Crystal structure, Hirshfeld surface analysis and energy
frameworks of 1-[( E
)-2-(2-fluorophenyl)diazan-1-ylidene]naphthalen-2(1 H
)-one

Hibet Errahmane Meroua Akkache, Noudjoud Hamdouni, Ali Boudjada, Mohamed Larbi Medjroubi, Assia Mili, Olivier Jeannin

► To cite this version:

Hibet Errahmane Meroua Akkache, Noudjoud Hamdouni, Ali Boudjada, Mohamed Larbi Medjroubi, Assia Mili, et al.. Crystal structure, Hirshfeld surface analysis and energy frameworks of 1-[( E )-2-(2-fluorophenyl)diazan-1-ylidene]naphthalen-2(1 H )-one. Acta crystallographica Section E: Crystallographic communications [2015-..], 2024, 80 (2), pp.137-142. 10.1107/S2056989024000227. hal-04434595

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Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 27 October 2023

Accepted 6 January 2024

Edited by F. F. Ferreira, Universidade Federal do ABC, Brazil

This article is part of a collection of articles to commemorate the founding of the African Crystallographic Association and the 75th anniversary of the IUCr.

**Keywords:** azo compounds; 2-naphthols; crystal structure; Hirshfeld surface calculations; two-dimensional fingerprint plot; energy frameworks.

CCDC reference: 2323843

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

# Crystal structure, Hirshfeld surface analysis and energy frameworks of 1-[(E)-2-(2-fluorophenyl)-diazan-1-ylidene]naphthalen-2(1H)-one

Hibet Errahmane Meroua Akkache,ª* Noudjoud Hamdouni,ª Ali Boudjada,ª Mohamed larbi Medjroubi,ª Assia Miliᵇ and Olivier Jeanninᶜ

ªLaboratoire de Cristallographie, Département de Physique, Université Mentouri-Constantine, 25000 Constantine, Algeria, ᵇUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Faculté du Sciences Exactes, Université de Constantine 1, 25000 Constantine, Algeria, and ᶜUMR 6226 CNRS-Université Rennes 1, 'Sciences Chimiques de Rennes', Equipe 'Matière Condensée et Systèmes Electroactifs', Bâtiment 10C Campus de Beaulieu, 263 Avenue du Général Leclerc, F-35042 Rennes, France. *Correspondence e-mail: hibeterrahmanemeroua.akkache@doc.umc.edu.dz

The title compound, C₁₆H₁₁N₂OF, is a member of the azo dye family. The dihedral angle subtended by the benzene ring and the naphthalene ring system measures 18.75 (7)°, indicating that the compound is not perfectly planar. An intramolecular N-H···O hydrogen bond occurs between the imino and carbonyl groups. In the crystal, the molecules are linked into inversion dimers by C-H···O interactions. Aromatic π-π stacking between the naphthalene ring systems lead to the formation of chains along [001]. A Hirshfeld surface analysis was undertaken to investigate and quantify the intermolecular interactions. In addition, energy frameworks were used to examine the cooperative effect of these intermolecular interactions across the crystal, showing dispersion energy to be the most influential factor in the crystal organization of the compound.

## 1. Chemical context

In dye chemistry, azo dyes are produced in the most significant quantities (Benkhaya et al., 2020). Azo compounds are commonly used in various industrial applications, including as colourants (Mohammadi et al., 2015) and pigments (Ramu-gade et al., 2019; Vafaei et al., 2012) and in printing (Nawwar et al., 2020). Azo dyes are generally used in the leather, food, and cosmetics industries because they have bright colours and good stability. Apart from this, they have been widely employed in a variety of areas including the food (Yamjala et al., 2016) and cosmetics industries (Leulescu et al., 2021) and as metal-organic frameworks (MOFs) (Ayati et al., 2016), covalent-organic frameworks (COFs) (Xue et al., 2023), corrosion inhibitors for iron (Madkour et al., 2018), catalysis (Liu et al., 2016), non-linear optics (Kato et al., 1994) and fibre optics (Kavitha et al., 2022). In addition to this, azo dyes have been found to have biological, biomedical, and pharmacolo-gical applications, such as in DNA binding and antioxidants (Qamar et al., 2019), drug design (Demirçalı & Topal, 2023), and virology (Meng et al., 2021). However, it is important to understand that some azo dyes can harm human health and the environment. This is because of their potential to release carcinogenic aromatic amines when they undergo degradation processes triggered by bacteria or sunlight (Golka et al., 2004). Following our interest in azo dyes, we present the crystal structure of a new azo compound 1-[(E)-2-(2-fluorophenyl) diazan-1-ylidene]naphthalen-2(1H)-one.

