# Crystal structure, hirshfeld surface analysis and inter-action energy and dft studies of 5,5-diphenyl-1,3-bis-(prop-2-yn-1-yl)imidazolidine-2,4-dione

Ismail Ghandour, Abdelouahed Bouayad, Tuncer Hokelek, Amal Haoudi, Frederic Capet, Catherine Renard, Youssef Kandri Rodi

► To cite this version:

Ismail Ghandour, Abdelouahed Bouayad, Tuncer Hokelek, Amal Haoudi, Frederic Capet, et al. Crystal structure, hirshfeld surface analysis and inter-action energy and dft studies of 5,5-diphenyl-1,3-bis-(prop-2-yn-1-yl)imidazolidine-2,4-dione. Acta crystallographica Section E: Crystallographic communications [2015-..], 2019. Acta crystallographica Section E: Crystallographic communications [2015-..], 75, pp.951-956. 10.1107/S2056989019007801. hal-04442625

HAL Id: hal-04442625

https://hal.univ-lille.fr/hal-04442625

Submitted on 6 Feb 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_1.png" /></figure>

Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 15 May 2019

Accepted 30 May 2019

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

**Keywords:** crystal structure; imidazolidine;
oxazole; π-stacking; Hirshfeld surface.

CCDC reference: 1919743

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

# Crystal structure, Hirshfeld surface analysis and interaction energy and DFT studies of 5,5-diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

Ismail Ghandour,ª Abdelouahed Bouayad,ª Tuncer Hökelek,ᵇ Amal Haoudi,ᶜ* Frédéric Capet,ᵈ Catherine Renardᵈ and Youssef Kandri Rodiᶜ

ªLaboratoire de Chimie de la Matière Condensée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202, Fez, Morocco, ᵇDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ᶜLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202, Fez, Morocco, and ᵈUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Université Lille 1, 59650 Villeneuve, d'Ascq, Cedex, France. ᶜCorrespondence e-mail: amalhaoudi2017@gmail.com

The title compound, C₂₁H₁₆N₂O₂, consists of an imidazolidine unit linked to two phenyl rings and two prop-2-yn-1-yl moieties. The imidazolidine ring is oriented at dihedral angles of 79.10 (5) and 82.61 (5)° with respect to the phenyl rings, while the dihedral angle between the two phenyl rings is 62.06 (5)°. In the crystal, intermolecular C—Hₚρop··Oᵢmdzln (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds link the molecules into infinite chains along the *b*-axis direction. Two weak C—Hₚhen··π interactions are also observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H···H (43.3%), H···C/ C···H (37.8%) and H···O/O···H (18.0%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that the C—Hₚρop··Oᵢmdzln hydrogen-bond energy in the crystal is −40.7 kJ mol⁻¹. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(d,p) level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

## 1. Chemical context

Pyrazolones are an important class of heterocyclic compounds that occur in many drugs and their derivatives have long been of interest to medicinal chemists for their wide range of biological activities (Pawar & Patil, 1994), including anti-bacterial, antidiabetic, immunosuppressive agents, and substances displaying hypoglycemic, antiviral and anti-neoplastic actions (Pathak & Bahel, 1980; Naik & Malik, 2010; Srivalli et al., 2011). Their pharmaceutical applications include use as a non-steroidal anti-inflammatory agent in the treatment of arthritis and other musculoskeletal and joint disorders (Amir & Kumar, 2005), and as analgesic, antipyretic (Badawey & El-Ashmawey, 1998) and hypoglycemic agents (Das et al., 2008). They also have fungicidal (Singh & Singh, 1991) and antimicrobial properties (Sahu et al., 2007), and some have been tested as potential cardiovascular drugs (Higashi et al., 2006). In the past few years, research has been focused on existing molecules and their modifications in order to reduce side effects and to explore other pharmacological and biological activity (Sahu et al., 2007; Naik & Malik, 2010; Srivalli et al., 2011). As a continuation of our research on the development of new N-substituted pyrazolone derivatives and the

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

OPEN

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

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

Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 15 May 2019

Accepted 30 May 2019

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

**Keywords:** crystal structure; imidazolidine;
oxazole; π-stacking; Hirshfeld surface.

CCDC reference: 1919743

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

# Crystal structure, Hirshfeld surface analysis and interaction energy and DFT studies of 5,5-diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

Ismail Ghandour,ª Abdelouahed Bouayad,ª Tuncer Hökelek,ᵇ Amal Haoudi,ᶜ* Frédéric Capet,ᵈ Catherine Renardᵈ and Youssef Kandri Rodiᶜ

The title compound, C₂₁H₁₆N₂O₂, consists of an imidazolidine unit linked to two phenyl rings and two prop-2-yn-1-yl moieties. The imidazolidine ring is oriented at dihedral angles of 79.10 (5) and 82.61 (5)° with respect to the phenyl rings, while the dihedral angle between the two phenyl rings is 62.06 (5)°. In the crystal, intermolecular C—Hₚρop··Oᵢmdzln (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds link the molecules into infinite chains along the *b*-axis direction. Two weak C—Hₚhen··π interactions are also observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H···H (43.3%), H···C/ C···H (37.8%) and H···O/O···H (18.0%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that the C—Hₚop··Oᵢmdzln hydrogen-bond energy in the crystal is −40.7 kJ mol⁻¹. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(d,p) level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

## 1. Chemical context

Pyrazolones are an important class of heterocyclic compounds that occur in many drugs and their derivatives have long been of interest to medicinal chemists for their wide range of biological activities (Pawar & Patil, 1994), including anti-bacterial, antidiabetic, immunosuppressive agents, and substances displaying hypoglycemic, antiviral and anti-neoplastic actions (Pathak & Bahel, 1980; Naik & Malik, 2010; Srivalli et al., 2011). Their pharmaceutical applications include use as a non-steroidal anti-inflammatory agent in the treatment of arthritis and other musculoskeletal and joint disorders (Amir & Kumar, 2005), and as analgesic, antipyretic (Badawey & El-Ashmawey, 1998) and hypoglycemic agents (Das et al., 2008). They also have fungicidal (Singh & Singh, 1991) and antimicrobial properties (Sahu et al., 2007), and some have been tested as potential cardiovascular drugs (Higashi et al., 2006). In the past few years, research has been focused on existing molecules and their modifications in order to reduce side effects and to explore other pharmacological and biological activity (Sahu et al., 2007; Naik & Malik, 2010; Srivalli et al., 2011). As a continuation of our research on the development of new N-substituted pyrazolone derivatives and the

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

OPEN

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

ACCESS

<footnote>ªLaboratoire de Chimie de la Matière Condensée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202, Fez, Morocco, ᵇDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ᶜLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202, Fez, Morocco, and ᵈUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Université Lille 1, 59650 Villeneuve, d'Ascq, Cedex, France. ᶜCorrespondence e-mail: amalhaoudi2017@gmail.com</footnote>
evaluation of their potential pharmacological activities, we report herein the synthesis, the molecular and crystal structures, the Hirshfeld surface analysis and intermolecular interaction energies and density functional theory (DFT) computational calculation of the title compound, (I).

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

## 2. Structural commentary

The title molecule consists of an imidazolidine unit linked to two phenyl rings and two prop-2-yn-1-yl moieties (Fig. 1). The planar five-membered imidazolidine ring, A (N1/N2/C1–C3), is oriented at dihedral angles of 79.10 (5) and 82.61 (5)°, respectively, to phenyl rings B (C4–C9) and C (C10–C15), while the dihedral angle between the two phenyl rings is 62.06 (5)°. Atoms O1, O2, C16 and C19 are at distances of 0.0271 (12), −0.1040 (12), 0.1657 (19) and −0.0336 (19) Å from the mean plane of the imidazolidine ring, A. The orientation of the prop-2-yn-1-yl moieties with respect to the imidazolidine unit can be described by the C3–N1–C16–C17 and C3–N2–C19–C20 torsion angles of −115.3 (2) and 76.6 (2)°, respectively.

