# Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-trimethylquinoxaline-2,3(1 H ,4 H )-dione monohydrate

Ayman Zouitini, Md. Serajul Haque Faizi, Younes Ouzidan, Fouad Ouazzani

Chahdi, Jérôme Marrot, Damien Prim, Necmi Dege, Ashraf Mashrai

► To cite this version:

Ayman Zouitini, Md. Serajul Haque Faizi, Younes Ouzidan, Fouad Ouazzani Chahdi, Jérôme Marrot, et al. Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-trimethylquinoxaline-2,3(1 H ,4 H )-dione monohydrate. Acta crystallographica Section E: Crystallographic communications [2015-..], 2020, 76 (8), pp.1296-1301. 10.1107/S2056989020009573 . hal-03119312

HAL Id: hal-03119312

https://hal.science/hal-03119312

Submitted on 7 Jun 2023

**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>

Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 17 June 2020

Accepted 13 July 2020

Edited by A. V. Yatsenko, Moscow State
University, Russia

**Keywords:** crystal structure; quinoxaline-2,3-dione; Hirshfeld surface analysis; disorder; hydrogen bonding.

CCDC reference: 1936663

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

# Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione monohydrate

Ayman Zouitini,ª Md. Serajul Haque Faizi,ᵇ Younes Ouzidan,ᶜ Fouad Ouazzani Chahdi,ª Jérôme Marrot,ᵈ Damien Prim,ᵈ Necmi Degee and Ashraf Mashraif*

ªLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, BP 2202, Fez, Morocco, ᵇDepartment of Chemistry, Langat Singh College, B.R.A. Bihar University, Muzaffarpur, Bihar-842001, India, ᶜLaboratoire de Chimie Physique et Chimie Bio-organique, Faculté des Sciences et Techniques Mohammedia, Université Hassan II, Casablanca, BP 146, 28800, Mohammedia, Morocco, ᵈInstitut Lavoisier de Versailles, UVSQ, CNRS, Université Paris-Saclay, 78035 Versailles, France, ᵉDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, Samsun, 55200, Turkey, and ᵈDepartment of Pharmacy, University of Science and Technology, Ibb Branch, Ibb, Yemen. *Correspondence e-mail: ashraf.yemen7@gmail.com

The asymmetric unit of the title compound, C₁₁H₁₂N₂O₂·H₂O, contains a molecule of 1,4,6-trimethyl-1,4-dihydroquinoxaline-2,3-dione and a solvent water molecule. Four atoms of the benzene ring are disordered over two sets of sites in a 0.706 (7):0.294 (7) ratio while the N-bound methyl groups are rotationally disordered with occupancy ratios of 0.78 (4):0.22 (4) and 0.76 (5):0.24 (5). In the crystal, molecules are linked by O—H···O and C—H···O hydrogen bonds into layers lying parallel to (101). The Hirshfeld surface analysis indicates that the most important contributions to the packing arrangement are due to H···H (51.3%) and O···H/H···O (28.6%) interactions. The molecular structure calculated by density functional theory is compared with the experimentally determined molecular structure, and the HOMO–LUMO energy gap has been calculated.

## 1. Chemical context

Quinoxalines are well-known important nitrogen-containing heterocyclic compounds with fused benzene and pyrazine rings. Quinoxalines and their derivatives display various pharmacological and biological activities, such as anticancer (Carta *et al.*, 2006), antidiabetic (Bahekar *et al.*, 2007), antiviral (Fonseca *et al.*, 2004), antibacterial (El-Sabbagh *et al.*, 2009), anti-inflammatory (Wagle *et al.*, 2008) and antiprotozoal (Hui *et al.*, 2006). The present work is a part of an ongoing structural study of quinoxaline derivatives (Faizi & Parashchenko 2015; Faizi *et al.*, 2015, 2018).

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

As a continuation of our research devoted to the synthesis and applications of new heterocyclic compounds obtained by N-alkylation reactions (Tribak *et al.*, 2017; Qachchachi *et al.*, 2016; Belaziz *et al.*, 2012), we report here the synthesis of 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione obtained by the action of iodomethane on 6-methylquinoxaline-2,3(1H,4H)-dione, and the crystal structure of its monohydrate derivative

<figure><img src="image_4.png" /></figure>

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

OPEN

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

ACCESS
<figure><img src="image_7.png" /><figcaption>Figure 1</figcaption></figure>

The asymmetric unit of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 40% probability level. O—H···O hydrogen bonds are indicated by dashed lines. The benzene fragment of the organic molecule, C2/C3/C4/C5/C7, is disordered over two sets of sites.

along with the Hirshfeld surface analysis. The experimentally determined molecular structure is compared with that calculated at the DFT/B3LYP/6-311 G(d,p) level.

## 2. Structural commentary

The title compound crystallizes in space group *P*2₁/*n* with one quinoxaline and one water molecule per asymmetric unit. The organic molecule is disordered over two sets of sites with an occupancy ratio of 0.706 (7):0.294 (7). The disorder involves not only the orientation of the methyl group attached to the benzene ring, but also the positions of four carbon atoms of this ring, which are split (Fig. 1). Only the predominant

<figure><img src="image_8.png" /><figcaption>Figure 2</figcaption></figure>

A view along the *a* axis of a hydrogen-bonded fragment. The O—H···O and C—H···O hydrogen bonds (shown as dashed lines) form an *R*<sub>4</sub><sup>2</sup>(8) ring motif.

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

<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>O3—H3A···O1</td><td>0.86</td><td>2.09</td><td>2.936 (4)</td><td>170</td></tr><tr><td>O3—H3C···O1<sup>i</sup></td><td>0.86</td><td>2.38</td><td>3.062 (4)</td><td>137</td></tr><tr><td>O3—H3C···O2<sup>i</sup></td><td>0.86</td><td>2.19</td><td>2.972 (5)</td><td>150</td></tr><tr><td>C5A—H5A···O3<sup>ii</sup></td><td>0.94</td><td>2.40</td><td>3.298 (13)</td><td>160</td></tr><tr><td>C8—H8E···O2<sup>iii</sup></td><td>0.97</td><td>2.45</td><td>3.335 (4)</td><td>151</td></tr></tbody></table>

Symmetry codes: (i) $-x+1, -y+3, -z$; (ii) $-x+\frac{1}{2}, y-\frac{1}{2}, -z-\frac{1}{2}$; (iii) $x-\frac{1}{2}, -y+\frac{5}{2}, z-\frac{1}{2}$.

orientation of the 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione molecule is discussed below. Besides this, the methyl groups attached to N1 and N2 nitrogen atoms are also rotationally disordered with occupancy ratios of 0.78 (4):0.22 (4) and 0.76 (5):0.24 (5), respectively. The quinoxaline ring system is essentially planar, the largest deviation from the mean plane being 0.015 (3) Å for the N2 atom. The C=O and Csp<sup>2</sup>—N bond lengths are typical of such type of compounds and indicate strong conjugation in the amide fragments.