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OPEN ACCESS

Published under a CC BY 4.0 licence
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## 2. Structural commentary

The structure of the title compound is illustrated in Fig. 1. The N19–N20 [1.310 (2) Å] and C8–O17 [1.264 (3) Å] bond lengths indicate that the compound adopts the neutral hydrazo tautomer form upon crystallization. This is common when an OH group is in the *ortho*-position relative to the azo group, leading to a proton being transferred from the naphthol group to the azo group (Benaouida *et al.*, 2023; Bougueria *et al.*, 2021). The internal alternate angles at N19 and N20 are identical within experimental error with an average value of 118.25 (2)°. This is not observed in the isotypic product (Bougueria *et al.*, 2017). Bond lengths are within normal ranges and resemble those observed in isotypic crystal structures (Bougueria *et al.*, 2017). The naphthol and benzene rings, which are connected to the hydrazo group, are not perfectly planar. The dihedral angle between these rings is 18.75 (7)°. However, in the isotopic variant of the molecule, this angle was slightly smaller at 15.33 (7)° (Bougueria *et al.*, 2017). An intramolecular hydrogen bond (Table 1) contributes to the molecular stability. The most significant exocyclic angle C7–C8–O17 [121.5 (2)°] adjacent to the C8–O17 bond could be attributed to the critical interaction between the O17 and H21 atoms. The smallest exocyclic angle C1–C6–F18 [117.4 (2)°] adjacent to the C6–F18 bond may be due to an attractive interaction between fluorine and hydrogen.

## 3. Supramolecular features

In the crystal, the molecules are linked by intermolecular C–H···O hydrogen bonds (Table 1), see Fig. 2. Cohesion of

<figure><img src="image_6.png" /><figcaption>**Figure 1**</figcaption></figure>

The molecular structure of the title compound with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

<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>N19–H21···O17</td><td>0.88</td><td>1.84</td><td>2.541 (3)</td><td>135</td></tr><tr><td>C2–H22···O17<sup>i</sup></td><td>0.95</td><td>2.63</td><td>3.242 (3)</td><td>122</td></tr><tr><td>C5–H25···O17<sup>ii</sup></td><td>0.95</td><td>2.64</td><td>3.539 (3)</td><td>159</td></tr></tbody></table>

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

the crystal is enhanced by the presence of parallel displaced π–π stacking interactions (Fig. 3), the most significant of which is between naphthalene ring systems [Cg···Cg(1/2 − x, y, 1/2 + z) = 3.6171 (4) Å where Cg is the centroid of the C7–C12 ring], forming sinusoidal chains along the c-axis direction.

## 4. Hirshfeld surface analysis (HS), interaction energies and energy frameworks

The weak intermolecular interactions within the crystal structure were examined by analysing Hirshfeld surfaces (Spackman & Jayatilaka, 2009). The associated 2D fingerprint plots (Spackman & McKinnon, 2002) were drawn using *CrystalExplorer21* (Spackman *et al.*, 2021). Measuring and interpreting the intermolecular interactions within the crystal packing is visualized through normalized contact distance ($d_{norm}$). In this context, white denotes contacts with distances equal to the van der Waals (vdW) radii. Connections that are short of the vdW radii are represented in red, while those that

<figure><img src="image_7.png" /><figcaption>**Figure 2**</figcaption></figure>

A view along the c axis of the crystal packing.
<figure><img src="image_8.png" /><figcaption>**Figure 3**</figcaption></figure>

$\pi-\pi$ stacking interactions in the title compound. Dotted black lines indicate $Cg \cdots Cg$ contacts.

exceed the vdW radii are shown in blue. In Fig. 4a, dark-red spots represent strong intermolecular $C-H \cdots O$ hydrogen bonds and light-red spots represent $C \cdots C$ close interactions. In addition, the shape-index is used to identify complementary hollows (red) and bumps (blue) where two molecular surfaces touch one another (Spackman & Jayatilaka, 2009). As depicted in Fig. 4b, the two sides of the molecule interact differently with adjacent molecules. This includes $\pi-\pi$ stacking, represented by adjacent red and blue triangles (McKinnon *et al.*, 2004). Curvedness is a tool for pinpointing planar stacking configurations and how neighbouring molecules interact (Spackman & Jayatilaka, 2009). Fig. 5a shows relatively large green planes in the benzene and naphthalene rings separated by blue edges. These green planes give us an idea of the flatness of complexes, and the fragment patch

<caption>**Table 2**</caption>

Percentage contributions of various intermolecular interactions to the Hirshfeld surface of the title compound.

<table><thead><tr><th>Contact</th><th>Contribution</th><th>Contact</th><th>Contribution</th></tr></thead><tbody><tr><td>F···F</td><td>1.1</td><td>N···C/C···N</td><td>5.9</td></tr><tr><td>F···H/H···F</td><td>10.2</td><td>N···H/H···N</td><td>1.3</td></tr><tr><td>F···C/C···F</td><td>0.2</td><td>H···H</td><td>41.7</td></tr><tr><td>O···H/H···O</td><td>8.5</td><td>H···C/C···H</td><td>18.8</td></tr><tr><td>O···C/C···O</td><td>1.4</td><td>C···C</td><td>10.9</td></tr></tbody></table>

(Fig. 5b) is designed to indicate the nearest neighbouring molecule (Spackman *et al.*, 2021). The electrostatic potential was mapped using TONTO (Spackman & Jayatilaka, 2009), integrated into CrystalExplorer, with the STO-3G basis/ Hartree-Fock function. The contacts are discernible as areas of electropositivity (blue) and electronegativity (red) that exhibit a complementary relationship (Spackman *et al.*, 2008). These short contacts correspond to $C-H \cdots O$. Blue and red areas around the atoms denote hydrogen-bond donors and acceptors, respectively. These colours indicate the positive and negative electrostatic potentials in Fig. 6.