<figure><img src="image_5.png" /><figcaption>Figure 1</figcaption></figure>

The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C4–C9 and C10–C15 rings, respectively.

<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>C16–H16B···O2<sup>vii</sup></td><td>0.98 (3)</td><td>2.33 (3)</td><td>3.178 (3)</td><td>144 (2)</td></tr><tr><td>C9–H9···Cg1<sup>vi</sup></td><td>0.93 (3)</td><td>2.93 (2)</td><td>3.778 (2)</td><td>152.7 (17)</td></tr><tr><td>C14–H14···Cg2<sup>viii</sup></td><td>1.00 (3)</td><td>2.87 (2)</td><td>3.762 (3)</td><td>149.6 (17)</td></tr></tbody></table>

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

## 3. Supramolecular features

In the crystal, C–H$_{Prop}$$^{··}$O$_{Imdzln}$ (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds (Table 1 and Fig. 2) link the molecules into infinite chains along the b-axis direction. Two weak C–H$_{Phen}$$^{··}$π interactions (Table 1) may also contribute to the stabilization of the crystal structure.

## 4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977; Spackman & Jayatilaka, 2009) was carried out by using *CrystalExplorer17.5* (Turner *et al.*, 2017). In the HS plotted over $d_{norm}$ (Fig. 3), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan *et al.*, 2016). The bright-red spots appearing near O2 and hydrogen atom H16B indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman *et al.*, 2008; Jayatilaka *et al.*, 2005) as shown in Fig. 4. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential

<figure><img src="image_6.png" /><figcaption>Figure 2</figcaption></figure>

A partial packing diagram viewed down the a-axis direction. C–H$_{Prop}$$^{··}$N$_{Imdzln}$ (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds (Table 1) are shown as dashed lines. Symmetry code: (vii) $-x, y - \frac{1}{2}, -z$.
evaluation of their potential pharmacological activities, we report herein the synthesis, the molecular and crystal structures, the Hirshfeld surface analysis and intermolecular interaction energies and density functional theory (DFT) computational calculation of the title compound, (I).

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

## 2. Structural commentary

The title molecule consists of an imidazolidine unit linked to two phenyl rings and two prop-2-yn-1-yl moieties (Fig. 1). The planar five-membered imidazolidine ring, A (N1/N2/C1–C3), is oriented at dihedral angles of 79.10 (5) and 82.61 (5)°, respectively, to phenyl rings B (C4–C9) and C (C10–C15), while the dihedral angle between the two phenyl rings is 62.06 (5)°. Atoms O1, O2, C16 and C19 are at distances of 0.0271 (12), −0.1040 (12), 0.1657 (19) and −0.0336 (19) Å from the mean plane of the imidazolidine ring, A. The orientation of the prop-2-yn-1-yl moieties with respect to the imidazolidine unit can be described by the C3–N1–C16–C17 and C3–N2–C19–C20 torsion angles of −115.3 (2) and 76.6 (2)°, respectively.

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

The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C4–C9 and C10–C15 rings, respectively.

<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>C16–H16B···O2<sup>vii</sup></td><td>0.98 (3)</td><td>2.33 (3)</td><td>3.178 (3)</td><td>144 (2)</td></tr><tr><td>C9–H9···Cg1<sup>vi</sup></td><td>0.93 (3)</td><td>2.93 (2)</td><td>3.778 (2)</td><td>152.7 (17)</td></tr><tr><td>C14–H14···Cg2<sup>viii</sup></td><td>1.00 (3)</td><td>2.87 (2)</td><td>3.762 (3)</td><td>149.6 (17)</td></tr></tbody></table>

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

## 3. Supramolecular features

In the crystal, C–H$_{Prop}$$^{··}$O$_{Imdzln}$ (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds (Table 1 and Fig. 2) link the molecules into infinite chains along the b-axis direction. Two weak C–H$_{Phen}$$^{··}$π interactions (Table 1) may also contribute to the stabilization of the crystal structure.

## 4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis (Hirshfeld, 1977; Spackman & Jayatilaka, 2009) was carried out by using *CrystalExplorer17.5* (Turner *et al.*, 2017). In the HS plotted over $d_{norm}$ (Fig. 3), the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan *et al.*, 2016). The bright-red spots appearing near O2 and hydrogen atom H16B indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman *et al.*, 2008; Jayatilaka *et al.*, 2005) as shown in Fig. 4. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential

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

A partial packing diagram viewed down the a-axis direction. C–H$_{Prop}$$^{··}$N$_{Imdzln}$ (Prop = prop-2-yn-1-yl and Imdzln = imidazolidine) hydrogen bonds (Table 1) are shown as dashed lines. Symmetry code: (vii) $-x, y - \frac{1}{2}, -z$.
<table><caption>**Table 2**
Selected interatomic distances (Å).</caption><tr><td>O1···H16B</td><td>2.84 (2)</td><td>C4···H11</td><td>2.679 (18)</td></tr><tr><td>O1···H13<sup>i</sup></td><td>2.61 (2)</td><td>C6···H9<sup>ii</sup></td><td>2.97 (2)</td></tr><tr><td>O1···H5</td><td>2.767 (18)</td><td>C6···H18<sup>v</sup></td><td>2.90 (4)</td></tr><tr><td>O1···H8<sup>ii</sup></td><td>2.62 (2)</td><td>C8···H11<sup>vi</sup></td><td>2.94 (2)</td></tr><tr><td>O2···H18<sup>iii</sup></td><td>2.68 (5)</td><td>C8···H19A<sup>ii</sup></td><td>2.83 (2)</td></tr><tr><td>O2···H19B</td><td>2.65 (2)</td><td>C9···H11</td><td>2.73 (2)</td></tr><tr><td>O2···H16A</td><td>2.50 (2)</td><td>C10···H9</td><td>2.75 (2)</td></tr><tr><td>O2···H16B<sup>iv</sup></td><td>2.33 (2)</td><td>C10···H19A</td><td>2.96 (2)</td></tr><tr><td>N2···H15</td><td>2.53 (2)</td><td>C11···H14<sup>i</sup></td><td>2.94 (2)</td></tr><tr><td>C4···C20</td><td>3.372 (3)</td><td>C11···H9</td><td>2.79 (2)</td></tr><tr><td>C9···C19</td><td>3.378 (3)</td><td>C12···H14<sup>i</sup></td><td>2.91 (2)</td></tr><tr><td>C9···C11</td><td>3.138 (3)</td><td>C14···H7<sup>vi</sup></td><td>2.97 (2)</td></tr><tr><td>C9···C20</td><td>3.472 (3)</td><td>H8···H11<sup>vi</sup></td><td>2.53 (3)</td></tr><tr><td>C15···C19</td><td>3.450 (3)</td><td>H9···H11</td><td>2.58 (3)</td></tr><tr><td>C2···H5</td><td>2.476 (18)</td><td></td><td></td></tr></table>

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

<figure><img src="image_7.png" /><figcaption>**Figure 3**
View of the three-dimensional Hirshfeld surface of the title compound plotted over $d_{norm}$ in the range −0.2703 to 1.2169 a.u.</figcaption></figure>

(hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the $\pi-\pi$ stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no $\pi-\pi$ interactions. Fig. 5 clearly suggest that there are no $\pi-\pi$ interactions in (I).