## 3. Supramolecular features

In the crystal, molecules are linked by O—H···O and C—H···O hydrogen bonds (Table 1) into double layers lying parallel to (101). The smallest element of the hydrogen-bonding motif, where the *R*<sub>4</sub><sup>2</sup>(8) rings are formed, is shown in Fig. 2, whereas the whole packing diagram is presented in Fig. 3. The water molecule behaves both as a donor and an acceptor of hydrogen atoms in the hydrogen bonds. As seen in Fig. 3, in centrosymmetric pairs of organic molecules, the aromatic and heterocyclic rings overlap with each other with an intercentroid distance of 3.522 (4) Å, indicating that some π–π interactions occur.

<figure><img src="image_9.png" /><figcaption>Figure 3</figcaption></figure>

Packing diagram of the title compound viewed along the *a*-axis direction. Only the major disorder component is shown.
4. Hirshfeld surface analysis

The intermolecular interactions were investigated quantitatively and visualized with *Crystal Explorer 17.5* (Turner *et al.*, 2017; Spackman *et al.*, 2009). The *d*<sub>norm</sub>, water interaction, curvedness and 2D finger print plots are depicted in Fig. 4a–c and 5a–h, respectively. The red spots on the Hirshfeld surface represent O–H···O contacts while the blue regions correspond to weak interactions such as C–H···O contacts. The H···H interactions (51.3%) are the major factor in the crystal packing with O···H/H···O interactions (28.6%) representing the next highest contribution. The percentage contributions of other weak interactions are: C···C (8.2%), C···H/H···C (5.8%), C···N/N···C (4.5%), N···H/H···N (1.1%) and O···C/C···O (0.5%).

<figure><img src="image_10.png" /><figcaption>**Figure 4**
Views of the three-dimensional Hirshfeld surface for the title compound plotted over (a, b) *d*<sub>norm</sub> and (c) shape-index.</figcaption></figure>

<figure><img src="image_11.png" /><figcaption>**Figure 5**
Two-dimensional fingerprint plots showing (a) all interactions and those delineated into (b) H···H, (c) O···H/H···O, (d) C···C, (e) C···H/H···C, (f) C···N/N···C, (g) N···H/H···N and (h) O···C/C···O.</figcaption></figure>

5. DFT calculations

The structure of the title organic molecule was optimized in the gas-phase approximation at the level of density functional theory (DFT) using the B3LYP functional (Becke, 1993) and 6-311 G(d,p) basis set as implemented in *GAUSSIAN 09* (Frisch *et al.*, 2009). The theoretical and experimental bond lengths and angles are in good agreement (Table 2). The energetic and spatial characteristics of the highest occupied molecular orbital (HOMO), acting as an electron donor, and the lowest unoccupied molecular orbital (LUMO), acting as an electron acceptor, are very important parameters for quantum chemistry. When the energy gap is small, the molecule is highly polarizable and has high chemical reactivity (Fukui, 1982; Khan *et al.*, 2015). The DFT calculations provide
<caption>**Table 2**</caption>

Comparison of observed (X-ray data) and calculated (DFT) geometric parameters (Å, °).

<table><thead><tr><th>Parameter</th><th>X-ray</th><th>B3LYP/6-311G(d,p)</th></tr></thead><tbody><tr><td>O1–C9</td><td>1.228 (4)</td><td>1.217</td></tr><tr><td>O2–C10</td><td>1.226 (4)</td><td>1.211</td></tr><tr><td>N1–C6</td><td>1.401 (4)</td><td>1.407</td></tr><tr><td>N1–C8</td><td>1.470 (4)</td><td>1.468</td></tr><tr><td>N1–C9</td><td>1.351 (4)</td><td>1.375</td></tr><tr><td>N2–C1</td><td>1.409 (4)</td><td>1.375</td></tr><tr><td>N2–C10</td><td>1.365 (5)</td><td>1.384</td></tr><tr><td>N2–C11</td><td>1.458 (5)</td><td>1.464</td></tr><tr><td>O1–C9–N1</td><td>123.5 (3)</td><td>123.9</td></tr><tr><td>O2–C10–N2</td><td>122.8 (3)</td><td>123.4</td></tr><tr><td>O1–C9–C10</td><td>118.3 (3)</td><td>118.3</td></tr></tbody></table>

some important information on the reactivity and site selectivity of the molecular framework, $E_{HOMO}$ and $E_{LUMO}$, electronegativity ($\chi$), hardness ($\eta$), electrophilicity ($\omega$), softness ($\sigma$) and fraction of electrons transferred ($\Delta N$). These data are given in Table 3. The parameters $\eta$ and $\sigma$ are significant for evaluation of both the reactivity and stability. The electron transition from HOMO to LUMO is shown in Fig. 6. The HOMO and LUMO are localized in the plane of the whole 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione bicyclic ring system. The energy gap [$\Delta E = E_{LUMO} - E_{HOMO}$] of the molecule is 4.6907 eV, the frontier molecular orbital energies $E_{HOMO}$ and $E_{LUMO}$ being -6.1139 eV and -1.4232 eV, respectively. The dipole moment of (I) is estimated to be 5.56 Debye.

## 6. Database survey

A search of the Cambridge Structural Database (CSD, version 5.39; Groom *et al.*, 2016) gave nine hits for the 1,4,6-tri-

<figure><img src="image_12.png" /><figcaption>**Figure 6**</figcaption></figure>

Frontier molecular orbitals of the 1,4,6-trimethylquinoxaline-2,3(1H,4H)-dione molecule.

<caption>**Table 3**</caption>

DFT-calculated molecular characteristics for the title compound.

<table><tr><td>Total Energy, TE (eV)</td><td>-20757.4747</td></tr><tr><td>E<sub>HOMO</sub> (eV)</td><td>-6.1139</td></tr><tr><td>E<sub>LUMO</sub> (eV)</td><td>-1.4232</td></tr><tr><td>Gap, ΔE (eV)</td><td>4.6907</td></tr><tr><td>Dipole moment, μ (D)</td><td>5.56</td></tr><tr><td>Ionization potential, I (eV)</td><td>6.1139</td></tr><tr><td>Electron affinity, A (eV)</td><td>1.4232</td></tr><tr><td>Electronegativity, χ</td><td>3.929</td></tr><tr><td>Hardness, η</td><td>2.345</td></tr><tr><td>Electrophilicity index, ω</td><td>3.291</td></tr><tr><td>Softness, σ</td><td>0.213</td></tr><tr><td>Fraction of electron transferred, ΔN</td><td>0.655</td></tr></table>