The proportional contribution of the contacts over the surface is visualized in the fingerprint plots with the Hirshfeld surface of the contribution (Table 2). The fingerprint plots of the $H \cdots H$ contacts, which represent the most significant contribution to the Hirshfeld surfaces at 41.7%, show a distinct pattern with a minimum value of $d_e = d_i \approx 1.2$ Å (Fig. 7a). The contribution of the $C \cdots H/H \cdots C$ contacts appears as the second largest region of the fingerprint plot,

<figure><img src="image_9.png" /><figcaption>**Figure 5**</figcaption></figure>

(a) Curvedness and (b) fragment patch along [001].

<figure><img src="image_10.png" /><figcaption>**Figure 4**</figcaption></figure>

Hirshfeld surface mapped over (a) $d_{norm}$ and (b) shape-index.

<figure><img src="image_11.png" /><figcaption>**Figure 6**</figcaption></figure>

Electrostatic potential mapped on the Hirshfeld surface along [001].
<caption>**Table 3**
Interaction energies (kJ mol⁻¹) between a reference molecule and its neighbours.</caption>

N is the number of equivalent neighbours, and R is the distance between molecular centroids (mean atomic position) in Å. The colours identify molecules in Fig. 8a, with the reference molecule shown in grey.

<table><thead><tr><th>Colour</th><th>N</th><th>Symmetry</th><th>R</th><th>Electron density</th><th>E<sub>ele</sub></th><th>E<sub>pol</sub></th><th>E<sub>dis</sub></th><th>E<sub>rep</sub></th><th>E<sub>tot</sub></th></tr></thead><tbody><tr><td>Red</td><td>2</td><td>x + 1/2, -y, z</td><td>11.92</td><td>HF/3-21G</td><td>-5.2</td><td>-1.1</td><td>-10.7</td><td>4.7</td><td>-11.8</td></tr><tr><td>Yellow</td><td>2</td><td>-x + 1/2, y, z + 1/2</td><td>5.00</td><td>HF/3-21G</td><td>-10.3</td><td>-2.7</td><td>-75.0</td><td>37.4</td><td>-49.5</td></tr><tr><td>Green</td><td>2</td><td>x + 1/2, -y, z</td><td>13.06</td><td>HF/3-21G</td><td>2.3</td><td>-0.5</td><td>-7.2</td><td>0.0</td><td>-4.5</td></tr><tr><td>Lime</td><td>2</td><td>-x, -y, z + 1/2</td><td>10.67</td><td>HF/3-21G</td><td>-3.4</td><td>-1.0</td><td>-17.8</td><td>10.8</td><td>-11.5</td></tr><tr><td>Aqua</td><td>2</td><td>x, y, z</td><td>7.24</td><td>HF/3-21G</td><td>-7.4</td><td>-3.7</td><td>-24.0</td><td>11.4</td><td>-22.3</td></tr><tr><td>Indigo</td><td>2</td><td>-x + 1/2, y, z + 1/2</td><td>8.80</td><td>HF/3-21G</td><td>-1.2</td><td>-1.8</td><td>-15.2</td><td>5.3</td><td>-11.8</td></tr><tr><td>Magenta</td><td>2</td><td>-x, -y, z + 1/2</td><td>9.23</td><td>HF/3-21G</td><td>-6.2</td><td>-2.1</td><td>-9.9</td><td>2.9</td><td>-14.3</td></tr></tbody></table>

heavily concentrated on the edges with $d_e + d_i \simeq 2.8$ Å and an overall Hirshfeld surface contribution of 18.8% (Fig. 7b). The C···C contacts occupy 10.9% of the Hirshfeld surface with $d_e + d_i \simeq 1.7$ Å. Bonds are observed around light-red spots among these contacts (Fig. 7c). The H···F···F···H contacts contribute 10.2% of the Hirshfeld surface with $d_e + d_i \simeq 2.6$ Å (Fig. 7d). The O···H···O···C contacts, with a contribution of 8.5% and $d_e + d_i \simeq 2.5$ Å, appear as dark-red spots on the Hirshfeld surfaces mapped over $d_{norm}$ (Fig. 7e). The percentage contribution of the C···N···N···C contacts is 5.9% with $d_e + d_i \simeq 3.3$ Å (Fig. 7f) while the O···C···C···O interaction, with a contribution of 1.4% is in the form of symmetrical claws with the two ends pointing towards pairs at $d_e + d_i \simeq 3.5$ Å and

$d_e + d_i \simeq 3.6$ Å (Fig. 7g). The N···H···H···N (Fig. 7h), F···F (Fig. 7i) and F···C···C···F (Fig. 7j) interactions are the weakest with contributions of 1.3%, 1.1% and 0.2% and $d_e + d_i \simeq 3.6$ Å, 3.8 Å and 3.5 Å, respectively.

The total intermolecular energy $E_{tot}$ (kJ mol⁻¹) is the sum of four main energy components: electrostatic, polarisation, dispersion and exchange repulsion (Mackenzie et al., 2017; Spackman et al., 2021). The calculation was performed for a cluster of molecules within a 3.8 Å radius surrounding the selected molecule (Fig. 8a) using the HF/3-21G energy model in conjunction with adjustment coefficients for energy models that have been benchmarked to determine $E_{tot}$ (kJ mol⁻¹): $K_{ele}=1.019$, $K_{dis}=0.651$, $K_{rep}=0.901$. The interaction energies, as determined by the energy model, suggest that interactions in the crystal are significantly influenced by dispersion components (Table 3). The interaction between the selected molecule and the symmetry-related molecule at $-x + 1/2, y, z + 1/2$ (coloured yellow) is the most important interaction between neighbouring molecules, with energy: $E_{ele} = -10.3$, $E_{pol} = -2.7$, $E_{dis} = -75.0$, $E_{rep} = 37.4$ and $E_{tot} = -49.5$ kJ mol⁻¹. Using energy frameworks (Turner et al., 2015) built for $E_{ele}$ (red cylinders) Fig. 8b, $E_{dis}$ (green cylinders) Fig. 8c, and $E_{tot}$ (blue cylinders) Fig. 8d, the energies between molecular pairs are represented as cylinders joining the centroids of pairs of