The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H···H, H···C/C···H, H···O/O···H,

C···C and H···N/N···H contacts (McKinnon *et al.*, 2007) are illustrated in Fig. 6b–f, together with their relative contributions to the Hirshfeld surface while details of the various contacts are given in Table 2. The most important interaction is H···H contributing 43.3% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at $d_e + d_i \sim 2.44$ Å. In the presence of two weak C–H···π interactions, the pair of the scattered points of wings resulting from H···C/C···H contacts, with a 37.8% contribution to the HS, have a symmetrical distribution of points, Fig. 6c, with the thin edges at $d_e + d_i = 2.67$ Å. The fingerprint

<figure><img src="image_8.png" /><figcaption>**Figure 4**
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree-Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>**Figure 5**
Hirshfeld surface of the title compound plotted over shape-index.</figcaption></figure>
<table><caption>**Table 2**
Selected interatomic distances (Å).</caption><tr><td>O1···H16B</td><td>2.84 (2)</td><td>C4···H11</td><td>2.679 (18)</td></tr><tr><td>O1···H13<sup>i</sup></td><td>2.61 (2)</td><td>C6···H9<sup>ii</sup></td><td>2.97 (2)</td></tr><tr><td>O1···H5</td><td>2.767 (18)</td><td>C6···H18<sup>v</sup></td><td>2.90 (4)</td></tr><tr><td>O1···H8<sup>ii</sup></td><td>2.62 (2)</td><td>C8···H11<sup>vi</sup></td><td>2.94 (2)</td></tr><tr><td>O2···H18<sup>iii</sup></td><td>2.68 (5)</td><td>C8···H19A<sup>ii</sup></td><td>2.83 (2)</td></tr><tr><td>O2···H19B</td><td>2.65 (2)</td><td>C9···H11</td><td>2.73 (2)</td></tr><tr><td>O2···H16A</td><td>2.50 (2)</td><td>C10···H9</td><td>2.75 (2)</td></tr><tr><td>O2···H16B<sup>iv</sup></td><td>2.33 (2)</td><td>C10···H19A</td><td>2.96 (2)</td></tr><tr><td>N2···H15</td><td>2.53 (2)</td><td>C11···H14<sup>i</sup></td><td>2.94 (2)</td></tr><tr><td>C4···C20</td><td>3.372 (3)</td><td>C11···H9</td><td>2.79 (2)</td></tr><tr><td>C9···C19</td><td>3.378 (3)</td><td>C12···H14<sup>i</sup></td><td>2.91 (2)</td></tr><tr><td>C9···C11</td><td>3.138 (3)</td><td>C14···H7<sup>vi</sup></td><td>2.97 (2)</td></tr><tr><td>C9···C20</td><td>3.472 (3)</td><td>H8···H11<sup>vi</sup></td><td>2.53 (3)</td></tr><tr><td>C15···C19</td><td>3.450 (3)</td><td>H9···H11</td><td>2.58 (3)</td></tr><tr><td>C2···H5</td><td>2.476 (18)</td><td></td><td></td></tr></table>

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

C···C and H···N/N···H contacts (McKinnon *et al.*, 2007) are illustrated in Fig. 6b–f, together with their relative contributions to the Hirshfeld surface while details of the various contacts are given in Table 2. The most important interaction is H···H contributing 43.3% to the overall crystal packing, which is reflected in Fig. 6b as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at $d_e + d_i \sim 2.44$ Å. In the presence of two weak C–H···π interactions, the pair of the scattered points of wings resulting from H···C/C···H contacts, with a 37.8% contribution to the HS, have a symmetrical distribution of points, Fig. 6c, with the thin edges at $d_e + d_i = 2.67$ Å. The fingerprint

<figure><img src="image_8.png" /><figcaption>**Figure 3**
View of the three-dimensional Hirshfeld surface of the title compound plotted over $d_{norm}$ in the range −0.2703 to 1.2169 a.u.</figcaption></figure>

(hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 clearly suggest that there are no π–π interactions in (I).

The overall two-dimensional fingerprint plot, Fig. 6a, and those delineated into H···H, H···C/C···H, H···O/O···H,

<figure><img src="image_9.png" /><figcaption>**Figure 4**
View of the three-dimensional Hirshfeld surface of the title compound plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.</figcaption></figure>

<figure><img src="image_10.png" /><figcaption>**Figure 5**
Hirshfeld surface of the title compound plotted over shape-index.</figcaption></figure>
plot for H···O/O···H contacts (18.0% contribution), Fig. 6d, has a pair of spikes with the tips at $d_e + d_i = 2.24$ Å.

The Hirshfeld surface representations with the function $d_{norm}$ plotted onto the surface are shown for the H···H, H···C/C···H and H···O/O···H interactions in Fig. 7a-c.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H···H, H···C/C···H and H···O/O···H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar *et al.*, 2015).

## 5. Interaction energy calculations

The intermolecular interaction energies (Table 3) were calculated using the CE-B3LYP/6-311G(d,p) energy model available in CrystalExplorer17.5 (Turner *et al.*, 2017), where a cluster of molecules is generated by applying crystallographic symmetry operations with respect to a selected central molecule within a default radius of 3.8 Å (Turner *et al.*, 2014). The total intermolecular energy ($E_{tot}$) is the sum of electrostatic

<table><caption>Table 3
Calculated energies and other parameters for (I).</caption><thead><tr><th>Parameter</th><th>Value in (I)</th></tr></thead><tbody><tr><td>Total energy <i>E</i><sub>tot</sub> (eV)</td><td>-30168.2025</td></tr><tr><td><i>E</i><sub>HOMO</sub> (eV)</td><td>-6.6964</td></tr><tr><td><i>E</i><sub>LUMO</sub> (eV)</td><td>-0.8090</td></tr><tr><td>Energy gap, Δ<i>E</i> (eV)</td><td>5.8878</td></tr><tr><td>Dipole moment, μ (Debye)</td><td>2.5919</td></tr><tr><td>Ionization potential, I (eV)</td><td>6.6964</td></tr><tr><td>Electron affinity, A</td><td>0.8090</td></tr><tr><td>Electro negativity, χ</td><td>4.0554</td></tr><tr><td>Hardness, η</td><td>2.9437</td></tr><tr><td>Electrophilicity index, ω</td><td>2.3920</td></tr><tr><td>Softness, σ</td><td>0.3397</td></tr><tr><td>Fraction of electrons transferred, Δ<i>N</i></td><td>0.5516</td></tr></tbody></table>

($E_{ele}$), polarization ($E_{pol}$), dispersion ($E_{dis}$) and exchange-repulsion ($E_{rep}$) energies (Turner *et al.*, 2015) with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie *et al.*, 2017). The hydrogen-bonding interaction energy (in kJ mol⁻¹) was calculated to be -15.3 ($E_{ele}$), -3.2 ($E_{pol}$), -52.2 ($E_{dis}$), 37.6 ($E_{rep}$) and -40.7 ($E_{tot}$) for the C—H$_{Prop}$$\cdot$$\cdot$$\cdot$N$_{Imdzln}$ interaction.

<figure><img src="image_10.png" /><figcaption>Figure 6</figcaption></figure>

The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H···H, (c) H···C/C···H, (d) H···O/O···H, (e) C···C and (f) H···N/N···H interactions. The $d_i$ and $d_e$ values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

## 6. DFT calculations

The optimized structure of the title compound in the gas phase was generated theoretically via density functional theory (DFT) calculations using the standard B3LYP functional and

<figure><img src="image_11.png" /><figcaption>Figure 7</figcaption></figure>

The Hirshfeld surface representations with the function $d_{norm}$ plotted onto the surface for (a) H···H, (b) H···C/C···H and H···O/O···H interactions.
plot for H···O/O···H contacts (18.0% contribution), Fig. 6d, has a pair of spikes with the tips at $d_e + d_i = 2.24$ Å.

The Hirshfeld surface representations with the function $d_{norm}$ plotted onto the surface are shown for the H···H, H···C/C···H and H···O/O···H interactions in Fig. 7a-c.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H···H, H···C/C···H and H···O/O···H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing (Hathwar *et al.*, 2015).

