td><td>8.0175 (2), 14.4611 (3), 18.5612 (4)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>2152.02 (8)</td></tr><tr><td>Z</td><td>8</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.27</td></tr><tr><td>Crystal size (mm)</td><td>0.30 × 0.10 × 0.06</td></tr><tr><td colspan="2"><strong>Data collection</strong></td></tr><tr><td>Diffractometer</td><td>Bruker CCD area detector</td></tr><tr><td>Absorption correction</td><td>Multi-scan (<i>SADABS</i>; Krause <i>et al.</i>, 2015)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.922, 0.984</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>67637, 3155, 2560</td></tr><tr><td>R<sub>int</sub></td><td>0.032</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.705</td></tr><tr><td colspan="2"><strong>Refinement</strong></td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.041, 0.129, 1.08</td></tr><tr><td>No. of reflections</td><td>3155</td></tr><tr><td>No. of parameters</td><td>138</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.32, -0.19</td></tr></tbody></table>

Computer programs: *APEX3* (Bruker, 2018), *SAINT* (Bruker, 2016), *SIR2019* (Burla *et al.*, 2015), *PLATON* (Spek, 2020), *WinGX* (Farrugia, 2012), *SHELXL2018/3* (Sheldrick, 2015) and *publCIF* (Westrip, 2010).

Jäger, V. & Buss, V. (1980). *Liebigs Ann. Chem.* pp. 101–121.

King, S. W., Riordan, J. M., Holt, E. M. & Stammer, C. H. (1982). *J. Org. Chem.* **47**, 3270–3273.

Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). *J. Appl. Cryst.* **48**, 3–10.

Liu, K. C. & Howe, R. K. (1983). *J. Org. Chem.* **48**, 4590–4592.

Mallesha, H., Ravi kumar, K. R., Mantelingu, K. & Rangappa, K. S. (2001). *Synthesis*, **10**, 1459–1461.

Saha, A. & Bhattacharjya, A. (1997). *Chem. Commun.* pp. 495–496.

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

Spek, A. L. (2020). *Acta Cryst.* **E76**, 1–11.

Westrip, S. P. (2010). *J. Appl. Cryst.* **43**, 920–925.

You, Z., Khalil, M. A., Ko, D. & Lee, H. J. (1995). *Tetrahedron Lett.* **36**, 3303–3306.
full crystallographic data

IUCrData (2021). **6**, x210674 [https://doi.org/10.1107/S241431462100674X]

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya and Jean-Marie Coustard

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Crystal data

$C_{11}H_{12}N_2OS$

$M_r = 220.29$

Orthorhombic, Pbca

Hall symbol: -P 2ac 2ab

$a = 8.0175 (2) Å$

$b = 14.4611 (3) Å$

$c = 18.5612 (4) Å$

$V = 2152.02 (8) Å^3$

$Z = 8$

$F(000) = 928$

$D_x = 1.360 \text{ Mg m}^{-3}$

Melting point: 393.1 K

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 8401 reflections

$\theta = 2.2-29.8°$

$\mu = 0.27 \text{ mm}^{-1}$

$T = 293 K$

Parallelepiped, colorless

$0.30 \times 0.10 \times 0.06 \text{ mm}$

Data collection

Bruker CCD area detector
diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

Detector resolution: 512 pixels mm⁻¹

phi and ω scans

Absorption correction: multi-scan
(SADABS; Krause et al., 2015)

$T_{\text{min}} = 0.922, T_{\text{max}} = 0.984$

67637 measured reflections

3155 independent reflections

2560 reflections with $I > 2\sigma(I)$

$R_{\text{int}} = 0.032$

$\theta_{\text{max}} = 30.1°, \theta_{\text{min}} = 2.8°$

$h = -11 \rightarrow 11$

$k = -20 \rightarrow 20$

$l = -26 \rightarrow 26$

Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.041$

$wR(F^2) = 0.129$

$S = 1.08$

3155 reflections

138 parameters

0 restraints

0 constraints

Primary atom site location: structure-invariant
direct methods

Secondary atom site location: difference Fourier
map

Hydrogen site location: inferred from
neighbouring sites

H-atom parameters constrained

$w = 1/[\sigma^2(F_o^2) + (0.0606P)^2 + 0.5724P]$ where $P = (F_o^2 + 2F_c^2)/3$

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

$\Delta\rho_{\text{max}} = 0.32 \text{ e Å}^{-3}$

$\Delta\rho_{\text{min}} = -0.19 \text{ e Å}^{-3}$

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.
full crystallographic data