methylquinoxaline-2,3(1H,4H)-dione moiety. Two of them are metal complexes, bis($\mu_2$-nitrato-O,O,O')-bis[1,4-bis(N,N-diisopropyl-acetamido)quinoxaline-2,3-dione-O,O']tetrakis(nitrato-O,O')diaquadineodymium(III) monohydrate (WIKSOZ; Song *et al.*, 2007) and catena-($\mu_2$-iodo)-bis(1,4-dimethylquinoxalin-2,3-dionato)potassium (FADQOS; Benali *et al.*, 2008). Seven organic compounds similar to the title compound are reported in the literature. In 1,4-dihexyl-1,4-dihydroquinoxaline-2,3-dione (FECROX; El Bourakadi *et al.*, 2017a), the methyl groups attached to the N atoms are replaced by hexyl groups. In 1,4-diallylquinoxaline-2,3(1H,4H)-dione (GURGAB; Mustaphi *et al.*, 2001), the allyl groups are bound to the N atoms. In 1-ethyl-4-phenylethyl-1,4-dihydroquinoxaline-2,3-dione (IXATOQ; Akkurt *et al.*, 2004), one N atom is bound to an ethyl group, and the other to an ethylphenyl group. In 6-methyl-1,4-bis[(pyridin-2-yl)methyl]-1,4-dihydroquinoxaline-2,3-dione (KELMIA; Zouitini *et al.*, 2017), methylpyridinyl groups are attached to both N atoms. In 1,4-dibenzyl-6-chloro-1,4-dihydroquinoxaline-2,3-dione (PAWFEB; El Janati *et al.*, 2017a), the N atoms are attached to the benzyl groups, and the methyl group on the benzene ring is substituted by chlorine. In 1,4-dioctyl-1,4-dihydroquinoxaline-2,3-dione (WAPWAO; El Bourakadi *et al.*, 2017b), octyl groups are attached to the N atoms. In 6-chloro-1,4-diethyl-1,4-dihydroquinoxaline-2,3-dione (XEFMON; El Janati *et al.*, 2017b), the ethyl groups are attached to the N atoms, and the methyl group on the benzene ring is substituted by chlorine, as in PAWFEB. None of these structures contains solvent molecules.

## 7. Synthesis and crystallization

To a solution of 6-methyl-1,4-dihydroquinoxaline-2,3-dione (0.3 g, 1.73 mmol) in DMF (15 ml) potassium carbonate (0.47 g, 3.61 mmol) and tetra-n-butylammonium (0.07g, 0.23 mmol) were added. After 10 min of stirring, 0.27 ml (4.32 mmol) of iodomethane were added, and the mixture was stirred at room temperature for 6 h. The inorganic salts were filtered off, DMF was evaporated under reduced pressure and the residue was dissolved in dichloromethane. The organic phase was dried over $Na_2SO_4$ and then concentrated. The crude product was purified by chromatography on a silica gel column [eluent: hexane/ethylacetate (2/1)].
<table><caption>**Table 4**
Experimental details.</caption><tbody><tr><td>Crystal data</td><td></td></tr><tr><td>Chemical formula</td><td>C<sub>11</sub>H<sub>12</sub>N<sub>2</sub>O<sub>2</sub>·H<sub>2</sub>O</td></tr><tr><td>M<sub>r</sub></td><td>222.24</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, P2<sub>1</sub>/n</td></tr><tr><td>Temperature (K)</td><td>219</td></tr><tr><td>a, b, c (Å)</td><td>7.0695 (4), 10.8321 (5), 14.4349 (6)</td></tr><tr><td>β (°)</td><td>101.556 (3)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>1082.98 (9)</td></tr><tr><td>Z</td><td>4</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.10</td></tr><tr><td>Crystal size (mm)</td><td>0.30 × 0.18 × 0.04</td></tr><tr><td>Data collection</td><td>Bruker APEXII CCD</td></tr><tr><td>Diffractometer</td><td>Multi-scan (SADABS; Krause et al., 2015)</td></tr><tr><td>Absorption correction</td><td>32798, 1935, 1563</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td></td></tr><tr><td>R<sub>int</sub></td><td>0.062</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.598</td></tr><tr><td>Refinement</td><td></td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.067, 0.147, 1.24</td></tr><tr><td>No. of reflections</td><td>1935</td></tr><tr><td>No. of parameters</td><td>201</td></tr><tr><td>No. of restraints</td><td>30</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>0.21, -0.18</td></tr></tbody></table>

Computer programs: *APEX3* and *SAINT* (Bruker, 2016), *SHELXT* (Sheldrick, 2015a), *SHELXL2018* (Sheldrick, 2015b), *OLEX2* (Dolomanov *et al.*, 2009), *Mercury* (Macrae *et al.*, 2020), *WinGX* (Farrugia, 2012), *PLATON* (Spek, 2020) and *publCIF* (Westrip, 2010).

## 8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. Water molecules were refined as rigid groups with $U_{iso}(H) = 1.5U_{eq}(O)$. Other H atoms were positioned geometrically, with C-H = 0.94 and 0.97 Å for aromatic and aliphatic H atoms, respectively, and constrained to ride on their parent atoms, with $U_{iso}(H) = 1.2U_{eq}(C)$ or $U_{iso}(H) = 1.5U_{eq}(C-methyl). The disorder of the organic molecule was taken into account using free variables.

## Acknowledgements

Langat Singh College, B·R. Bihar University India is thanked for access to laboratory facilities.

## Funding information

Funding for this research was provided by: University Grants Commission, New Delhi. This study was supported financially by Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Morocco and the University of Science and Technology, Ibb Branch, Ibb, Yemen.

## References

Akkurt, M., Öztürk, S., Küçükbay, H., Orhan, E. & Büyükgüngör, O. (2004). *Acta Cryst.* **E60**, o1266–o1268.

Bahekar, R. H., Jain, M. R., Gupta, A. A., Goel, A., Jadav, P. A., Patel, D. N., Prajapati, V. M. & Patel, P. R. (2007). *Arch. Pharm. Chem. Life Sci.* **340**, 359–366.

Becke, A. D. (1993). *J. Chem. Phys.* **98**, 5648–5652.

Belaziz, D., Kandri Rodi, Y., Essassi, E. M. & El Ammari, L. (2012). *Acta Cryst.* **E68**, o1276.

Benali, B., Lazar, Z., Boucetta, A., El Assyry, A., Lakhrissi, B., Massoui, M., Jermoumi, C., Negrier, P., Leger, J. M. & Mondieig, D. (2008). *Spectrosc. Lett.* **41**, 64–71.

Bruker (2016). *APEX3* and *SAINT*. Bruker AXS Inc., Madison, Wisconsin, USA.

Carta, A., Loriga, M., Piras, S., Paglietti, G., La Colla, P., Busonera, B., Collu, G. & Loddo, R. (2006). *Med. Chem.* **2**, 113–122.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). *J. Appl. Cryst.* **42**, 339–341.

El Bourakadi, K., El Bakri, Y., Sebhaoui, J., Rayni, I., Essassi, E. M. & Mague, J. T. (2017a). *IUCrData*, **2**, x171019.

El Bourakadi, K., El Bakri, Y., Sebhaoui, J., Rayni, I., Essassi, E. M. & Mague, J. T. (2017b). *IUCrData*, **2**, x170520.

El Janati, A., Kandri Rodi, Y., Jasinski, J. P., Kaur, M., Ouzidan, Y. & Essassi, E. M. (2017a). *IUCrData*, **2**, x170901.