<figure><img src="image_12.png" /><figcaption>**Figure 7**
Two-dimensional fingerprint plots for the title compound showing the contributions of different types of interactions: (a) H···H, (b) C···H/H···C, (c) C···C, (d) H···F···F···H, (e) O···H···H···O, (f) C···N···N···C, (g) N···H···H···N, (h) F···F, (i) F···C···C···F, (j) F···C···C···F.</figcaption></figure>

<figure><img src="image_13.png" /><figcaption>**Figure 8**
(a) Interactions between the reference molecule and the molecules present in a 3.8 Å cluster around energy frameworks built for (b) $E_{ele}$ (red cylinders), (c) $E_{dis}$ (green cylinders) and $E_{tot}$ (blue cylinders) along [001].</figcaption></figure>
molecules. The diameter of these cylinders is adjusted to reflect the degree of change in the interaction.

## 5. Database survey

A search of the Cambridge Structural Database (CSD; Version 2023.2.0, last update September 2023; Groom *et al.*, 2016) for 1-phenylazo-2-naphthol derivatives revealed that numerous azo-2-naphthol compounds with similar structures have been synthesized using various aromatic primary amines. Examples include (E)-1-(3-chlorophenyl)-2-(2-oxidonaphthalen-1-yl)diazen-1-ium (AFOJUC; Benosmane *et al.*, 2013), 1-[(E)-2-(5-chloro-2 hydroxyphenyl) hydrazin-1-ylidene]naphthalen-2(1H)-one (UVIDOV; Bougueria *et al.*, 2021), (E)-1-(4-fluorophenyl)-2-(2-oxidonaphthalen-1-yl) diazenium (RAHHIU; Bougueria *et al.*, 2017), (1Z)-naphthalene-1,2-dione 1-[(2-fluorophenyl)hydrazone] (OGUXAP, OGUXAP01, OGUXAP02 and OGUXAP03; Gilli *et al.*, 2002), (E)-1-[2-(3-nitrophenyl)hydrazinylidene]naphthalen-2(1H)-one (FIFCEG; Benaouida *et al.*, 2023), 1-(phenylazo)-2-naphthol (JARPEX; Olivieri *et al.*, 2002), (Z)-1-(2-phenyl-diazen-2-ium-1-yl)naphthalen-2-olate (TIFTEJ01; Benosmane *et al.*, 2015). All these compounds belong to the azo dyes family and share a common base structure – a benzene ring and a naphthalene ring system linked with an oxygen in the *ortho* position relative to the azo group. This shared structure has almost the same properties. For instance, the azo group contributes to the vivid colors of these dyes, while the specific arrangement of the rings can influence their stability and reactivity.

## 6. Synthesis and crystallization

The title compound was synthesised by two successive reactions, diazotization and coupling. 3-Aminobenzaldehyde (0.02 mol) was treated in 6 ml of 12M HCl and NaNO₂ (0.0214 mol) in 8 ml of water for 30 min. To the solution obtained, a solution of naphthalene-2-ol was added dropwise as a coupler where the structural nature of the coupler determined the colour and molecular structure of the C₁₈H₁₆N₂O₃ monomer. The orange-red powder obtained was recrystallized from pentane, leading to prismatic air-stable crystals.

## 7. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 4. The H atoms were included in calculated positions and refined as riding: N—H = 0.88 Å, C—H = 0.95 Å with $U_{iso}(H) = 1.2U_{eq}(N,C)$.

## Acknowledgements

We would like to thank the diffractometer Center of Rennes 1 University for the opportunity to collect the X-ray diffraction data.

<table><caption>**Table 4**</caption><caption>Experimental details.</caption><tbody><tr><td colspan="2"><strong>Crystal data</strong></td></tr><tr><td>Chemical formula</td><td>C<sub>16</sub>H<sub>11</sub>FN<sub>2</sub>O</td></tr><tr><td>M<sub>r</sub></td><td>266.27</td></tr><tr><td>Crystal system, space group</td><td>Orthorhombic, <i>Pca</i>2<sub>1</sub></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>23.612 (3), 7.2392 (8), 7.2122 (7)</td></tr><tr><td><i>V</i> (Å<sup>3</sup>)</td><td>1232.8 (2)</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>0.10</td></tr><tr><td>Crystal size (mm)</td><td>0.18 × 0.16 × 0.06</td></tr><tr><td colspan="2"><strong>Data collection</strong></td></tr><tr><td>Diffractometer</td><td>Bruker D8 VENTURE</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>5289, 2803, 2700</td></tr><tr><td><i>R</i><sub>int</sub></td><td>0.021</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.650</td></tr><tr><td colspan="2"><strong>Refinement</strong></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>0.044, 0.109, 1.08</td></tr><tr><td>No. of reflections</td><td>2803</td></tr><tr><td>No. of parameters</td><td>181</td></tr><tr><td>No. of restraints</td><td>1</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, -0.23</td></tr><tr><td>Absolute structure</td><td>Flack x determined using 1169 quotients [(<i>I</i><sup>+</sup>)-(<i>I</i><sup>-</sup>)]/[(<i>I</i><sup>+</sup>)+(<i>I</i><sup>-</sup>)] (Parsons *et al.*, 2013)</td></tr><tr><td>Absolute structure parameter</td><td>0.0 (3)</td></tr></tbody></table>