IUCrData (2021). **6**, x210674 [https://doi.org/10.1107/S241431462100674X]

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Akoun Abou, Fanté Bamba, Jérôme Marrot, Soro Yaya and Jean-Marie Coustard

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Crystal data

$C_{11}H_{12}N_2OS$

$M_r = 220.29$

Orthorhombic, Pbca

Hall symbol: -P 2ac 2ab

$a = 8.0175 (2) Å$

$b = 14.4611 (3) Å$

$c = 18.5612 (4) Å$

$V = 2152.02 (8) Å^3$

$Z = 8$

$F(000) = 928$

Data collection

Bruker CCD area detector
diffractometer

Radiation source: fine-focus sealed tube

Graphite monochromator

Detector resolution: 512 pixels mm⁻¹

phi and ω scans

Absorption correction: multi-scan
(SADABS; Krause et al., 2015)

$T_{min} = 0.922, T_{max} = 0.984$

Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2σ(F^2)] = 0.041$

$wR(F^2) = 0.129$

$S = 1.08$

3155 reflections

138 parameters

0 restraints

0 constraints

Primary atom site location: structure-invariant
direct methods

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.

$D_x = 1.360 \text{ Mg m}^{-3}$

Melting point: 393.1 K

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 8401 reflections

$\theta = 2.2-29.8°$

$\mu = 0.27 \text{ mm}^{-1}$

$T = 293 K$

Parallelepiped, colorless

$0.30 \times 0.10 \times 0.06 \text{ mm}$

67637 measured reflections

3155 independent reflections

2560 reflections with $I > 2σ(I)$

$R_{int} = 0.032$

$\theta_{max} = 30.1°, \theta_{min} = 2.8°$

$h = -11 \rightarrow 11$

$k = -20 \rightarrow 20$

$l = -26 \rightarrow 26$

Secondary atom site location: difference Fourier
map

Hydrogen site location: inferred from
neighbouring sites

H-atom parameters constrained

$w = 1/[σ^2(F_o^2) + (0.0606P)^2 + 0.5724P]$ where $P = (F_o^2 + 2F_c^2)/3$

($\Delta/σ)_{max} = 0.001$

$\Delta\rho_{max} = 0.32 \text{ e Å}^{-3}$

$\Delta\rho_{min} = -0.19 \text{ e Å}^{-3}$
<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></tr></thead><tbody><tr><td>S1</td><td>0.87930 (6)</td><td>0.23268 (3)</td><td>0.81332 (2)</td><td>0.05945 (15)</td></tr><tr><td>C1</td><td>0.68279 (16)</td><td>0.11024 (8)</td><td>0.99475 (8)</td><td>0.0430 (3)</td></tr><tr><td>H1</td><td>0.567035</td><td>0.131511</td><td>0.991152</td><td>0.052*</td></tr><tr><td>C2</td><td>0.79398 (16)</td><td>0.16562 (8)</td><td>0.94630 (7)</td><td>0.0411 (3)</td></tr><tr><td>C3</td><td>0.78747 (16)</td><td>0.14749 (9)</td><td>0.86830 (8)</td><td>0.0441 (3)</td></tr><tr><td>N4</td><td>0.72257 (16)</td><td>0.07471 (9)</td><td>0.84198 (7)</td><td>0.0527 (3)</td></tr><tr><td>C5</td><td>0.6511 (2)</td><td>0.00367 (11)</td><td>0.89045 (9)</td><td>0.0581 (4)</td></tr><tr><td>H5A</td><td>0.685682</td><td>-0.056803</td><td>0.873466</td><td>0.070*</td></tr><tr><td>H5B</td><td>0.530492</td><td>0.006443</td><td>0.887046</td><td>0.070*</td></tr><tr><td>C6</td><td>0.69925 (16)</td><td>0.01268 (9)</td><td>0.96758 (8)</td><td>0.0458 (3)</td></tr><tr><td>C7</td><td>0.77226 (18)</td><td>-0.05134 (9)</td><td>1.00803 (9)</td><td>0.0512 (3)</td></tr><tr><td>H7</td><td>0.786148</td><td>-0.110657</td><td>0.989631</td><td>0.061*</td></tr><tr><td>C8</td><td>0.8308 (2)</td><td>-0.03094 (10)</td><td>1.08014 (9)</td><td>0.0543 (4)</td></tr><tr><td>H8</td><td>0.871921</td><td>-0.079538</td><td>1.107742</td><td>0.065*</td></tr><tr><td>C9</td><td>0.8293 (2)</td><td>0.05336 (11)</td><td>1.10934 (9)</td><td>0.0544 (3)</td></tr><tr><td>C10</td><td>0.7554 (2)</td><td>0.13333 (9)</td><td>1.06827 (8)</td><td>0.0492 (3)</td></tr><tr><td>H10</td><td>0.668392</td><td>0.162125</td><td>1.097811</td><td>0.059*</td></tr><tr><td>O11</td><td>0.88721 (16)</td><td>0.20355 (7)</td><td>1.05266 (6)</td><td>0.0584 (3)</td></tr><tr><td>N12</td><td>0.90369 (16)</td><td>0.21466 (8)</td><td>0.97783 (7)</td><td>0.0486 (3)</td></tr><tr><td>C13</td><td>0.8627 (3)</td><td>0.17816 (14)</td><td>0.72661 (9)</td><td>0.0685 (5)</td></tr><tr><td>H13A</td><td>0.748115</td><td>0.177828</td><td>0.711577</td><td>0.103*</td></tr><tr><td>H13B</td><td>0.902781</td><td>0.115738</td><td>0.729744</td><td>0.103*</td></tr><tr><td>H13C</td><td>0.928286</td><td>0.211794</td><td>0.692175</td><td>0.103*</td></tr><tr><td>C14</td><td>0.8944 (4)</td><td>0.07297 (16)</td><td>1.18338 (10)</td><td>0.0846 (7)</td></tr><tr><td>H14A</td><td>0.928090</td><td>0.016115</td><td>1.205768</td><td>0.127*</td></tr><tr><td>H14B</td><td>0.808424</td><td>0.101512</td><td>1.211680</td><td>0.127*</td></tr><tr><td>H14C</td><td>0.988454</td><td>0.113844</td><td>1.180153</td><td>0.127*</td></tr></tbody></table>