## 5. Interaction energy calculations

The intermolecular interaction energies (Table 3) were calculated using the CE-B3LYP/6-311G(d,p) energy model available in CrystalExplorer17.5 (Turner *et al.*, 2017), where a cluster of molecules is generated by applying crystallographic symmetry operations with respect to a selected central molecule within a default radius of 3.8 Å (Turner *et al.*, 2014). The total intermolecular energy ($E_{tot}$) is the sum of electrostatic

<table><caption>Table 3
Calculated energies and other parameters for (I).</caption><thead><tr><th>Parameter</th><th>Value in (I)</th></tr></thead><tbody><tr><td>Total energy <i>E</i><sub>tot</sub> (eV)</td><td>-30168.2025</td></tr><tr><td><i>E</i><sub>HOMO</sub> (eV)</td><td>-6.6964</td></tr><tr><td><i>E</i><sub>LUMO</sub> (eV)</td><td>-0.8090</td></tr><tr><td>Energy gap, Δ<i>E</i> (eV)</td><td>5.8878</td></tr><tr><td>Dipole moment, μ (Debye)</td><td>2.5919</td></tr><tr><td>Ionization potential, I (eV)</td><td>6.6964</td></tr><tr><td>Electron affinity, A</td><td>0.8090</td></tr><tr><td>Electro negativity, χ</td><td>4.0554</td></tr><tr><td>Hardness, η</td><td>2.9437</td></tr><tr><td>Electrophilicity index, ω</td><td>2.3920</td></tr><tr><td>Softness, σ</td><td>0.3397</td></tr><tr><td>Fraction of electrons transferred, Δ<i>N</i></td><td>0.5516</td></tr></tbody></table>

($E_{ele}$), polarization ($E_{pol}$), dispersion ($E_{dis}$) and exchange-repulsion ($E_{rep}$) energies (Turner *et al.*, 2015) with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie *et al.*, 2017). The hydrogen-bonding interaction energy (in kJ mol⁻¹) was calculated to be -15.3 ($E_{ele}$), -3.2 ($E_{pol}$), -52.2 ($E_{dis}$), 37.6 ($E_{rep}$) and -40.7 ($E_{tot}$) for the C—H$_{Prop}$$\cdot$$\cdot$N$_{Imdzln}$ interaction.

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

The full two-dimensional fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H···H, (c) H···C/C···H, (d) H···O/O···H, (e) C···C and (f) H···N/N···H interactions. The $d_i$ and $d_e$ values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

## 6. DFT calculations

The optimized structure of the title compound in the gas phase was generated theoretically via density functional theory (DFT) calculations using the standard B3LYP functional and

<figure><img src="image_12.png" /><figcaption>Figure 7</figcaption></figure>

The Hirshfeld surface representations with the function $d_{norm}$ plotted onto the surface for (a) H···H, (b) H···C/C···H and H···O/O···H interactions.
<table><caption>**Table 4**
Comparison of the selected (X-ray and DFT) geometric data (Å, °).</caption><thead><tr><th>Bonds/angles</th><th>X-ray</th><th>B3LYP/6-311G(d,p)</th></tr></thead><tbody><tr><td>O1–C2</td><td>1.203 (3)</td><td>1.237</td></tr><tr><td>O2–C3</td><td>1.208 (2)</td><td>1.242</td></tr><tr><td>N2–C3</td><td>1.346 (3)</td><td>1.379</td></tr><tr><td>N2–C1</td><td>1.472 (3)</td><td>1.494</td></tr><tr><td>N2–C19</td><td>1.454 (3)</td><td>1.470</td></tr><tr><td>N1–C3</td><td>1.399 (3)</td><td>1.414</td></tr><tr><td>N1–C2</td><td>1.360 (3)</td><td>1.384</td></tr><tr><td>N1–C16</td><td>1.453 (3)</td><td>1.467</td></tr><tr><td>C3–N2–C1</td><td>112.90 (16)</td><td>112.45</td></tr><tr><td>C3–N2–C19</td><td>121.81 (18)</td><td>120.14</td></tr><tr><td>N2–C3–N1</td><td>107.02 (17)</td><td>106.95</td></tr><tr><td>C3–N1–C16</td><td>122.9 (2)</td><td>122.80</td></tr><tr><td>C2–N1–C3</td><td>112.60 (17)</td><td>112.41</td></tr><tr><td>O2–C3–N2</td><td>128.0 (2)</td><td>127.88</td></tr><tr><td>O2–C3–N1</td><td>125.0 (2)</td><td>125.10</td></tr></tbody></table>

6–311G(d,p) basis set (Becke, 1993) as implemented in GAUSSIAN 09 (Frisch et al., 2009). The theoretical and experimental results are in good agreement (Table 4). 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. The DFT calculations provide some important information on the reactivity and site selectivity of the molecular framework. $E_{HOMO}$ and $E_{LUMO}$ clarify the inevitable charge-exchange collaboration inside the studied material; the electronegativity (χ), hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are recorded in Table 3. The significance of η and σ is to evaluate both the reactivity and

<figure><img src="image_12.png" /><figcaption>**Figure 8**
The energy band gap of the title compound.</figcaption></figure>

<table><caption>**Table 5**
Experimental details.</caption><tbody><tr><td>Crystal data</td><td></td></tr><tr><td>Chemical formula</td><td>C<sub>21</sub>H<sub>16</sub>N<sub>2</sub>O<sub>2</sub></td></tr><tr><td>M<sub>r</sub></td><td>328.36</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, <i>P</i>2<sub>1</sub></td></tr><tr><td>Temperature (K)</td><td>296</td></tr><tr><td><i>a</i>, <i>b</i>, <i>c</i> (Å)</td><td>10.144 (3), 7.952 (2), 10.928 (3)</td></tr><tr><td>β (°)</td><td>97.104 (12)</td></tr><tr><td><i>V</i> (Å<sup>3</sup>)</td><td>874.8 (4)</td></tr><tr><td><i>Z</i></td><td>2</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.08</td></tr><tr><td>Crystal size (mm)</td><td>0.34 × 0.17 × 0.12</td></tr><tr><td>Data collection</td><td></td></tr><tr><td>Diffractometer</td><td>Bruker APEXII CCD</td></tr><tr><td>Absorption correction</td><td>Multi-scan (<i>SADABS</i>; Bruker, 2016)</td></tr><tr><td><i>T</i><sub>min</sub>, <i>T</i><sub>max</sub></td><td>0.694, 0.746</td></tr><tr><td>No. of measured, independent and observed [<i>I</i> > 2σ(<i>I</i>)] reflections</td><td>21744, 3988, 3529</td></tr><tr><td><i>R</i><sub>int</sub></td><td>0.037</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.650</td></tr><tr><td>Refinement</td><td></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>0.035, 0.090, 1.03</td></tr><tr><td>No. of reflections</td><td>3988</td></tr><tr><td>No. of parameters</td><td>290</td></tr><tr><td>No. of restraints</td><td>1</td></tr><tr><td>H-atom treatment</td><td>All H-atom parameters refined</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.14, -0.16</td></tr><tr><td>Absolute structure</td><td>Flack x determined using 1436 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>-0.3 (4)</td></tr></tbody></table>

Computer programs: *APEX3* and *SAINT* (Bruker, 2016), *SHELXT* (Sheldrick, 2015a), *SHELXL* (Sheldrick, 2015b) and *OLEX2* (Dolomanov et al., 2009).

stability of a compound. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 8. The HOMO and LUMO are localized in the plane extending from the whole 5,5-diphenyl-1,3-di(prop-2-yn-1-yl)imidazolidine-2,4-dione ring. The energy band gap [$ΔE = E_{LUMO} - E_{HOMO}$] of the molecule is about 5.8874 eV, and the frontier molecular orbital energies, $E_{HOMO}$ and $E_{LUMO}$ are -6.6964 and -0.8090 eV, respectively.