El Janati, A., Kandri Rodi, Y., Jasinski, J. P., Kaur, M., Ouzidan, Y. & Essassi, E. M. (2017b). *IUCrData*, **2**, x171052.

El-Sabbagh, O. I., El-Sadek, M. E., Lashine, S. M., Yassin, S. H. & El-Nabtity, S. M. (2009). *Med. Chem. Res.* **18**, 782–797.

Faizi, M. S. H., Alam, M. J., Haque, A., Ahmad, S., Shahid, M. & Ahmad, M. (2018). *J. Mol. Struct.* **1156**, 457–464.

Faizi, M. S. H. & Parashchenko, Y. (2015). *Acta Cryst.* **E71**, 1332–1335.

Faizi, M. S. H., Sharkina, N. O. & Iskenderov, T. S. (2015). *Acta Cryst.* **E71**, o17–o18.

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

Fonseca, T., Gigante, B., Marques, M. M., Gilchrist, T. L. & De Clercq, E. (2004). *Bioorg. Med. Chem.* **12**, 103–112.

Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseeman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A. Jr, Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J. & Fox, D. J. (2009). *GAUSSIAN09*. Gaussian Inc., Wallingford, CT, USA.

Fukui, K. (1982). *Science*, **218**, 747–754.

Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). *Acta Cryst.* **B72**, 171–179.

Hui, X., Desrivot, J., Bories, C., Loiseau, P. M., Franck, X., Hocquemiller, R. & Figadère, B. (2006). *Bioorg. Med. Chem. Lett.* **16**, 815–820.

Khan, E., Shukla, A., Srivastava, A., Shweta, P. & Tandon, P. (2015). *New J. Chem.* **39**, 9800–9812.

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

Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). *J. Appl. Cryst.* **53**, 226–235.

Mustaphi, N. E., Ferfra, S., Essassi, E. M. & Pierrot, M. (2001). *Acta Cryst.* **E57**, o176–o177.

Oachchachi, F., Kandri Rodi, Y., Elmsellem, H., Steli, H., Haoudi, A., Mazzah, A., Ouzidan, Y., Sebbar, N. K. & Essassi, E. M. (2016). *J. Materials Environ. Sci.* **7**, 2897–2907.

Sheldrick, G. M. (2015a). *Acta Cryst.* **A71**, 3–8.

Sheldrick, G. M. (2015b). *Acta Cryst.* **C71**, 3–8.
Song, X.-Q., Yu, Y., Liu, W.-S., Dou, W., Zheng, J.-R. & Yao, J.-N. (2007). *J. Solid State Chem.* **180**, 2616–2624.

Spackman, M. A. & Jayatilaka, D. (2009). *CrystEngComm*, **11**, 19–32.

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

Tribak, Z., Kandri Rodi, Y., Haoudi, A., Skalli, M. K., Mazzah, A., Akhazzane, M. & Essassi, E. M. (2017). *J. Mar. Chim. Heterocycl.* **16**, 58–65.

Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). *Crystal Explorer 17.5*. The University of Western Australia.

Wagle, S., Adhikari, A. V. & Kumari, N. S. (2008). *Indian J. Chem.* **47**, 439–448.

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

Zouitini, A., Kandri Rodi, Y., Ouazzani Chahdi, F., Jasinski, J. P., Kaur, M. & Essassi, E. M. (2017). *IUCrData*, **2**, x171651.
supporting information

*Acta Cryst.* (2020). **E76**, 1296-1301 [https://doi.org/10.1107/S2056989020009573]

# Synthesis, crystal structure at 219 K and Hirshfeld surface analyses of 1,4,6-tri-
methylquinoxaline-2,3(1H,4H)-dione monohydrate

Ayman Zouitini, Md. Serajul Haque Faizi, Younes Ouzidan, Fouad Ouazzani Chahdi, Jérôme Marrot, Damien Prim, Necmi Dege and Ashraf Mashrai

## Computing details

Data collection: *APEX3* (Bruker, 2016); cell refinement: *SAINT* (Bruker, 2016); data reduction: *SAINT* (Bruker, 2016); program(s) used to solve structure: *SHELXT* (Sheldrick, 2015a); program(s) used to refine structure: *SHELXL2018* (Sheldrick, 2015b); molecular graphics: *OLEX2* (Dolomanov *et al.*, 2009) and *Mercury* (Macrae *et al.*, 2020); software used to prepare material for publication: *WinGX* (Farrugia, 2012), *PLATON* (Spek, 2020) and *publCIF* (Westrip, 2010).

## 1,4,6-Trimethylquinoxaline-2,3(1H,4H)-dione monohydrate

### Crystal data

$C_{11}H_{12}N_2O_2 \cdot H_2O$

$M_r = 222.24$

Monoclinic, $P2_1/n$

$a = 7.0695 (4) Å$

$b = 10.8321 (5) Å$

$c = 14.4349 (6) Å$

$\beta = 101.556 (3)°$

$V = 1082.98 (9) Å³$

$Z = 4$

$F(000) = 472$

$D_x = 1.363 \text{ Mg m}^{-3}$

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 7373 reflections

$\theta = 2.4-24.7°$

$\mu = 0.10 \text{ mm}^{-1}$

$T = 219$ K

Parallelepiped, yellow

0.30 × 0.18 × 0.04 mm

### Data collection

Bruker APEXII CCD

diffractometer

Radiation source: fine-focus sealed tube

$\varphi$ and $\omega$ scans

Absorption correction: multi-scan

(SADABS; Krause *et al.*, 2015)

1935 independent reflections

1563 reflections with $I > 2\sigma(I)$

$R_{int} = 0.062$

$\theta_{max} = 25.2°$, $\theta_{min} = 2.4°$

$h = -8 \rightarrow 8$

$k = -12 \rightarrow 12$

$l = -17 \rightarrow 17$

32798 measured reflections

### Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.067$

$wR(F^2) = 0.147$

$S = 1.24$

1935 reflections

201 parameters

30 restraints

Primary atom site location: structure-invariant
direct methods

Secondary atom site location: difference Fourier
map

Hydrogen site location: mixed

H-atom parameters constrained

$w = 1/[\sigma^2(F_o^2) + (0.0097P)^2 + 1.8308P]$

where $P = (F_o^2 + 2F_c^2)/3$
$$ 
\begin{aligned}
\Delta\rho_{\max} &= 0.21 \text{ e Å}^{-3} \\
\Delta\rho_{\min} &= -0.18 \text{ e Å}^{-3}
\end{aligned}
 $$

$$ 
\begin{array}{l}
\text{Extinction correction: SHELXL2018} \\
(\text{Sheldrick, 2015b}), \\
\text{Fc}^*=\text{kFc}[1+0.001\text{Fc}^2\lambda^3/\sin(2\theta)]^{-1/4}
\end{array}
 $$

Extinction coefficient: 0.0031 (9)

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.