<table><caption>Atomic displacement parameters (Å²)</caption><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>0.0740 (3)</td><td>0.0518 (2)</td><td>0.0525 (2)</td><td>-0.00919 (18)</td><td>0.00304 (17)</td><td>0.00618 (15)</td></tr><tr><td>C1</td><td>0.0366 (6)</td><td>0.0335 (5)</td><td>0.0588 (7)</td><td>0.0038 (4)</td><td>0.0087 (5)</td><td>0.0000 (5)</td></tr><tr><td>C2</td><td>0.0417 (6)</td><td>0.0302 (5)</td><td>0.0513 (7)</td><td>0.0016 (4)</td><td>0.0033 (5)</td><td>-0.0005 (5)</td></tr><tr><td>C3</td><td>0.0415 (6)</td><td>0.0407 (6)</td><td>0.0502 (7)</td><td>0.0004 (5)</td><td>-0.0010 (5)</td><td>0.0000 (5)</td></tr><tr><td>N4</td><td>0.0512 (6)</td><td>0.0494 (6)</td><td>0.0576 (7)</td><td>-0.0054 (5)</td><td>-0.0049 (5)</td><td>-0.0056 (5)</td></tr><tr><td>C5</td><td>0.0584 (8)</td><td>0.0449 (7)</td><td>0.0710 (10)</td><td>-0.0145 (7)</td><td>-0.0018 (7)</td><td>-0.0085 (7)</td></tr><tr><td>C6</td><td>0.0394 (6)</td><td>0.0339 (6)</td><td>0.0641 (8)</td><td>-0.0058 (5)</td><td>0.0093 (6)</td><td>-0.0037 (5)</td></tr><tr><td>C7</td><td>0.0477 (7)</td><td>0.0319 (5)</td><td>0.0739 (9)</td><td>-0.0012 (5)</td><td>0.0151 (7)</td><td>-0.0008 (6)</td></tr><tr><td>C8</td><td>0.0523 (8)</td><td>0.0436 (7)</td><td>0.0669 (9)</td><td>0.0072 (6)</td><td>0.0129 (7)</td><td>0.0123 (6)</td></tr><tr><td>C9</td><td>0.0590 (8)</td><td>0.0511 (8)</td><td>0.0530 (8)</td><td>0.0045 (7)</td><td>0.0112 (6)</td><td>0.0062 (6)</td></tr><tr><td>C10</td><td>0.0542 (7)</td><td>0.0393 (6)</td><td>0.0540 (7)</td><td>0.0051 (6)</td><td>0.0137 (6)</td><td>-0.0016 (5)</td></tr><tr><td>O11</td><td>0.0802 (8)</td><td>0.0458 (5)</td><td>0.0493 (6)</td><td>-0.0139 (5)</td><td>-0.0003 (5)</td><td>-0.0045 (4)</td></tr><tr><td>N12</td><td>0.0596 (7)</td><td>0.0358 (5)</td><td>0.0504 (6)</td><td>-0.0081 (5)</td><td>0.0009 (5)</td><td>-0.0014 (4)</td></tr><tr><td>C13</td><td>0.0823 (12)</td><td>0.0727 (11)</td><td>0.0507 (8)</td><td>0.0071 (9)</td><td>0.0068 (8)</td><td>-0.0005 (8)</td></tr></tbody></table>