## 7. Database survey

A non-alkylated analogue, namely 5,5-diphenylimidazolidine-2,4-dione, has been reported (Camerman & Camerman, 1971), as well as three similar structures, 3-*n*-pentyl-5,5-diphenylimidazolidine-2,4-dione (Guerrab *et al.*, 2017), 3-benzyl-5,5 diphenylimidazolidine-2,4-dione (Guerrab *et al.*, 2018) and 3-[2-(4-fluorophenyl)-2-oxoethyl]-5,5 diphenylimidazolidine-2,4-dione (Mague *et al.*, 2014).

## 8. Synthesis and crystallization

The appropriate bromide propagil (2.4 ml, 20.0 mmol) was added to a solution of 5,5 diphenylhydantoin (3.52 g, 10.0 mmol) in DMF (50 ml), potassium carbonate (2.76 g, 20.0 mmol) and tetra-*n*-butylammonium bromide (0.32 g,
<table><caption>**Table 4**
Comparison of the selected (X-ray and DFT) geometric data (Å, °).</caption><thead><tr><th>Bonds/angles</th><th>X-ray</th><th>B3LYP/6-311G(d,p)</th></tr></thead><tbody><tr><td>O1–C2</td><td>1.203 (3)</td><td>1.237</td></tr><tr><td>O2–C3</td><td>1.208 (2)</td><td>1.242</td></tr><tr><td>N2–C3</td><td>1.346 (3)</td><td>1.379</td></tr><tr><td>N2–C1</td><td>1.472 (3)</td><td>1.494</td></tr><tr><td>N2–C19</td><td>1.454 (3)</td><td>1.470</td></tr><tr><td>N1–C3</td><td>1.399 (3)</td><td>1.414</td></tr><tr><td>N1–C2</td><td>1.360 (3)</td><td>1.384</td></tr><tr><td>N1–C16</td><td>1.453 (3)</td><td>1.467</td></tr><tr><td>C3–N2–C1</td><td>112.90 (16)</td><td>112.45</td></tr><tr><td>C3–N2–C19</td><td>121.81 (18)</td><td>120.14</td></tr><tr><td>N2–C3–N1</td><td>107.02 (17)</td><td>106.95</td></tr><tr><td>C3–N1–C16</td><td>122.9 (2)</td><td>122.80</td></tr><tr><td>C2–N1–C3</td><td>112.60 (17)</td><td>112.41</td></tr><tr><td>O2–C3–N2</td><td>128.0 (2)</td><td>127.88</td></tr><tr><td>O2–C3–N1</td><td>125.0 (2)</td><td>125.10</td></tr></tbody></table>

6–311G(d,p) basis set (Becke, 1993) as implemented in GAUSSIAN 09 (Frisch et al., 2009). The theoretical and experimental results are in good agreement (Table 4). 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. The DFT calculations provide some important information on the reactivity and site selectivity of the molecular framework. $E_{HOMO}$ and $E_{LUMO}$ clarify the inevitable charge-exchange collaboration inside the studied material; the electronegativity (χ), hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are recorded in Table 3. The significance of η and σ is to evaluate both the reactivity and

<figure><img src="image_13.png" /><figcaption>**Figure 8**
The energy band gap of the title compound.</figcaption></figure>

<table><caption>**Table 5**
Experimental details.</caption><tbody><tr><td>Crystal data</td><td></td></tr><tr><td>Chemical formula</td><td>C<sub>21</sub>H<sub>16</sub>N<sub>2</sub>O<sub>2</sub></td></tr><tr><td>M<sub>r</sub></td><td>328.36</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, P2<sub>1</sub></td></tr><tr><td>Temperature (K)</td><td>296</td></tr><tr><td>a, b, c (Å)</td><td>10.144 (3), 7.952 (2), 10.928 (3)</td></tr><tr><td>β (°)</td><td>97.104 (12)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>874.8 (4)</td></tr><tr><td>Z</td><td>2</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.08</td></tr><tr><td>Crystal size (mm)</td><td>0.34 × 0.17 × 0.12</td></tr><tr><td>Data collection</td><td></td></tr><tr><td>Diffractometer</td><td>Bruker APEXII CCD</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Bruker, 2016)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.694, 0.746</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>21744, 3988, 3529</td></tr><tr><td>R<sub>int</sub></td><td>0.037</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.650</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>0.035, 0.090, 1.03</td></tr><tr><td>No. of reflections</td><td>3988</td></tr><tr><td>No. of parameters</td><td>290</td></tr><tr><td>No. of restraints</td><td>1</td></tr><tr><td>H-atom treatment</td><td>All H-atom parameters refined</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.14, -0.16</td></tr><tr><td>Absolute structure</td><td>Flack x determined using 1436 quotients [(I')-(I'')]/[(I')+(I'')] (Parsons et al., 2013)</td></tr><tr><td>Absolute structure parameter</td><td>-0.3 (4)</td></tr></tbody></table>

Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009).

stability of a compound. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 8. The HOMO and LUMO are localized in the plane extending from the whole 5,5-diphenyl-1,3-di(prop-2-yn-1-yl)imidazolidine-2,4-dione ring. The energy band gap [$ΔE = E_{LUMO} - E_{HOMO}$] of the molecule is about 5.8874 eV, and the frontier molecular orbital energies, $E_{HOMO}$ and $E_{LUMO}$ are -6.6964 and -0.8090 eV, respectively.

## 7. Database survey

A non-alkylated analogue, namely 5,5-diphenylimidazolidine-2,4-dione, has been reported (Camerman & Camerman, 1971), as well as three similar structures, 3-n-pentyl-5,5-diphenylimidazolidine-2,4-dione (Guerrab et al., 2017), 3-benzyl-5,5 diphenylimidazolidine-2,4-dione (Guerrab et al., 2018) and 3-[2-(4-fluorophenyl)-2-oxoethyl]-5,5 diphenylimidazolidine-2,4-dione (Mague et al., 2014).

## 8. Synthesis and crystallization

The appropriate bromide propagil (2.4 ml, 20.0 mmol) was added to a solution of 5,5 diphenylhydantoin (3.52 g, 10.0 mmol) in DMF (50 ml), potassium carbonate (2.76 g, 20.0 mmol) and tetra-n-butylammonium bromide (0.32 g,
1.0 mmol) at room temperature. The reaction was monitored using TLC. After removal of the inorganic salt by filtration, the solution was evaporated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate-hexane (v:v 3:7) as eluent. The isolated solid was crystallized from ethanol solution to afford colourless crystals (yield: 82%).

## 9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. Hydrogen atoms were located in a difference-Fourier map, and refined freely. The Flack absolute structure parameter (Parsons et al., 2013) was refined; expected values are 0 for the correct and +1 for the inverted absolute structure. The refined value is -0.3 (4) (Sheldrick, 2015b). Since the large e.s.d. means that the assignment is not unambiguous, the absolute structure was not determined reliably.

## Funding information

TH is grateful to the Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

## References

* Amir, M. & Kumar, S. (2005). *Indian J. Chem.* **44B**, 2532–2537.

* Badawey, E. A. M. & El-Ashmawey, I. M. (1998). *Eur. J. Med. Chem.* **33**, 349–361.

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

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

* Camerman, A. & Camerman, N. (1971). *Acta Cryst.* **B27**, 2205–2211.

* Das, N., Verma, A., Shrivastava, P. K. & Shrivastava, S. K. (2008). *Indian J. Chem.* **B47**, 1555–1558.

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

* Frisch, M. J., et al. (2009). *GAUSSIAN09*. Gaussian Inc., Wallingford, CT, USA.

* Guerrab, W., Akrad, R., Ansar, M., Taoufik, J., Mague, J. T. & Ramli, Y. (2017). *IUCrData*, **2**, x171693.

* Guerrab, W., Akrad, R., Ansar, M., Taoufik, J., Mague, J. T. & Ramli, Y. (2018). *IUCrData*, **3**, x171832.

* Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). *IUCrJ*, **2**, 563–574.