Computer programs: *APEX3* and *SAINT* (Bruker, 2015), *SHELXT20182* (Sheldrick, 2015a), *SHELXL20183* (Sheldrick, 2015b), *ORTEP-3* for Windows and WinGX publication routines (Farrugia, 2012), *Mercury* (Macrae *et al.*, 2020) and *OLEX2* (Dolomanov *et al.*, 2009).

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supporting information

Acta Cryst. (2024). E80, 137-142 [https://doi.org/10.1107/S2056989024000227]

# Crystal structure, Hirshfeld surface analysis and energy frameworks of 1-[(E)-2-(2-fluorophenyl)diazan-1-ylidene]naphthalen-2(1H)-one

Hibet Errahmane Meroua Akkache, Noudjoud Hamdouni, Ali Boudjada, Mohamed larbi Medjroubi, Assia Mili and Olivier Jeannin

Computing details

1-[(E)-2-(2-Fluorophenyl)diazan-1-ylidene]naphthalen-2(1H)-one

## Crystal data

C₁₆H₁₁FN₂O
M_r = 266.27
Orthorhombic, Pca2₁
Hall symbol: P 2c -2ac
a = 23.612 (3) Å
b = 7.2392 (8) Å
c = 7.2122 (7) Å
V = 1232.8 (2) Å³
Z = 4

F(000) = 552
Dₓ = 1.435 Mg m⁻³
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9942 reflections
θ = 2.9–27.5°
μ = 0.10 mm⁻¹
T = 150 K
Prism, orange-red
0.18 × 0.16 × 0.06 mm

## Data collection

Bruker D8 VENTURE
diffractometer
Radiation source: Enraf-Nonius FR590
Multilayer monochromator
Detector resolution: 7.39 pixels mm⁻¹
CCD rotation images, thick slices scans
5289 measured reflections

2803 independent reflections
2700 reflections with *I* > 2σ(*I*)
*R*<sub>int</sub> = 0.021
θ<sub>max</sub> = 27.5°, θ<sub>min</sub> = 2.9°
h = 0→30
k = −9→9
l = −9→9

## Refinement

Refinement on *F*²
Least-squares matrix: full
R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.109
S = 1.08
2803 reflections
181 parameters
1 restraint
0 constraints
Primary atom site location: dual
Secondary atom site location: dual

Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ²(F₀²) + (0.0633P)² + 0.187P]
where P = (F₀² + 2Fₐ²)/3
(Δ/σ)max < 0.001
Δρmax = 0.32 e Å⁻³
Δρmin = −0.23 e Å⁻³
Absolute structure: Flack *x* determined using
1169 quotients [(I⁺)-(I)]/[(I⁺)+(I)] (Parsons *et al.*, 2013)
Absolute structure parameter: 0.0 (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.