<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>O1</td><td>0.3712 (4)</td><td>1.3409 (2)</td><td>0.00205 (17)</td><td>0.0479 (7)</td><td></td></tr><tr><td>O2</td><td>0.3853 (4)</td><td>1.2710 (3)</td><td>0.18106 (17)</td><td>0.0581 (8)</td><td></td></tr><tr><td>C1</td><td>0.2612 (4)</td><td>0.9861 (3)</td><td>0.0618 (3)</td><td>0.0409 (8)</td><td></td></tr><tr><td>C2A</td><td>0.2177 (14)</td><td>0.8598 (10)</td><td>0.0725 (6)</td><td>0.034 (2)</td><td>0.706 (7)</td></tr><tr><td>H2A</td><td>0.219201</td><td>0.830335</td><td>0.133895</td><td>0.041*</td><td>0.706 (7)</td></tr><tr><td>C2B</td><td>0.228 (5)</td><td>0.879 (3)</td><td>0.1074 (16)</td><td>0.048 (7)</td><td>0.294 (7)</td></tr><tr><td>H2B</td><td>0.237848</td><td>0.867991</td><td>0.172811</td><td>0.057*</td><td>0.294 (7)</td></tr><tr><td>C3A</td><td>0.1723 (13)</td><td>0.7756 (12)</td><td>-0.0031 (7)</td><td>0.037 (2)</td><td>0.706 (7)</td></tr><tr><td>C3B</td><td>0.175 (4)</td><td>0.788 (3)</td><td>0.0367 (16)</td><td>0.037 (5)</td><td>0.294 (7)</td></tr><tr><td>H3B</td><td>0.152151</td><td>0.706837</td><td>0.055446</td><td>0.045*</td><td>0.294 (7)</td></tr><tr><td>C4A</td><td>0.1703 (14)</td><td>0.8174 (10)</td><td>-0.0933 (6)</td><td>0.038 (2)</td><td>0.706 (7)</td></tr><tr><td>H4A</td><td>0.142000</td><td>0.761812</td><td>-0.144148</td><td>0.045*</td><td>0.706 (7)</td></tr><tr><td>C4B</td><td>0.156 (3)</td><td>0.811 (2)</td><td>-0.0554 (16)</td><td>0.035 (6)</td><td>0.294 (7)</td></tr><tr><td>C5A</td><td>0.210 (2)</td><td>0.9418 (16)</td><td>-0.1111 (9)</td><td>0.039 (3)</td><td>0.706 (7)</td></tr><tr><td>H5A</td><td>0.207157</td><td>0.970180</td><td>-0.172834</td><td>0.047*</td><td>0.706 (7)</td></tr><tr><td>C5B</td><td>0.193 (5)</td><td>0.923 (4)</td><td>-0.087 (2)</td><td>0.032 (6)</td><td>0.294 (7)</td></tr><tr><td>H5B</td><td>0.176018</td><td>0.933494</td><td>-0.153049</td><td>0.038*</td><td>0.294 (7)</td></tr><tr><td>C6</td><td>0.2535 (4)</td><td>1.0233 (3)</td><td>-0.0314 (2)</td><td>0.0369 (8)</td><td></td></tr><tr><td>N1</td><td>0.2915 (4)</td><td>1.1465 (2)</td><td>-0.05089 (18)</td><td>0.0359 (7)</td><td></td></tr><tr><td>C9</td><td>0.3382 (4)</td><td>1.2324 (3)</td><td>0.0177 (2)</td><td>0.0354 (7)</td><td></td></tr><tr><td>C10</td><td>0.3472 (5)</td><td>1.1936 (3)</td><td>0.1182 (2)</td><td>0.0402 (8)</td><td></td></tr><tr><td>N2</td><td>0.3101 (4)</td><td>1.0729 (3)</td><td>0.1354 (2)</td><td>0.0440 (7)</td><td></td></tr><tr><td>C8</td><td>0.2761 (6)</td><td>1.1869 (4)</td><td>-0.1493 (2)</td><td>0.0540 (10)</td><td></td></tr><tr><td>H8A</td><td>0.223018</td><td>1.120497</td><td>-0.191729</td><td>0.081*</td><td>0.22 (4)</td></tr><tr><td>H8B</td><td>0.403194</td><td>1.208575</td><td>-0.159941</td><td>0.081*</td><td>0.22 (4)</td></tr><tr><td>H8C</td><td>0.191973</td><td>1.258317</td><td>-0.161254</td><td>0.081*</td><td>0.22 (4)</td></tr><tr><td>H8D</td><td>0.322439</td><td>1.271095</td><td>-0.150220</td><td>0.081*</td><td>0.78 (4)</td></tr><tr><td>H8E</td><td>0.142263</td><td>1.183017</td><td>-0.182009</td><td>0.081*</td><td>0.78 (4)</td></tr><tr><td>H8F</td><td>0.353484</td><td>1.133275</td><td>-0.180695</td><td>0.081*</td><td>0.78 (4)</td></tr><tr><td>C11</td><td>0.3169 (7)</td><td>1.0381 (4)</td><td>0.2335 (3)</td><td>0.0696 (13)</td><td></td></tr><tr><td>H11A</td><td>0.279949</td><td>0.952205</td><td>0.236449</td><td>0.104*</td><td>0.24 (5)</td></tr><tr><td>H11B</td><td>0.228285</td><td>1.089532</td><td>0.259797</td><td>0.104*</td><td>0.24 (5)</td></tr><tr><td>H11C</td><td>0.446948</td><td>1.049549</td><td>0.269709</td><td>0.104*</td><td>0.24 (5)</td></tr><tr><td>H11D</td><td>0.356839</td><td>1.108652</td><td>0.274187</td><td>0.104*</td><td>0.76 (5)</td></tr><tr><td>H11E</td><td>0.408503</td><td>0.971326</td><td>0.250839</td><td>0.104*</td><td>0.76 (5)</td></tr></tbody></table>
<table><tr><td>H11F</td><td>0.189839</td><td>1.011308</td><td>0.240928</td><td>0.104*</td><td>0.76 (5)</td></tr><tr><td>O3</td><td>0.3982 (6)</td><td>1.4989 (3)</td><td>-0.1600 (2)</td><td>0.0833 (11)</td><td></td></tr><tr><td>H3A</td><td>0.382975</td><td>1.460410</td><td>-0.109907</td><td>0.125*</td><td></td></tr><tr><td>H3C</td><td>0.477462</td><td>1.559146</td><td>-0.144450</td><td>0.125*</td><td></td></tr><tr><td>C7A</td><td>0.1315 (8)</td><td>0.6428 (5)</td><td>0.0165 (4)</td><td>0.0528 (17)</td><td>0.706 (7)</td></tr><tr><td>H7A2</td><td>0.035271</td><td>0.639039</td><td>0.055782</td><td>0.079*</td><td>0.706 (7)</td></tr><tr><td>H7A3</td><td>0.249382</td><td>0.603381</td><td>0.049019</td><td>0.079*</td><td>0.706 (7)</td></tr><tr><td>H7A1</td><td>0.083495</td><td>0.600399</td><td>-0.042761</td><td>0.079*</td><td>0.706 (7)</td></tr><tr><td>C7B</td><td>0.0926 (19)</td><td>0.7135 (13)</td><td>-0.1317 (10)</td><td>0.062 (5)</td><td>0.294 (7)</td></tr><tr><td>H7B1</td><td>0.025634</td><td>0.753011</td><td>-0.189272</td><td>0.093*</td><td>0.294 (7)</td></tr><tr><td>H7B2</td><td>0.006626</td><td>0.655227</td><td>-0.110056</td><td>0.093*</td><td>0.294 (7)</td></tr><tr><td>H7B3</td><td>0.205065</td><td>0.670198</td><td>-0.143967</td><td>0.093*</td><td>0.294 (7)</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>O1</td><td>0.0528 (15)</td><td>0.0419 (15)</td><td>0.0475 (14)</td><td>-0.0027 (12)</td><td>0.0067 (11)</td><td>0.0004 (12)</td></tr><tr><td>O2</td><td>0.0675 (18)</td><td>0.0632 (18)</td><td>0.0414 (14)</td><td>-0.0097 (14)</td><td>0.0057 (12)</td><td>-0.0075 (14)</td></tr><tr><td>C1</td><td>0.0219 (15)</td><td>0.0408 (19)</td><td>0.059 (2)</td><td>0.0014 (14)</td><td>0.0050 (14)</td><td>0.0022 (17)</td></tr><tr><td>C2A</td><td>0.026 (3)</td><td>0.038 (6)</td><td>0.038 (5)</td><td>0.003 (3)</td><td>0.007 (4)</td><td>0.000 (5)</td></tr><tr><td>C2B</td><td>0.051 (9)</td><td>0.040 (10)</td><td>0.051 (13)</td><td>-0.009 (7)</td><td>0.008 (11)</td><td>-0.016 (11)</td></tr><tr><td>C3A</td><td>0.029 (3)</td><td>0.039 (5)</td><td>0.043 (8)</td><td>-0.003 (3)</td><td>0.006 (5)</td><td>-0.005 (6)</td></tr><tr><td>C3B</td><td>0.040 (8)</td><td>0.034 (10)</td><td>0.036 (13)</td><td>0.003 (7)</td><td>0.003 (10)</td><td>-0.004 (11)</td></tr><tr><td>C4A</td><td>0.035 (3)</td><td>0.039 (4)</td><td>0.037 (5)</td><td>0.003 (2)</td><td>0.002 (4)</td><td>-0.005 (4)</td></tr><tr><td>C4B</td><td>0.033 (7)</td><td>0.042 (11)</td><td>0.029 (14)</td><td>-0.002 (7)</td><td>0.008 (10)</td><td>-0.013 (11)</td></tr><tr><td>C5A</td><td>0.038 (5)</td><td>0.038 (5)</td><td>0.039 (6)</td><td>-0.002 (4)</td><td>0.002 (4)</td><td>0.006 (4)</td></tr><tr><td>C5B</td><td>0.014 (7)</td><td>0.042 (14)</td><td>0.038 (13)</td><td>0.005 (7)</td><td>0.003 (8)</td><td>0.005 (10)</td></tr><tr><td>C6</td><td>0.0200 (15)</td><td>0.0367 (18)</td><td>0.050 (2)</td><td>0.0025 (13)</td><td>-0.0020 (13)</td><td>-0.0011 (15)</td></tr><tr><td>N1</td><td>0.0297 (14)</td><td>0.0393 (15)</td><td>0.0358 (15)</td><td>0.0005 (12)</td><td>-0.0002 (11)</td><td>-0.0006 (12)</td></tr><tr><td>C9</td><td>0.0259 (16)</td><td>0.0385 (19)</td><td>0.0407 (18)</td><td>0.0022 (14)</td><td>0.0037 (13)</td><td>-0.0001 (15)</td></tr><tr><td>C10</td><td>0.0318 (17)</td><td>0.052 (2)</td><td>0.0362 (18)</td><td>-0.0002 (15)</td><td>0.0048 (14)</td><td>-0.0006 (16)</td></tr><tr><td>N2</td><td>0.0360 (15)</td><td>0.0523 (18)</td><td>0.0448 (17)</td><td>0.0004 (14)</td><td>0.0108 (13)</td><td>0.0091 (14)</td></tr><tr><td>C8</td><td>0.063 (3)</td><td>0.057 (2)</td><td>0.037 (2)</td><td>0.002 (2)</td><td>-0.0016 (17)</td><td>0.0010 (17)</td></tr><tr><td>C11</td><td>0.081 (3)</td><td>0.078 (3)</td><td>0.054 (3)</td><td>0.002 (3)</td><td>0.023 (2)</td><td>0.017 (2)</td></tr><tr><td>O3</td><td>0.127 (3)</td><td>0.069 (2)</td><td>0.0480 (17)</td><td>-0.041 (2)</td><td>0.0053 (18)</td><td>0.0030 (16)</td></tr><tr><td>C7A</td><td>0.055 (3)</td><td>0.041 (3)</td><td>0.063 (4)</td><td>-0.001 (2)</td><td>0.013 (3)</td><td>0.002 (3)</td></tr><tr><td>C7B</td><td>0.048 (8)</td><td>0.063 (9)</td><td>0.077 (10)</td><td>-0.005 (7)</td><td>0.014 (7)</td><td>-0.045 (8)</td></tr></tbody></table>