* Higashi, Y., Jitsuiki, D., Chayama, K. & Yoshizumi, M. (2006). *Recent. Patents Cardiovasc. Drug. Discov.* **1**, 85–93.

* Hirshfeld, H. L. (1977). *Theor. Chim. Acta*, **44**, 129–138.

* Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). *TONTO* - A System for Computational Chemistry. Available at: http://hirshfeldsurface.net/

* Mackenzie, C. F., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). *IUCrJ*, **4**, 575–587.

* Mague, J. T., Abdel-Aziz, A. A.-M. & El-Azab, A. S. (2014). *Acta Cryst.* **E70**, o226–o227.

* McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). *Chem. Commun.* pp. 3814–3816.

* Naik, C. G. & Malik, C. M. (2010). *Orient. J. Chem.* **26**, 113–116.

* Parsons, S., Flack, H. D. & Wagner, T. (2013). *Acta Cryst.* **B69**, 249–259.

* Pathak, R. B. & Bahel, S. C. (1980). *J. Indian Chem. Soc.* **57**, 1108–1111.

* Pawar, R. A. & Patil, A. A. (1994). *Indian J. Chem.* **33B**, 156–158.

* Sahu, S. K., Azam, A. M., Banerjee, M., Choudhary, P., Sutradhar, S., Panda, P. K. & Misra, P. K. (2007). *J. Indian Chem. Soc.* **84**, 1011–1015.

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

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

* Singh, D. & Singh, D. (1991). *J. Indian Chem. Soc.* **68**, 165–167.

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

* Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). *CrystEngComm*, **10**, 377–388.

* Srivalli, T., Satish, K. & Suthakaran, R. (2011). *Int. J. Innov. Pharm. Res.* **2**, 172–174.

* Turner, M. J., Grabowsky, S., Jayatilaka, D. & Spackman, M. A. (2014). *J. Phys. Chem. Lett.* **5**, 4249–4255.

* Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). *CrystalExplorer17*. The University of Western Australia.

* Turner, M. J., Thomas, S. P., Shi, M. W., Jayatilaka, D. & Spackman, M. A. (2015). *Chem. Commun.* **51**, 3735–3738.

* Venkatesan, P., Thamotharan, S., Ilangovan, A., Liang, H. & Sundius, T. (2016). *Spectrochim. Acta Part A*, **153**, 625–636.
1.0 mmol) at room temperature. The reaction was monitored using TLC. After removal of the inorganic salt by filtration, the solution was evaporated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate-hexane (v:v 3:7) as eluent. The isolated solid was crystallized from ethanol solution to afford colourless crystals (yield: 82%).

## 9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. Hydrogen atoms were located in a difference-Fourier map, and refined freely. The Flack absolute structure parameter (Parsons et al., 2013) was refined; expected values are 0 for the correct and +1 for the inverted absolute structure. The refined value is -0.3 (4) (Sheldrick, 2015b). Since the large e.s.d. means that the assignment is not unambiguous, the absolute structure was not determined reliably.

## Funding information

TH is grateful to the Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004).

## References

* Amir, M. & Kumar, S. (2005). *Indian J. Chem.* **44B**, 2532–2537.

* Badawey, E. A. M. & El-Ashmawey, I. M. (1998). *Eur. J. Med. Chem.* **33**, 349–361.

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

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

* Camerman, A. & Camerman, N. (1971). *Acta Cryst.* **B27**, 2205–2211.

* Das, N., Verma, A., Shrivastava, P. K. & Shrivastava, S. K. (2008). *Indian J. Chem.* **B47**, 1555–1558.

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

* Frisch, M. J., et al. (2009). *GAUSSIAN09*. Gaussian Inc., Wallingford, CT, USA.

* Guerrab, W., Akrad, R., Ansar, M., Taoufik, J., Mague, J. T. & Ramli, Y. (2017). *IUCrData*, **2**, x171693.

* Guerrab, W., Akrad, R., Ansar, M., Taoufik, J., Mague, J. T. & Ramli, Y. (2018). *IUCrData*, **3**, x171832.

* Hathwar, V. R., Sist, M., Jørgensen, M. R. V., Mamakhel, A. H., Wang, X., Hoffmann, C. M., Sugimoto, K., Overgaard, J. & Iversen, B. B. (2015). *IUCrJ*, **2**, 563–574.

* Higashi, Y., Jitsuiki, D., Chayama, K. & Yoshizumi, M. (2006). *Recent. Patents Cardiovasc. Drug. Discov.* **1**, 85–93.

* Hirshfeld, H. L. (1977). *Theor. Chim. Acta*, **44**, 129–138.

* Jayatilaka, D., Grimwood, D. J., Lee, A., Lemay, A., Russel, A. J., Taylor, C., Wolff, S. K., Cassam-Chenai, P. & Whitton, A. (2005). *TONTO* - A System for Computational Chemistry. Available at: http://hirshfeldsurface.net/

* Mackenzie, C. F., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). *IUCrJ*, **4**, 575–587.

* Mague, J. T., Abdel-Aziz, A. A.-M. & El-Azab, A. S. (2014). *Acta Cryst.* **E70**, o226–o227.

* McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). *Chem. Commun.* pp. 3814–3816.

* Naik, C. G. & Malik, C. M. (2010). *Orient. J. Chem.* **26**, 113–116.

* Parsons, S., Flack, H. D. & Wagner, T. (2013). *Acta Cryst.* **B69**, 249–259.

* Pathak, R. B. & Bahel, S. C. (1980). *J. Indian Chem. Soc.* **57**, 1108–1111.

* Pawar, R. A. & Patil, A. A. (1994). *Indian J. Chem.* **33B**, 156–158.

* Sahu, S. K., Azam, A. M., Banerjee, M., Choudhary, P., Sutradhar, S., Panda, P. K. & Misra, P. K. (2007). *J. Indian Chem. Soc.* **84**, 1011–1015.

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

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

* Singh, D. & Singh, D. (1991). *J. Indian Chem. Soc.* **68**, 165–167.

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

* Spackman, M. A., McKinnon, J. J. & Jayatilaka, D. (2008). *CrystEngComm*, **10**, 377–388.

* Srivalli, T., Satish, K. & Suthakaran, R. (2011). *Int. J. Innov. Pharm. Res.* **2**, 172–174.

* Turner, M. J., Grabowsky, S., Jayatilaka, D. & Spackman, M. A. (2014). *J. Phys. Chem. Lett.* **5**, 4249–4255.

* Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). *CrystalExplorer17*. The University of Western Australia.

* Turner, M. J., Thomas, S. P., Shi, M. W., Jayatilaka, D. & Spackman, M. A. (2015). *Chem. Commun.* **51**, 3735–3738.

* Venkatesan, P., Thamotharan, S., Ilangovan, A., Liang, H. & Sundius, T. (2016). *Spectrochim. Acta Part A*, **153**, 625–636.
supporting information

*Acta Cryst.* (2019). **E75**, 951-956 [https://doi.org/10.1107/S2056989019007801]

Crystal structure, Hirshfeld surface analysis and interaction energy and DFT
studies of 5,5-diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

Ismail Ghandour, Abdelouahed Bouayad, Tuncer Hökelek, Amal Haoudi, Frédéric Capet,
Catherine Renard and Youssef Kandri Rodi

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: *SHELXL*
(Sheldrick, 2015b); molecular graphics: *OLEX2* (Dolomanov *et al.*, 2009); software used to prepare material for
publication: *OLEX2* (Dolomanov *et al.*, 2009).