<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></tr></thead><tbody><tr><td>S1</td><td>0.87930 (6)</td><td>0.23268 (3)</td><td>0.81332 (2)</td><td>0.05945 (15)</td></tr><tr><td>C1</td><td>0.68279 (16)</td><td>0.11024 (8)</td><td>0.99475 (8)</td><td>0.0430 (3)</td></tr><tr><td>H1</td><td>0.567035</td><td>0.131511</td><td>0.991152</td><td>0.052*</td></tr><tr><td>C2</td><td>0.79398 (16)</td><td>0.16562 (8)</td><td>0.94630 (7)</td><td>0.0411 (3)</td></tr><tr><td>C3</td><td>0.78747 (16)</td><td>0.14749 (9)</td><td>0.86830 (8)</td><td>0.0441 (3)</td></tr><tr><td>N4</td><td>0.72257 (16)</td><td>0.07471 (9)</td><td>0.84198 (7)</td><td>0.0527 (3)</td></tr><tr><td>C5</td><td>0.6511 (2)</td><td>0.00367 (11)</td><td>0.89045 (9)</td><td>0.0581 (4)</td></tr><tr><td>H5A</td><td>0.685682</td><td>-0.056803</td><td>0.873466</td><td>0.070*</td></tr><tr><td>H5B</td><td>0.530492</td><td>0.006443</td><td>0.887046</td><td>0.070*</td></tr><tr><td>C6</td><td>0.69925 (16)</td><td>0.01268 (9)</td><td>0.96758 (8)</td><td>0.0458 (3)</td></tr><tr><td>C7</td><td>0.77226 (18)</td><td>-0.05134 (9)</td><td>1.00803 (9)</td><td>0.0512 (3)</td></tr><tr><td>H7</td><td>0.786148</td><td>-0.110657</td><td>0.989631</td><td>0.061*</td></tr><tr><td>C8</td><td>0.8308 (2)</td><td>-0.03094 (10)</td><td>1.08014 (9)</td><td>0.0543 (4)</td></tr><tr><td>H8</td><td>0.871921</td><td>-0.079538</td><td>1.107742</td><td>0.065*</td></tr><tr><td>C9</td><td>0.8293 (2)</td><td>0.05336 (11)</td><td>1.10934 (9)</td><td>0.0544 (3)</td></tr><tr><td>C10</td><td>0.7554 (2)</td><td>0.13333 (9)</td><td>1.06827 (8)</td><td>0.0492 (3)</td></tr><tr><td>H10</td><td>0.668392</td><td>0.162125</td><td>1.097811</td><td>0.059*</td></tr><tr><td>O11</td><td>0.88721 (16)</td><td>0.20355 (7)</td><td>1.05266 (6)</td><td>0.0584 (3)</td></tr><tr><td>N12</td><td>0.90369 (16)</td><td>0.21466 (8)</td><td>0.97783 (7)</td><td>0.0486 (3)</td></tr><tr><td>C13</td><td>0.8627 (3)</td><td>0.17816 (14)</td><td>0.72661 (9)</td><td>0.0685 (5)</td></tr><tr><td>H13A</td><td>0.748115</td><td>0.177828</td><td>0.711577</td><td>0.103*</td></tr><tr><td>H13B</td><td>0.902781</td><td>0.115738</td><td>0.729744</td><td>0.103*</td></tr><tr><td>H13C</td><td>0.928286</td><td>0.211794</td><td>0.692175</td><td>0.103*</td></tr><tr><td>C14</td><td>0.8944 (4)</td><td>0.07297 (16)</td><td>1.18338 (10)</td><td>0.0846 (7)</td></tr><tr><td>H14A</td><td>0.928090</td><td>0.016115</td><td>1.205768</td><td>0.127*</td></tr><tr><td>H14B</td><td>0.808424</td><td>0.101512</td><td>1.211680</td><td>0.127*</td></tr><tr><td>H14C</td><td>0.988454</td><td>0.113844</td><td>1.180153</td><td>0.127*</td></tr></tbody></table>