Geometric parameters (Å, °)

<table><tr><td>O1—C9</td><td>1.228 (4)</td><td>N1—C8</td><td>1.470 (4)</td></tr><tr><td>O2—C10</td><td>1.226 (4)</td><td>C9—C10</td><td>1.499 (5)</td></tr><tr><td>C1—C2B</td><td>1.38 (3)</td><td>C10—N2</td><td>1.365 (5)</td></tr><tr><td>C1—C6</td><td>1.394 (5)</td><td>N2—C11</td><td>1.458 (5)</td></tr><tr><td>C1—N2</td><td>1.409 (4)</td><td>C8—H8A</td><td>0.9700</td></tr><tr><td>C1—C2A</td><td>1.418 (12)</td><td>C8—H8B</td><td>0.9700</td></tr><tr><td>C2A—C3A</td><td>1.409 (11)</td><td>C8—H8C</td><td>0.9700</td></tr><tr><td>C2A—H2A</td><td>0.9400</td><td>C8—H8D</td><td>0.9700</td></tr></table>
<table><tr><td>C2B—C3B</td><td>1.41 (2)</td><td>C8—H8E</td><td>0.9700</td></tr><tr><td>C2B—H2B</td><td>0.9400</td><td>C8—H8F</td><td>0.9700</td></tr><tr><td>C3A—C4A</td><td>1.375 (11)</td><td>C11—H11A</td><td>0.9700</td></tr><tr><td>C3A—C7A</td><td>1.504 (14)</td><td>C11—H11B</td><td>0.9700</td></tr><tr><td>C3B—C4B</td><td>1.34 (3)</td><td>C11—H11C</td><td>0.9700</td></tr><tr><td>C3B—H3B</td><td>0.9400</td><td>C11—H11D</td><td>0.9700</td></tr><tr><td>C4A—C5A</td><td>1.41 (2)</td><td>C11—H11E</td><td>0.9700</td></tr><tr><td>C4A—H4A</td><td>0.9400</td><td>C11—H11F</td><td>0.9700</td></tr><tr><td>C4B—C5B</td><td>1.34 (4)</td><td>O3—H3A</td><td>0.8603</td></tr><tr><td>C4B—C7B</td><td>1.53 (2)</td><td>O3—H3C</td><td>0.8598</td></tr><tr><td>C5A—C6</td><td>1.434 (17)</td><td>C7A—H7A2</td><td>0.9700</td></tr><tr><td>C5A—H5A</td><td>0.9400</td><td>C7A—H7A3</td><td>0.9700</td></tr><tr><td>C5B—C6</td><td>1.37 (4)</td><td>C7A—H7A1</td><td>0.9700</td></tr><tr><td>C5B—H5B</td><td>0.9400</td><td>C7B—H7B1</td><td>0.9700</td></tr><tr><td>C6—N1</td><td>1.401 (4)</td><td>C7B—H7B2</td><td>0.9700</td></tr><tr><td>N1—C9</td><td>1.351 (4)</td><td>C7B—H7B3</td><td>0.9700</td></tr></table>