5,5-Diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

Crystal data

C₂₁H₁₆N₂O₂
M_r = 328.36
Monoclinic, P2₁
a = 10.144 (3) Å
b = 7.952 (2) Å
c = 10.928 (3) Å
β = 97.104 (12)°
V = 874.8 (4) Å³
Z = 2

F(000) = 344
Dₓ = 1.247 Mg m⁻³
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9652 reflections
θ = 3.2–27.2°
μ = 0.08 mm⁻¹
T = 296 K
Prism, colourless
0.34 × 0.17 × 0.12 mm

Data collection

Bruker APEXII CCD
diffractometer
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
T_min = 0.694, T_max = 0.746
21744 measured reflections

3988 independent reflections
3529 reflections with *I* > 2σ(*I*)
*R*<sub>int</sub> = 0.037
θ<sub>max</sub> = 27.5°, θ<sub>min</sub> = 1.9°
h = -13→13
k = -10→10
l = -13→14

Refinement

Refinement on *F*²
Least-squares matrix: full
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.03
3988 reflections
290 parameters
1 restraint

Primary atom site location: dual
Hydrogen site location: difference Fourier map
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0457P)² + 0.0829P]
where P = (F_o² + 2F_c²)/3
(Δ/σ)max < 0.001
Δρmax = 0.14 e Å⁻³
Δρmin = -0.16 e Å⁻³
supporting information

Acta Cryst. (2019). E75, 951-956 [https://doi.org/10.1107/S2056989019007801]

# Crystal structure, Hirshfeld surface analysis and interaction energy and DFT studies of 5,5-diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

Ismail Ghandour, Abdelouahed Bouayad, Tuncer Hökelek, Amal Haoudi, Frédéric Capet, Catherine Renard and Youssef Kandri Rodi

## 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: *SHELXL* (Sheldrick, 2015b); molecular graphics: *OLEX2* (Dolomanov *et al.*, 2009); software used to prepare material for publication: *OLEX2* (Dolomanov *et al.*, 2009).

## 5,5-Diphenyl-1,3-bis(prop-2-yn-1-yl)imidazolidine-2,4-dione

### Crystal data

C₂₁H₁₆N₂O₂
M_r = 328.36
Monoclinic, P2₁
a = 10.144 (3) Å
b = 7.952 (2) Å
c = 10.928 (3) Å
β = 97.104 (12)°
V = 874.8 (4) Å³
Z = 2

F(000) = 344
Dₓ = 1.247 Mg m⁻³
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 9652 reflections
θ = 3.2–27.2°
μ = 0.08 mm⁻¹
T = 296 K
Prism, colourless
0.34 × 0.17 × 0.12 mm

### Data collection

Bruker APEXII CCD
diffractometer
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
T_min = 0.694, T_max = 0.746
21744 measured reflections

3988 independent reflections
3529 reflections with *I* > 2σ(*I*)
R_int = 0.037
θ_max = 27.5°, θ_min = 1.9°
h = -13→13
k = -10→10
l = -13→14

### Refinement

Refinement on *F*²
Least-squares matrix: full
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.03
3988 reflections
290 parameters
1 restraint

Primary atom site location: dual
Hydrogen site location: difference Fourier map
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0457P)² + 0.0829P]
where P = (F_o² + 2F_c²)/3
(Δ/σ)max < 0.001
Δρ_max = 0.14 e Å⁻³
Δρ_min = -0.16 e Å⁻³
Absolute structure: Flack *x* determined using
1436 quotients [(I')-(I)]/[(I')+(I)] (Parsons et
al., 2013)

Absolute structure parameter: -0.3 (4)

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>O1</td><td>0.27390 (15)</td><td>0.2664 (2)</td><td>0.19321 (15)</td><td>0.0502 (4)</td></tr><tr><td>O2</td><td>-0.01151 (15)</td><td>0.7093 (2)</td><td>0.18041 (16)</td><td>0.0521 (4)</td></tr><tr><td>N1</td><td>0.10965 (17)</td><td>0.4650 (2)</td><td>0.16652 (16)</td><td>0.0421 (4)</td></tr><tr><td>N2</td><td>0.20794 (16)</td><td>0.6856 (2)</td><td>0.26052 (16)</td><td>0.0408 (4)</td></tr><tr><td>C1</td><td>0.30827 (18)</td><td>0.5513 (3)</td><td>0.27974 (18)</td><td>0.0380 (4)</td></tr><tr><td>C2</td><td>0.2324 (2)</td><td>0.4054 (3)</td><td>0.20923 (18)</td><td>0.0387 (4)</td></tr><tr><td>C3</td><td>0.09114 (19)</td><td>0.6317 (3)</td><td>0.20165 (18)</td><td>0.0390 (4)</td></tr><tr><td>C4</td><td>0.33794 (18)</td><td>0.5114 (2)</td><td>0.41722 (19)</td><td>0.0385 (4)</td></tr><tr><td>C5</td><td>0.2604 (2)</td><td>0.3960 (3)</td><td>0.4718 (2)</td><td>0.0458 (5)</td></tr><tr><td>C6</td><td>0.2784 (3)</td><td>0.3712 (4)</td><td>0.5987 (2)</td><td>0.0565 (6)</td></tr><tr><td>C7</td><td>0.3738 (3)</td><td>0.4604 (4)</td><td>0.6713 (2)</td><td>0.0572 (6)</td></tr><tr><td>C8</td><td>0.4520 (2)</td><td>0.5750 (3)</td><td>0.6180 (2)</td><td>0.0526 (6)</td></tr><tr><td>C9</td><td>0.4342 (2)</td><td>0.6008 (3)</td><td>0.4921 (2)</td><td>0.0454 (5)</td></tr><tr><td>C10</td><td>0.42895 (19)</td><td>0.5861 (3)</td><td>0.21163 (19)</td><td>0.0395 (4)</td></tr><tr><td>C11</td><td>0.5495 (2)</td><td>0.5070 (3)</td><td>0.2474 (2)</td><td>0.0441 (5)</td></tr><tr><td>C12</td><td>0.6546 (2)</td><td>0.5272 (3)</td><td>0.1782 (2)</td><td>0.0543 (6)</td></tr><tr><td>C13</td><td>0.6410 (3)</td><td>0.6249 (4)</td><td>0.0733 (2)</td><td>0.0606 (6)</td></tr><tr><td>C14</td><td>0.5225 (3)</td><td>0.7025 (4)</td><td>0.0372 (2)</td><td>0.0622 (7)</td></tr><tr><td>C15</td><td>0.4163 (2)</td><td>0.6834 (3)</td><td>0.1052 (2)</td><td>0.0538 (6)</td></tr><tr><td>C16</td><td>0.0113 (3)</td><td>0.3724 (4)</td><td>0.0851 (2)</td><td>0.0541 (6)</td></tr><tr><td>C17</td><td>-0.0433 (2)</td><td>0.2305 (3)</td><td>0.1448 (3)</td><td>0.0613 (7)</td></tr><tr><td>C18</td><td>-0.0849 (4)</td><td>0.1125 (5)</td><td>0.1895 (5)</td><td>0.1046 (14)</td></tr><tr><td>C19</td><td>0.2236 (3)</td><td>0.8536 (3)</td><td>0.3129 (2)</td><td>0.0504 (5)</td></tr><tr><td>C20</td><td>0.1674 (3)</td><td>0.8738 (4)</td><td>0.4290 (3)</td><td>0.0701 (8)</td></tr><tr><td>C21</td><td>0.1218 (5)</td><td>0.8918 (10)</td><td>0.5191 (5)</td><td>0.136 (2)</td></tr><tr><td>H5</td><td>0.189 (2)</td><td>0.328 (3)</td><td>0.420 (2)</td><td>0.051 (7)*</td></tr><tr><td>H6</td><td>0.228 (3)</td><td>0.296 (4)</td><td>0.632 (3)</td><td>0.068 (8)*</td></tr><tr><td>H7</td><td>0.389 (3)</td><td>0.445 (4)</td><td>0.763 (3)</td><td>0.080 (10)*</td></tr><tr><td>H8</td><td>0.522 (3)</td><td>0.636 (4)</td><td>0.669 (2)</td><td>0.059 (7)*</td></tr><tr><td>H9</td><td>0.486 (3)</td><td>0.677 (4)</td><td>0.455 (3)</td><td>0.075 (9)*</td></tr><tr><td>H11</td><td>0.562 (2)</td><td>0.435 (4)</td><td>0.323 (2)</td><td>0.054 (7)*</td></tr><tr><td>H12</td><td>0.736 (3)</td><td>0.474 (4)</td><td>0.203 (3)</td><td>0.069 (8)*</td></tr><tr><td>H13</td><td>0.720 (3)</td><td>0.641 (4)</td><td>0.027 (3)</td><td>0.068 (8)*</td></tr><tr><td>H14</td><td>0.511 (3)</td><td>0.777 (4)</td><td>-0.037 (3)</td><td>0.072 (8)*</td></tr><tr><td>H15</td><td>0.330 (3)</td><td>0.737 (4)</td><td>0.076 (3)</td><td>0.060 (7)*</td></tr></tbody></table>
Absolute structure: Flack *x* determined using
1436 quotients [(I')-(I)]/[(I')+(I)] (Parsons et
al., 2013)