<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>F18</td><td>0.48474 (6)</td><td>0.5004 (2)</td><td>0.4401 (3)</td><td>0.0471 (5)</td></tr><tr><td>O17</td><td>0.35348 (8)</td><td>0.7103 (2)</td><td>0.6361 (3)</td><td>0.0358 (4)</td></tr><tr><td>N20</td><td>0.32550 (7)</td><td>0.3449 (2)</td><td>0.5164 (3)</td><td>0.0229 (4)</td></tr><tr><td>N19</td><td>0.37924 (7)</td><td>0.3898 (3)</td><td>0.5197 (3)</td><td>0.0254 (4)</td></tr><tr><td>H21</td><td>0.390131</td><td>0.49963</td><td>0.557997</td><td>0.03*</td></tr><tr><td>C1</td><td>0.41885 (9)</td><td>0.2586 (3)</td><td>0.4609 (3)</td><td>0.0250 (5)</td></tr><tr><td>C2</td><td>0.40634 (9)</td><td>0.0731 (3)</td><td>0.4374 (3)</td><td>0.0283 (5)</td></tr><tr><td>H22</td><td>0.369604</td><td>0.028034</td><td>0.466435</td><td>0.034*</td></tr><tr><td>C7</td><td>0.28796 (9)</td><td>0.4712 (3)</td><td>0.5655 (3)</td><td>0.0226 (4)</td></tr><tr><td>C4</td><td>0.50093 (12)</td><td>0.0177 (4)</td><td>0.3267 (4)</td><td>0.0345 (5)</td></tr><tr><td>H24</td><td>0.528484</td><td>-0.06543</td><td>0.279197</td><td>0.041*</td></tr><tr><td>C9</td><td>0.25667 (12)</td><td>0.7806 (3)</td><td>0.6729 (3)</td><td>0.0314 (5)</td></tr><tr><td>H27</td><td>0.265059</td><td>0.901517</td><td>0.71613</td><td>0.038*</td></tr><tr><td>C14</td><td>0.15584 (10)</td><td>0.1955 (3)</td><td>0.4718 (4)</td><td>0.0334 (5)</td></tr><tr><td>H26</td><td>0.145461</td><td>0.075616</td><td>0.430408</td><td>0.04*</td></tr><tr><td>C13</td><td>0.21242 (9)</td><td>0.2415 (3)</td><td>0.4897 (3)</td><td>0.0269 (5)</td></tr><tr><td>H28</td><td>0.240645</td><td>0.152688</td><td>0.460149</td><td>0.032*</td></tr><tr><td>C10</td><td>0.20214 (11)</td><td>0.7276 (3)</td><td>0.6565 (4)</td><td>0.0326 (5)</td></tr><tr><td>H29</td><td>0.173167</td><td>0.813258</td><td>0.687556</td><td>0.039*</td></tr><tr><td>C3</td><td>0.44734 (11)</td><td>-0.0462 (3)</td><td>0.3718 (4)</td><td>0.0328 (5)</td></tr><tr><td>H23</td><td>0.438708</td><td>-0.173543</td><td>0.357452</td><td>0.039*</td></tr><tr><td>C8</td><td>0.30254 (10)</td><td>0.6573 (3)</td><td>0.6261 (3)</td><td>0.0273 (5)</td></tr><tr><td>C11</td><td>0.18627 (10)</td><td>0.5474 (3)</td><td>0.5941 (3)</td><td>0.0273 (5)</td></tr><tr><td>C6</td><td>0.47345 (10)</td><td>0.3187 (3)</td><td>0.4186 (4)</td><td>0.0304 (5)</td></tr><tr><td>C12</td><td>0.22854 (9)</td><td>0.4166 (3)</td><td>0.5506 (3)</td><td>0.0238 (5)</td></tr><tr><td>C15</td><td>0.11400 (10)</td><td>0.3244 (4)</td><td>0.5144 (4)</td><td>0.0364 (6)</td></tr><tr><td>H30</td><td>0.07518</td><td>0.292542</td><td>0.501361</td><td>0.044*</td></tr><tr><td>C16</td><td>0.12878 (10)</td><td>0.4969 (4)</td><td>0.5748 (4)</td><td>0.0342 (6)</td></tr><tr><td>H31</td><td>0.100014</td><td>0.5839</td><td>0.604186</td><td>0.041*</td></tr><tr><td>C5</td><td>0.51440 (10)</td><td>0.2024 (4)</td><td>0.3506 (4)</td><td>0.0354 (6)</td></tr><tr><td>H25</td><td>0.551065</td><td>0.247445</td><td>0.320609</td><td>0.042*</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>F18</td><td>0.0293 (7)</td><td>0.0333 (7)</td><td>0.0787 (14)</td><td>-0.0085 (6)</td><td>0.0016 (8)</td><td>-0.0001 (8)</td></tr><tr><td>O17</td><td>0.0368 (9)</td><td>0.0295 (8)</td><td>0.0412 (10)</td><td>-0.0081 (7)</td><td>-0.0010 (8)</td><td>0.0006 (8)</td></tr><tr><td>N20</td><td>0.0227 (8)</td><td>0.0246 (8)</td><td>0.0213 (9)</td><td>-0.0011 (7)</td><td>-0.0005 (7)</td><td>0.0043 (7)</td></tr><tr><td>N19</td><td>0.0219 (8)</td><td>0.0250 (8)</td><td>0.0293 (10)</td><td>-0.0030 (7)</td><td>-0.0011 (7)</td><td>0.0023 (8)</td></tr></tbody></table>