<table><tr><td>C2B—C1—C6</td><td>136.5 (10)</td><td>H8B—C8—H8C</td><td>109.5</td></tr><tr><td>C2B—C1—N2</td><td>104.1 (10)</td><td>N1—C8—H8D</td><td>109.5</td></tr><tr><td>C6—C1—N2</td><td>119.4 (3)</td><td>H8A—C8—H8D</td><td>141.1</td></tr><tr><td>C6—C1—C2A</td><td>114.6 (5)</td><td>H8B—C8—H8D</td><td>56.3</td></tr><tr><td>N2—C1—C2A</td><td>126.0 (5)</td><td>H8C—C8—H8D</td><td>56.3</td></tr><tr><td>C3A—C2A—C1</td><td>124.1 (8)</td><td>N1—C8—H8E</td><td>109.5</td></tr><tr><td>C3A—C2A—H2A</td><td>117.9</td><td>H8A—C8—H8E</td><td>56.3</td></tr><tr><td>C1—C2A—H2A</td><td>117.9</td><td>H8B—C8—H8E</td><td>141.1</td></tr><tr><td>C1—C2B—C3B</td><td>107 (2)</td><td>H8C—C8—H8E</td><td>56.3</td></tr><tr><td>C1—C2B—H2B</td><td>126.6</td><td>H8D—C8—H8E</td><td>109.5</td></tr><tr><td>C3B—C2B—H2B</td><td>126.6</td><td>N1—C8—H8F</td><td>109.5</td></tr><tr><td>C4A—C3A—C2A</td><td>118.5 (11)</td><td>H8A—C8—H8F</td><td>56.3</td></tr><tr><td>C4A—C3A—C7A</td><td>121.8 (10)</td><td>H8B—C8—H8F</td><td>56.3</td></tr><tr><td>C2A—C3A—C7A</td><td>119.7 (9)</td><td>H8C—C8—H8F</td><td>141.1</td></tr><tr><td>C4B—C3B—C2B</td><td>123 (3)</td><td>H8D—C8—H8F</td><td>109.5</td></tr><tr><td>C4B—C3B—H3B</td><td>118.5</td><td>H8E—C8—H8F</td><td>109.5</td></tr><tr><td>C2B—C3B—H3B</td><td>118.5</td><td>N2—C11—H11A</td><td>109.5</td></tr><tr><td>C3A—C4A—C5A</td><td>121.5 (11)</td><td>N2—C11—H11B</td><td>109.5</td></tr><tr><td>C3A—C4A—H4A</td><td>119.2</td><td>H11A—C11—H11B</td><td>109.5</td></tr><tr><td>C5A—C4A—H4A</td><td>119.2</td><td>N2—C11—H11C</td><td>109.5</td></tr><tr><td>C3B—C4B—C5B</td><td>122 (3)</td><td>H11A—C11—H11C</td><td>109.5</td></tr><tr><td>C3B—C4B—C7B</td><td>123 (2)</td><td>H11B—C11—H11C</td><td>109.5</td></tr><tr><td>C5B—C4B—C7B</td><td>115 (2)</td><td>N2—C11—H11D</td><td>109.5</td></tr><tr><td>C4A—C5A—C6</td><td>117.4 (9)</td><td>H11A—C11—H11D</td><td>141.1</td></tr><tr><td>C4A—C5A—H5A</td><td>121.3</td><td>H11B—C11—H11D</td><td>56.3</td></tr><tr><td>C6—C5A—H5A</td><td>121.3</td><td>H11C—C11—H11D</td><td>56.3</td></tr><tr><td>C4B—C5B—C6</td><td>125 (2)</td><td>N2—C11—H11E</td><td>109.5</td></tr><tr><td>C4B—C5B—H5B</td><td>117.5</td><td>H11A—C11—H11E</td><td>56.3</td></tr><tr><td>C6—C5B—H5B</td><td>117.5</td><td>H11B—C11—H11E</td><td>141.1</td></tr><tr><td>C5B—C6—C1</td><td>106.7 (11)</td><td>H11C—C11—H11E</td><td>56.3</td></tr><tr><td>C5B—C6—N1</td><td>133.4 (11)</td><td>H11D—C11—H11E</td><td>109.5</td></tr></table>
<table><tr><td>C1—C6—N1</td><td>119.8 (3)</td></tr><tr><td>C1—C6—C5A</td><td>123.8 (6)</td></tr><tr><td>N1—C6—C5A</td><td>116.4 (6)</td></tr><tr><td>C9—N1—C6</td><td>122.5 (3)</td></tr><tr><td>C9—N1—C8</td><td>117.6 (3)</td></tr><tr><td>C6—N1—C8</td><td>119.9 (3)</td></tr><tr><td>O1—C9—N1</td><td>123.5 (3)</td></tr><tr><td>O1—C9—C10</td><td>118.3 (3)</td></tr><tr><td>N1—C9—C10</td><td>118.2 (3)</td></tr><tr><td>O2—C10—N2</td><td>122.8 (3)</td></tr><tr><td>O2—C10—C9</td><td>119.0 (3)</td></tr><tr><td>N2—C10—C9</td><td>118.2 (3)</td></tr><tr><td>C10—N2—C1</td><td>121.9 (3)</td></tr><tr><td>C10—N2—C11</td><td>117.0 (3)</td></tr><tr><td>C1—N2—C11</td><td>121.0 (3)</td></tr><tr><td>N1—C8—H8A</td><td>109.5</td></tr><tr><td>N1—C8—H8B</td><td>109.5</td></tr><tr><td>H8A—C8—H8B</td><td>109.5</td></tr><tr><td>N1—C8—H8C</td><td>109.5</td></tr><tr><td>H8A—C8—H8C</td><td>109.5</td></tr></table>