<table><caption>Atomic displacement parameters (Å²)</caption><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>0.0740 (3)</td><td>0.0518 (2)</td><td>0.0525 (2)</td><td>-0.00919 (18)</td><td>0.00304 (17)</td><td>0.00618 (15)</td></tr><tr><td>C1</td><td>0.0366 (6)</td><td>0.0335 (5)</td><td>0.0588 (7)</td><td>0.0038 (4)</td><td>0.0087 (5)</td><td>0.0000 (5)</td></tr><tr><td>C2</td><td>0.0417 (6)</td><td>0.0302 (5)</td><td>0.0513 (7)</td><td>0.0016 (4)</td><td>0.0033 (5)</td><td>-0.0005 (5)</td></tr><tr><td>C3</td><td>0.0415 (6)</td><td>0.0407 (6)</td><td>0.0502 (7)</td><td>0.0004 (5)</td><td>-0.0010 (5)</td><td>0.0000 (5)</td></tr><tr><td>N4</td><td>0.0512 (6)</td><td>0.0494 (6)</td><td>0.0576 (7)</td><td>-0.0054 (5)</td><td>-0.0049 (5)</td><td>-0.0056 (5)</td></tr><tr><td>C5</td><td>0.0584 (8)</td><td>0.0449 (7)</td><td>0.0710 (10)</td><td>-0.0145 (7)</td><td>-0.0018 (7)</td><td>-0.0085 (7)</td></tr><tr><td>C6</td><td>0.0394 (6)</td><td>0.0339 (6)</td><td>0.0641 (8)</td><td>-0.0058 (5)</td><td>0.0093 (6)</td><td>-0.0037 (5)</td></tr><tr><td>C7</td><td>0.0477 (7)</td><td>0.0319 (5)</td><td>0.0739 (9)</td><td>-0.0012 (5)</td><td>0.0151 (7)</td><td>-0.0008 (6)</td></tr><tr><td>C8</td><td>0.0523 (8)</td><td>0.0436 (7)</td><td>0.0669 (9)</td><td>0.0072 (6)</td><td>0.0129 (7)</td><td>0.0123 (6)</td></tr><tr><td>C9</td><td>0.0590 (8)</td><td>0.0511 (8)</td><td>0.0530 (8)</td><td>0.0045 (7)</td><td>0.0112 (6)</td><td>0.0062 (6)</td></tr><tr><td>C10</td><td>0.0542 (7)</td><td>0.0393 (6)</td><td>0.0540 (7)</td><td>0.0051 (6)</td><td>0.0137 (6)</td><td>-0.0016 (5)</td></tr><tr><td>O11</td><td>0.0802 (8)</td><td>0.0458 (5)</td><td>0.0493 (6)</td><td>-0.0139 (5)</td><td>-0.0003 (5)</td><td>-0.0045 (4)</td></tr><tr><td>N12</td><td>0.0596 (7)</td><td>0.0358 (5)</td><td>0.0504 (6)</td><td>-0.0081 (5)</td><td>0.0009 (5)</td><td>-0.0014 (4)</td></tr><tr><td>C13</td><td>0.0823 (12)</td><td>0.0727 (11)</td><td>0.0507 (8)</td><td>0.0071 (9)</td><td>0.0068 (8)</td><td>-0.0005 (8)</td></tr></tbody></table>
<table><caption>Geometric parameters (Å, °)</caption><tr><td>C14</td><td>0.123 (2)</td><td>0.0730 (12)</td><td>0.0575 (10)</td><td>0.0118 (12)</td><td>-0.0060 (11)</td><td>0.0052 (9)</td></tr></table>