<table><tr><td>C1</td><td>0.0235 (9)</td><td>0.0278 (10)</td><td>0.0236 (10)</td><td>0.0007 (8)</td><td>-0.0017 (8)</td><td>0.0047 (8)</td></tr><tr><td>C2</td><td>0.0270 (10)</td><td>0.0285 (10)</td><td>0.0294 (12)</td><td>-0.0016 (8)</td><td>-0.0028 (9)</td><td>0.0031 (10)</td></tr><tr><td>C7</td><td>0.0278 (10)</td><td>0.0228 (10)</td><td>0.0173 (9)</td><td>0.0007 (8)</td><td>-0.0001 (8)</td><td>0.0046 (8)</td></tr><tr><td>C4</td><td>0.0323 (11)</td><td>0.0434 (14)</td><td>0.0277 (12)</td><td>0.0092 (10)</td><td>0.0011 (10)</td><td>0.0002 (10)</td></tr><tr><td>C9</td><td>0.0452 (14)</td><td>0.0251 (9)</td><td>0.0239 (12)</td><td>0.0024 (10)</td><td>0.0028 (10)</td><td>0.0007 (9)</td></tr><tr><td>C14</td><td>0.0314 (11)</td><td>0.0358 (12)</td><td>0.0332 (14)</td><td>-0.0046 (9)</td><td>-0.0002 (10)</td><td>0.0053 (10)</td></tr><tr><td>C13</td><td>0.0249 (9)</td><td>0.0284 (11)</td><td>0.0276 (13)</td><td>0.0024 (8)</td><td>0.0011 (9)</td><td>0.0033 (9)</td></tr><tr><td>C10</td><td>0.0412 (13)</td><td>0.0333 (12)</td><td>0.0233 (12)</td><td>0.0114 (10)</td><td>0.0048 (10)</td><td>0.0022 (10)</td></tr><tr><td>C3</td><td>0.0360 (12)</td><td>0.0292 (11)</td><td>0.0334 (13)</td><td>0.0009 (9)</td><td>-0.0015 (11)</td><td>-0.0003 (10)</td></tr><tr><td>C8</td><td>0.0345 (11)</td><td>0.0271 (10)</td><td>0.0204 (11)</td><td>-0.0010 (9)</td><td>-0.0003 (9)</td><td>0.0042 (9)</td></tr><tr><td>C11</td><td>0.0297 (11)</td><td>0.0323 (11)</td><td>0.0200 (11)</td><td>0.0077 (9)</td><td>0.0030 (8)</td><td>0.0066 (9)</td></tr><tr><td>C6</td><td>0.0253 (10)</td><td>0.0307 (11)</td><td>0.0352 (13)</td><td>-0.0034 (9)</td><td>-0.0027 (10)</td><td>0.0042 (10)</td></tr><tr><td>C12</td><td>0.0262 (10)</td><td>0.0289 (11)</td><td>0.0161 (10)</td><td>0.0023 (8)</td><td>0.0013 (8)</td><td>0.0059 (8)</td></tr><tr><td>C15</td><td>0.0242 (10)</td><td>0.0528 (14)</td><td>0.0322 (14)</td><td>0.0008 (10)</td><td>-0.0003 (10)</td><td>0.0070 (12)</td></tr><tr><td>C16</td><td>0.0266 (11)</td><td>0.0464 (14)</td><td>0.0296 (13)</td><td>0.0115 (10)</td><td>0.0040 (10)</td><td>0.0066 (11)</td></tr><tr><td>C5</td><td>0.0240 (10)</td><td>0.0462 (14)</td><td>0.0358 (14)</td><td>0.0008 (10)</td><td>0.0017 (10)</td><td>0.0064 (12)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>F18—C6</td><td>1.351 (3)</td><td>C9—H27</td><td>0.95</td></tr><tr><td>O17—C8</td><td>1.264 (3)</td><td>C14—C13</td><td>1.383 (3)</td></tr><tr><td>N20—N19</td><td>1.310 (2)</td><td>C14—C15</td><td>1.393 (4)</td></tr><tr><td>N20—C7</td><td>1.322 (3)</td><td>C14—H26</td><td>0.95</td></tr><tr><td>N19—C1</td><td>1.399 (3)</td><td>C13—C12</td><td>1.395 (3)</td></tr><tr><td>N19—H21</td><td>0.88</td><td>C13—H28</td><td>0.95</td></tr><tr><td>C1—C2</td><td>1.386 (3)</td><td>C10—C11</td><td>1.430 (4)</td></tr><tr><td>C1—C6</td><td>1.394 (3)</td><td>C10—H29</td><td>0.95</td></tr><tr><td>C2—C3</td><td>1.381 (3)</td><td>C3—H23</td><td>0.95</td></tr><tr><td>C2—H22</td><td>0.95</td><td>C11—C12</td><td>1.411 (3)</td></tr><tr><td>C7—C8</td><td>1.457 (3)</td><td>C11—C16</td><td>1.413 (3)</td></tr><tr><td>C7—C12</td><td>1.462 (3)</td><td>C6—C5</td><td>1.373 (4)</td></tr><tr><td>C4—C5</td><td>1.385 (4)</td><td>C15—C16</td><td>1.368 (4)</td></tr><tr><td>C4—C3</td><td>1.386 (4)</td><td>C15—H30</td><td>0.95</td></tr><tr><td>C4—H24</td><td>0.95</td><td>C16—H31</td><td>0.95</td></tr><tr><td>C9—C10</td><td>1.349 (4)</td><td>C5—H25</td><td>0.95</td></tr><tr><td>C9—C8</td><td>1.444 (3)</td><td></td><td></td></tr><tr><td>N19—N20—C7</td><td>118.22 (18)</td><td>C9—C10—H29</td><td>118.7</td></tr><tr><td>N20—N19—C1</td><td>118.27 (18)</td><td>C11—C10—H29</td><td>118.7</td></tr><tr><td>N20—N19—H21</td><td>120.9</td><td>C2—C3—C4</td><td>120.8 (2)</td></tr><tr><td>C1—N19—H21</td><td>120.9</td><td>C2—C3—H23</td><td>119.6</td></tr><tr><td>C2—C1—C6</td><td>118.2 (2)</td><td>C4—C3—H23</td><td>119.6</td></tr><tr><td>C2—C1—N19</td><td>123.5 (2)</td><td>O17—C8—C9</td><td>120.8 (2)</td></tr><tr><td>C6—C1—N19</td><td>118.2 (2)</td><td>O17—C8—C7</td><td>121.5 (2)</td></tr><tr><td>C3—C2—C1</td><td>119.9 (2)</td><td>C9—C8—C7</td><td>117.7 (2)</td></tr><tr><td>C3—C2—H22</td><td>120.1</td><td>C12—C11—C16</td><td>119.0 (2)</td></tr><tr><td>C1—C2—H22</td><td>120.1</td><td>C12—C11—C10</td><td>119.8 (2)</td></tr><tr><td>N20—C7—C8</td><td>124.1 (2)</td><td>C16—C11—C10</td><td>121.2 (2)</td></tr></table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><tbody><tr><td>N20—C7—C12</td><td>115.91 (19)</td><td>F18—C6—C5</td><td>120.0 (2)</td></tr><tr><td>C8—C7—C12</td><td>119.92 (19)</td><td>F18—C6—C1</td><td>117.4 (2)</td></tr><tr><td>C5—C4—C3</td><td>120.2 (2)</td><td>C5—C6—C1</td><td>122.6 (2)</td></tr><tr><td>C5—C4—H24</td><td>119.9</td><td>C13—C12—C11</td><td>119.1 (2)</td></tr><tr><td>C3—C4—H24</td><td>119.9</td><td>C13—C12—C7</td><td>122.07 (19)</td></tr><tr><td>C10—C9—C8</td><td>121.3 (2)</td><td>C11—C12—C7</td><td>118.8 (2)</td></tr><tr><td>C10—C9—H27</td><td>119.3</td><td>C16—C15—C14</td><td>120.1 (2)</td></tr><tr><td>C8—C9—H27</td><td>119.3</td><td>C16—C15—H30</td><td>120</td></tr><tr><td>C13—C14—C15</td><td>120.2 (2)</td><td>C14—C15—H30</td><td>120</td></tr><tr><td>C13—C14—H26</td><td>119.9</td><td>C15—C16—C11</td><td>120.8 (2)</td></tr><tr><td>C15—C14—H26</td><td>119.9</td><td>C15—C16—H31</td><td>119.6</td></tr><tr><td>C14—C13—C12</td><td>120.8 (2)</td><td>C11—C16—H31</td><td>119.6</td></tr><tr><td>C14—C13—H28</td><td>119.6</td><td>C6—C5—C4</td><td>118.3 (2)</td></tr><tr><td>C12—C13—H28</td><td>119.6</td><td>C6—C5—H25</td><td>120.8</td></tr><tr><td>C9—C10—C11</td><td>122.5 (2)</td><td>C4—C5—H25</td><td>120.8</td></tr><tr><td>C7—N20—N19—C1</td><td>-177.5 (2)</td><td>N19—C1—C6—F18</td><td>1.0 (3)</td></tr><tr><td>N20—N19—C1—C2</td><td>-14.4 (3)</td><td>C2—C1—C6—C5</td><td>1.8 (4)</td></tr><tr><td>N20—N19—C1—C6</td><td>163.7 (2)</td><td>N19—C1—C6—C5</td><td>-176.5 (2)</td></tr><tr><td>C6—C1—C2—C3</td><td>-0.7 (4)</td><td>C14—C13—C12—C11</td><td>0.0 (3)</td></tr><tr><td>N19—C1—C2—C3</td><td>177.4 (2)</td><td>C14—C13—C12—C7</td><td>-178.1 (2)</td></tr><tr><td>N19—N20—C7—C8</td><td>-1.0 (3)</td><td>C16—C11—C12—C13</td><td>0.0 (3)</td></tr><tr><td>N19—N20—C7—C12</td><td>177.15 (19)</td><td>C10—C11—C12—C13</td><td>-179.9 (2)</td></tr><tr><td>C15—C14—C13—C12</td><td>0.1 (4)</td><td>C16—C11—C12—C7</td><td>178.2 (2)</td></tr><tr><td>C8—C9—C10—C11</td><td>0.6 (4)</td><td>C10—C11—C12—C7</td><td>-1.7 (3)</td></tr><tr><td>C1—C2—C3—C4</td><td>-0.8 (4)</td><td>N20—C7—C12—C13</td><td>0.5 (3)</td></tr><tr><td>C5—C4—C3—C2</td><td>1.3 (4)</td><td>C8—C7—C12—C13</td><td>178.7 (2)</td></tr><tr><td>C10—C9—C8—O17</td><td>177.6 (2)</td><td>N20—C7—C12—C11</td><td>-177.6 (2)</td></tr><tr><td>C10—C9—C8—C7</td><td>-1.7 (3)</td><td>C8—C7—C12—C11</td><td>0.6 (3)</td></tr><tr><td>N20—C7—C8—O17</td><td>-0.2 (4)</td><td>C13—C14—C15—C16</td><td>-0.3 (4)</td></tr><tr><td>C12—C7—C8—O17</td><td>-178.3 (2)</td><td>C14—C15—C16—C11</td><td>0.3 (4)</td></tr><tr><td>N20—C7—C8—C9</td><td>179.2 (2)</td><td>C12—C11—C16—C15</td><td>-0.2 (4)</td></tr><tr><td>C12—C7—C8—C9</td><td>1.1 (3)</td><td>C10—C11—C16—C15</td><td>179.7 (2)</td></tr><tr><td>C9—C10—C11—C12</td><td>1.2 (4)</td><td>F18—C6—C5—C4</td><td>-178.6 (3)</td></tr><tr><td>C9—C10—C11—C16</td><td>-178.7 (2)</td><td>C1—C6—C5—C4</td><td>-1.3 (4)</td></tr><tr><td>C2—C1—C6—F18</td><td>179.2 (2)</td><td>C3—C4—C5—C6</td><td>-0.3 (4)</td></tr></tbody></table>

<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>N19—H21···O17</td><td>0.88</td><td>1.84</td><td>2.541 (3)</td><td>135</td></tr><tr><td>C2—H22···O17<sup>i</sup></td><td>0.95</td><td>2.63</td><td>3.242 (3)</td><td>122</td></tr><tr><td>C5—H25···O17<sup>ii</sup></td><td>0.95</td><td>2.64</td><td>3.539 (3)</td><td>159</td></tr></tbody></table>

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