<table><tr><td>C6—C1—C2A—C3A</td><td>0.8 (11)</td></tr><tr><td>N2—C1—C2A—C3A</td><td>-179.0 (7)</td></tr><tr><td>C6—C1—C2B—C3B</td><td>1 (4)</td></tr><tr><td>N2—C1—C2B—C3B</td><td>179.2 (19)</td></tr><tr><td>C1—C2A—C3A—C4A</td><td>0.2 (15)</td></tr><tr><td>C1—C2A—C3A—C7A</td><td>179.0 (7)</td></tr><tr><td>C1—C2B—C3B—C4B</td><td>-3 (4)</td></tr><tr><td>C2A—C3A—C4A—C5A</td><td>-0.9 (17)</td></tr><tr><td>C7A—C3A—C4A—C5A</td><td>-179.7 (10)</td></tr><tr><td>C2B—C3B—C4B—C5B</td><td>2 (5)</td></tr><tr><td>C2B—C3B—C4B—C7B</td><td>-178 (2)</td></tr><tr><td>C3A—C4A—C5A—C6</td><td>0.5 (19)</td></tr><tr><td>C3B—C4B—C5B—C6</td><td>0 (5)</td></tr><tr><td>C7B—C4B—C5B—C6</td><td>-179 (2)</td></tr><tr><td>C4B—C5B—C6—C1</td><td>-2 (3)</td></tr><tr><td>C4B—C5B—C6—N1</td><td>-177.0 (19)</td></tr><tr><td>C2B—C1—C6—C5B</td><td>1 (2)</td></tr><tr><td>N2—C1—C6—C5B</td><td>-176.8 (15)</td></tr><tr><td>C2B—C1—C6—N1</td><td>177.2 (19)</td></tr><tr><td>N2—C1—C6—N1</td><td>-0.9 (4)</td></tr><tr><td>C2A—C1—C6—N1</td><td>179.2 (5)</td></tr><tr><td>N2—C1—C6—C5A</td><td>178.5 (9)</td></tr><tr><td>C2A—C1—C6—C5A</td><td>-1.3 (10)</td></tr><tr><td>C4A—C5A—C6—C1</td><td>0.7 (17)</td></tr><tr><td>C4A—C5A—C6—N1</td><td>-179.8 (9)</td></tr></table>

<table><tr><td>N2—C11—H11F</td><td>109.5</td></tr><tr><td>H11A—C11—H11F</td><td>56.3</td></tr><tr><td>H11B—C11—H11F</td><td>56.3</td></tr><tr><td>H11C—C11—H11F</td><td>141.1</td></tr><tr><td>H11D—C11—H11F</td><td>109.5</td></tr><tr><td>H11E—C11—H11F</td><td>109.5</td></tr><tr><td>H3A—O3—H3C</td><td>109.5</td></tr><tr><td>C3A—C7A—H7A2</td><td>109.5</td></tr><tr><td>C3A—C7A—H7A3</td><td>109.5</td></tr><tr><td>H7A2—C7A—H7A3</td><td>109.5</td></tr><tr><td>C3A—C7A—H7A1</td><td>109.5</td></tr><tr><td>H7A2—C7A—H7A1</td><td>109.5</td></tr><tr><td>H7A3—C7A—H7A1</td><td>109.5</td></tr><tr><td>C4B—C7B—H7B1</td><td>109.5</td></tr><tr><td>C4B—C7B—H7B2</td><td>109.5</td></tr><tr><td>H7B1—C7B—H7B2</td><td>109.5</td></tr><tr><td>C4B—C7B—H7B3</td><td>109.5</td></tr><tr><td>H7B1—C7B—H7B3</td><td>109.5</td></tr><tr><td>H7B2—C7B—H7B3</td><td>109.5</td></tr></table>

<table><tr><td>C5B—C6—N1—C9</td><td>175.2 (19)</td></tr><tr><td>C1—C6—N1—C9</td><td>0.7 (4)</td></tr><tr><td>C5A—C6—N1—C9</td><td>-178.8 (8)</td></tr><tr><td>C5B—C6—N1—C8</td><td>-3 (2)</td></tr><tr><td>C1—C6—N1—C8</td><td>-177.6 (3)</td></tr><tr><td>C5A—C6—N1—C8</td><td>2.8 (9)</td></tr><tr><td>C6—N1—C9—O1</td><td>-179.7 (3)</td></tr><tr><td>C8—N1—C9—O1</td><td>-1.3 (5)</td></tr><tr><td>C6—N1—C9—C10</td><td>-0.6 (4)</td></tr><tr><td>C8—N1—C9—C10</td><td>177.8 (3)</td></tr><tr><td>O1—C9—C10—O2</td><td>0.6 (5)</td></tr><tr><td>N1—C9—C10—O2</td><td>-178.5 (3)</td></tr><tr><td>O1—C9—C10—N2</td><td>179.9 (3)</td></tr><tr><td>N1—C9—C10—N2</td><td>0.8 (4)</td></tr><tr><td>O2—C10—N2—C1</td><td>178.2 (3)</td></tr><tr><td>C9—C10—N2—C1</td><td>-1.0 (4)</td></tr><tr><td>O2—C10—N2—C11</td><td>0.1 (5)</td></tr><tr><td>C9—C10—N2—C11</td><td>-179.1 (3)</td></tr><tr><td>C2B—C1—N2—C10</td><td>-177.6 (14)</td></tr><tr><td>C6—C1—N2—C10</td><td>1.1 (4)</td></tr><tr><td>C2A—C1—N2—C10</td><td>-179.0 (5)</td></tr><tr><td>C2B—C1—N2—C11</td><td>0.4 (14)</td></tr><tr><td>C6—C1—N2—C11</td><td>179.1 (3)</td></tr><tr><td>C2A—C1—N2—C11</td><td>-1.1 (7)</td></tr></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>O3—H3A···O1</td><td>0.86</td><td>2.09</td><td>2.936 (4)</td><td>170</td></tr><tr><td>O3—H3C···O1<sup>i</sup></td><td>0.86</td><td>2.38</td><td>3.062 (4)</td><td>137</td></tr><tr><td>O3—H3C···O2<sup>i</sup></td><td>0.86</td><td>2.19</td><td>2.972 (5)</td><td>150</td></tr><tr><td>C5A—H5A···O3<sup>ii</sup></td><td>0.94</td><td>2.40</td><td>3.298 (13)</td><td>160</td></tr><tr><td>C8—H8E···O2<sup>iii</sup></td><td>0.97</td><td>2.45</td><td>3.335 (4)</td><td>151</td></tr></tbody></table>

Symmetry codes: (i) $-x+1, -y+3, -z$; (ii) $-x+1/2, y-1/2, -z-1/2$; (iii) $x-1/2, -y+5/2, z-1/2$.