<table><tr><td>S1—C3</td><td>1.7610 (14)</td><td>C7—H7</td><td>0.9300</td></tr><tr><td>S1—C13</td><td>1.7972 (18)</td><td>C8—C9</td><td>1.334 (2)</td></tr><tr><td>C1—C2</td><td>1.4984 (18)</td><td>C8—H8</td><td>0.9300</td></tr><tr><td>C1—C6</td><td>1.5039 (17)</td><td>C9—C14</td><td>1.497 (3)</td></tr><tr><td>C1—C10</td><td>1.521 (2)</td><td>C9—C10</td><td>1.506 (2)</td></tr><tr><td>C1—H1</td><td>0.9800</td><td>C10—O11</td><td>1.4942 (18)</td></tr><tr><td>C2—N12</td><td>1.2724 (17)</td><td>C10—H10</td><td>0.9800</td></tr><tr><td>C2—C3</td><td>1.4723 (19)</td><td>O11—N12</td><td>1.4045 (16)</td></tr><tr><td>C3—N4</td><td>1.2717 (17)</td><td>C13—H13A</td><td>0.9600</td></tr><tr><td>N4—C5</td><td>1.481 (2)</td><td>C13—H13B</td><td>0.9600</td></tr><tr><td>C5—C6</td><td>1.489 (2)</td><td>C13—H13C</td><td>0.9600</td></tr><tr><td>C5—H5A</td><td>0.9700</td><td>C14—H14A</td><td>0.9600</td></tr><tr><td>C5—H5B</td><td>0.9700</td><td>C14—H14B</td><td>0.9600</td></tr><tr><td>C6—C7</td><td>1.328 (2)</td><td>C14—H14C</td><td>0.9600</td></tr><tr><td>C7—C8</td><td>1.449 (2)</td><td></td><td></td></tr><tr><td>C3—S1—C13</td><td>100.43 (8)</td><td>C9—C8—C7</td><td>123.94 (14)</td></tr><tr><td>C2—C1—C6</td><td>104.35 (10)</td><td>C9—C8—H8</td><td>118.0</td></tr><tr><td>C2—C1—C10</td><td>101.16 (11)</td><td>C7—C8—H8</td><td>118.0</td></tr><tr><td>C6—C1—C10</td><td>118.25 (12)</td><td>C8—C9—C14</td><td>122.87 (16)</td></tr><tr><td>C2—C1—H1</td><td>110.8</td><td>C8—C9—C10</td><td>119.97 (15)</td></tr><tr><td>C6—C1—H1</td><td>110.8</td><td>C14—C9—C10</td><td>117.15 (15)</td></tr><tr><td>C10—C1—H1</td><td>110.8</td><td>O11—C10—C9</td><td>109.97 (13)</td></tr><tr><td>N12—C2—C3</td><td>125.17 (12)</td><td>O11—C10—C1</td><td>104.24 (10)</td></tr><tr><td>N12—C2—C1</td><td>115.67 (12)</td><td>C9—C10—C1</td><td>115.85 (12)</td></tr><tr><td>C3—C2—C1</td><td>118.29 (11)</td><td>O11—C10—H10</td><td>108.8</td></tr><tr><td>N4—C3—C2</td><td>122.66 (13)</td><td>C9—C10—H10</td><td>108.8</td></tr><tr><td>N4—C3—S1</td><td>121.83 (12)</td><td>C1—C10—H10</td><td>108.8</td></tr><tr><td>C2—C3—S1</td><td>115.49 (9)</td><td>N12—O11—C10</td><td>109.64 (10)</td></tr><tr><td>C3—N4—C5</td><td>119.94 (13)</td><td>C2—N12—O11</td><td>109.03 (11)</td></tr><tr><td>N4—C5—C6</td><td>115.04 (12)</td><td>S1—C13—H13A</td><td>109.5</td></tr><tr><td>N4—C5—H5A</td><td>108.5</td><td>S1—C13—H13B</td><td>109.5</td></tr><tr><td>C6—C5—H5A</td><td>108.5</td><td>H13A—C13—H13B</td><td>109.5</td></tr><tr><td>N4—C5—H5B</td><td>108.5</td><td>S1—C13—H13C</td><td>109.5</td></tr><tr><td>C6—C5—H5B</td><td>108.5</td><td>H13A—C13—H13C</td><td>109.5</td></tr><tr><td>H5A—C5—H5B</td><td>107.5</td><td>H13B—C13—H13C</td><td>109.5</td></tr><tr><td>C7—C6—C5</td><td>126.65 (14)</td><td>C9—C14—H14A</td><td>109.5</td></tr><tr><td>C7—C6—C1</td><td>120.20 (14)</td><td>C9—C14—H14B</td><td>109.5</td></tr><tr><td>C5—C6—C1</td><td>112.45 (13)</td><td>H14A—C14—H14B</td><td>109.5</td></tr><tr><td>C6—C7—C8</td><td>121.55 (13)</td><td>C9—C14—H14C</td><td>109.5</td></tr><tr><td>C6—C7—H7</td><td>119.2</td><td>H14A—C14—H14C</td><td>109.5</td></tr><tr><td>C8—C7—H7</td><td>119.2</td><td>H14B—C14—H14C</td><td>109.5</td></tr></table>
<table><caption>Geometric parameters (Å, °)</caption><tr><td>C14</td><td>0.123 (2)</td><td>0.0730 (12)</td><td>0.0575 (10)</td><td>0.0118 (12)</td><td>-0.0060 (11)</td><td>0.0052 (9)</td></tr></table>

<table><tr><td>S1—C3</td><td>1.7610 (14)</td><td>C7—H7</td><td>0.9300</td></tr><tr><td>S1—C13</td><td>1.7972 (18)</td><td>C8—C9</td><td>1.334 (2)</td></tr><tr><td>C1—C2</td><td>1.4984 (18)</td><td>C8—H8</td><td>0.9300</td></tr><tr><td>C1—C6</td><td>1.5039 (17)</td><td>C9—C14</td><td>1.497 (3)</td></tr><tr><td>C1—C10</td><td>1.521 (2)</td><td>C9—C10</td><td>1.506 (2)</td></tr><tr><td>C1—H1</td><td>0.9800</td><td>C10—O11</td><td>1.4942 (18)</td></tr><tr><td>C2—N12</td><td>1.2724 (17)</td><td>C10—H10</td><td>0.9800</td></tr><tr><td>C2—C3</td><td>1.4723 (19)</td><td>O11—N12</td><td>1.4045 (16)</td></tr><tr><td>C3—N4</td><td>1.2717 (17)</td><td>C13—H13A</td><td>0.9600</td></tr><tr><td>N4—C5</td><td>1.481 (2)</td><td>C13—H13B</td><td>0.9600</td></tr><tr><td>C5—C6</td><td>1.489 (2)</td><td>C13—H13C</td><td>0.9600</td></tr><tr><td>C5—H5A</td><td>0.9700</td><td>C14—H14A</td><td>0.9600</td></tr><tr><td>C5—H5B</td><td>0.9700</td><td>C14—H14B</td><td>0.9600</td></tr><tr><td>C6—C7</td><td>1.328 (2)</td><td>C14—H14C</td><td>0.9600</td></tr><tr><td>C7—C8</td><td>1.449 (2)</td><td></td><td></td></tr><tr><td>C3—S1—C13</td><td>100.43 (8)</td><td>C9—C8—C7</td><td>123.94 (14)</td></tr><tr><td>C2—C1—C6</td><td>104.35 (10)</td><td>C9—C8—H8</td><td>118.0</td></tr><tr><td>C2—C1—C10</td><td>101.16 (11)</td><td>C7—C8—H8</td><td>118.0</td></tr><tr><td>C6—C1—C10</td><td>118.25 (12)</td><td>C8—C9—C14</td><td>122.87 (16)</td></tr><tr><td>C2—C1—H1</td><td>110.8</td><td>C8—C9—C10</td><td>119.97 (15)</td></tr><tr><td>C6—C1—H1</td><td>110.8</td><td>C14—C9—C10</td><td>117.15 (15)</td></tr><tr><td>C10—C1—H1</td><td>110.8</td><td>O11—C10—C9</td><td>109.97 (13)</td></tr><tr><td>N12—C2—C3</td><td>125.17 (12)</td><td>O11—C10—C1</td><td>104.24 (10)</td></tr><tr><td>N12—C2—C1</td><td>115.67 (12)</td><td>C9—C10—C1</td><td>115.85 (12)</td></tr><tr><td>C3—C2—C1</td><td>118.29 (11)</td><td>O11—C10—H10</td><td>108.8</td></tr><tr><td>N4—C3—C2</td><td>122.66 (13)</td><td>C9—C10—H10</td><td>108.8</td></tr><tr><td>N4—C3—S1</td><td>121.83 (12)</td><td>C1—C10—H10</td><td>108.8</td></tr><tr><td>C2—C3—S1</td><td>115.49 (9)</td><td>N12—O11—C10</td><td>109.64 (10)</td></tr><tr><td>C3—N4—C5</td><td>119.94 (13)</td><td>C2—N12—O11</td><td>109.03 (11)</td></tr><tr><td>N4—C5—C6</td><td>115.04 (12)</td><td>S1—C13—H13A</td><td>109.5</td></tr><tr><td>N4—C5—H5A</td><td>108.5</td><td>S1—C13—H13B</td><td>109.5</td></tr><tr><td>C6—C5—H5A</td><td>108.5</td><td>H13A—C13—H13B</td><td>109.5</td></tr><tr><td>N4—C5—H5B</td><td>108.5</td><td>S1—C13—H13C</td><td>109.5</td></tr><tr><td>C6—C5—H5B</td><td>108.5</td><td>H13A—C13—H13C</td><td>109.5</td></tr><tr><td>H5A—C5—H5B</td><td>107.5</td><td>H13B—C13—H13C</td><td>109.5</td></tr><tr><td>C7—C6—C5</td><td>126.65 (14)</td><td>C9—C14—H14A</td><td>109.5</td></tr><tr><td>C7—C6—C1</td><td>120.20 (14)</td><td>C9—C14—H14B</td><td>109.5</td></tr><tr><td>C5—C6—C1</td><td>112.45 (13)</td><td>H14A—C14—H14B</td><td>109.5</td></tr><tr><td>C6—C7—C8</td><td>121.55 (13)</td><td>C9—C14—H14C</td><td>109.5</td></tr><tr><td>C6—C7—H7</td><td>119.2</td><td>H14A—C14—H14C</td><td>109.5</td></tr><tr><td>C8—C7—H7</td><td>119.2</td><td>H14B—C14—H14C</td><td>109.5</td></tr></table>
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the cyclohexa-1,3-diene ring.

<table><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>C1—H1···N12<sup>i</sup></td><td>0.98</td><td>2.64</td><td>3.4173 (16)</td><td>136</td></tr><tr><td>C5—H5B···Cg3<sup>ii</sup></td><td>0.97</td><td>2.80</td><td>3.6158 (17)</td><td>142</td></tr></tbody></table>

Symmetry codes: (i) x−1/2, −y+1/2, −z+2; (ii) −x, −y+1, −z.
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the cyclohexa-1,3-diene ring.

<table><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>C1—H1···N12<sup>i</sup></td><td>0.98</td><td>2.64</td><td>3.4173 (16)</td><td>136</td></tr><tr><td>C5—H5B···Cg3<sup>ii</sup></td><td>0.97</td><td>2.80</td><td>3.6158 (17)</td><td>142</td></tr></tbody></table>

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