Absolute structure parameter: -0.3 (4)

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>O1</td><td>0.27390 (15)</td><td>0.2664 (2)</td><td>0.19321 (15)</td><td>0.0502 (4)</td></tr><tr><td>O2</td><td>-0.01151 (15)</td><td>0.7093 (2)</td><td>0.18041 (16)</td><td>0.0521 (4)</td></tr><tr><td>N1</td><td>0.10965 (17)</td><td>0.4650 (2)</td><td>0.16652 (16)</td><td>0.0421 (4)</td></tr><tr><td>N2</td><td>0.20794 (16)</td><td>0.6856 (2)</td><td>0.26052 (16)</td><td>0.0408 (4)</td></tr><tr><td>C1</td><td>0.30827 (18)</td><td>0.5513 (3)</td><td>0.27974 (18)</td><td>0.0380 (4)</td></tr><tr><td>C2</td><td>0.2324 (2)</td><td>0.4054 (3)</td><td>0.20923 (18)</td><td>0.0387 (4)</td></tr><tr><td>C3</td><td>0.09114 (19)</td><td>0.6317 (3)</td><td>0.20165 (18)</td><td>0.0390 (4)</td></tr><tr><td>C4</td><td>0.33794 (18)</td><td>0.5114 (2)</td><td>0.41722 (19)</td><td>0.0385 (4)</td></tr><tr><td>C5</td><td>0.2604 (2)</td><td>0.3960 (3)</td><td>0.4718 (2)</td><td>0.0458 (5)</td></tr><tr><td>C6</td><td>0.2784 (3)</td><td>0.3712 (4)</td><td>0.5987 (2)</td><td>0.0565 (6)</td></tr><tr><td>C7</td><td>0.3738 (3)</td><td>0.4604 (4)</td><td>0.6713 (2)</td><td>0.0572 (6)</td></tr><tr><td>C8</td><td>0.4520 (2)</td><td>0.5750 (3)</td><td>0.6180 (2)</td><td>0.0526 (6)</td></tr><tr><td>C9</td><td>0.4342 (2)</td><td>0.6008 (3)</td><td>0.4921 (2)</td><td>0.0454 (5)</td></tr><tr><td>C10</td><td>0.42895 (19)</td><td>0.5861 (3)</td><td>0.21163 (19)</td><td>0.0395 (4)</td></tr><tr><td>C11</td><td>0.5495 (2)</td><td>0.5070 (3)</td><td>0.2474 (2)</td><td>0.0441 (5)</td></tr><tr><td>C12</td><td>0.6546 (2)</td><td>0.5272 (3)</td><td>0.1782 (2)</td><td>0.0543 (6)</td></tr><tr><td>C13</td><td>0.6410 (3)</td><td>0.6249 (4)</td><td>0.0733 (2)</td><td>0.0606 (6)</td></tr><tr><td>C14</td><td>0.5225 (3)</td><td>0.7025 (4)</td><td>0.0372 (2)</td><td>0.0622 (7)</td></tr><tr><td>C15</td><td>0.4163 (2)</td><td>0.6834 (3)</td><td>0.1052 (2)</td><td>0.0538 (6)</td></tr><tr><td>C16</td><td>0.0113 (3)</td><td>0.3724 (4)</td><td>0.0851 (2)</td><td>0.0541 (6)</td></tr><tr><td>C17</td><td>-0.0433 (2)</td><td>0.2305 (3)</td><td>0.1448 (3)</td><td>0.0613 (7)</td></tr><tr><td>C18</td><td>-0.0849 (4)</td><td>0.1125 (5)</td><td>0.1895 (5)</td><td>0.1046 (14)</td></tr><tr><td>C19</td><td>0.2236 (3)</td><td>0.8536 (3)</td><td>0.3129 (2)</td><td>0.0504 (5)</td></tr><tr><td>C20</td><td>0.1674 (3)</td><td>0.8738 (4)</td><td>0.4290 (3)</td><td>0.0701 (8)</td></tr><tr><td>C21</td><td>0.1218 (5)</td><td>0.8918 (10)</td><td>0.5191 (5)</td><td>0.136 (2)</td></tr><tr><td>H5</td><td>0.189 (2)</td><td>0.328 (3)</td><td>0.420 (2)</td><td>0.051 (7)*</td></tr><tr><td>H6</td><td>0.228 (3)</td><td>0.296 (4)</td><td>0.632 (3)</td><td>0.068 (8)*</td></tr><tr><td>H7</td><td>0.389 (3)</td><td>0.445 (4)</td><td>0.763 (3)</td><td>0.080 (10)*</td></tr><tr><td>H8</td><td>0.522 (3)</td><td>0.636 (4)</td><td>0.669 (2)</td><td>0.059 (7)*</td></tr><tr><td>H9</td><td>0.486 (3)</td><td>0.677 (4)</td><td>0.455 (3)</td><td>0.075 (9)*</td></tr><tr><td>H11</td><td>0.562 (2)</td><td>0.435 (4)</td><td>0.323 (2)</td><td>0.054 (7)*</td></tr><tr><td>H12</td><td>0.736 (3)</td><td>0.474 (4)</td><td>0.203 (3)</td><td>0.069 (8)*</td></tr><tr><td>H13</td><td>0.720 (3)</td><td>0.641 (4)</td><td>0.027 (3)</td><td>0.068 (8)*</td></tr><tr><td>H14</td><td>0.511 (3)</td><td>0.777 (4)</td><td>-0.037 (3)</td><td>0.072 (8)*</td></tr><tr><td>H15</td><td>0.330 (3)</td><td>0.737 (4)</td><td>0.076 (3)</td><td>0.060 (7)*</td></tr></tbody></table>
<table><tr><td>H16A</td><td>-0.051 (3)</td><td>0.446 (4)</td><td>0.056 (3)</td><td>0.060 (8)*</td></tr><tr><td>H16B</td><td>0.053 (3)</td><td>0.332 (4)</td><td>0.014 (3)</td><td>0.070 (9)*</td></tr><tr><td>H18</td><td>-0.113 (6)</td><td>0.010 (8)</td><td>0.228 (6)</td><td>0.18 (2)*</td></tr><tr><td>H19A</td><td>0.315 (3)</td><td>0.879 (4)</td><td>0.328 (2)</td><td>0.061 (7)*</td></tr><tr><td>H19B</td><td>0.182 (3)</td><td>0.926 (4)</td><td>0.250 (3)</td><td>0.067 (8)*</td></tr><tr><td>H21</td><td>0.087 (5)</td><td>0.905 (8)</td><td>0.590 (5)</td><td>0.16 (2)*</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 (9)</td><td>0.0399 (8)</td><td>0.0585 (10)</td><td>0.0036 (7)</td><td>0.0088 (7)</td><td>-0.0076 (7)</td></tr><tr><td>O2</td><td>0.0430 (8)</td><td>0.0499 (9)</td><td>0.0606 (10)</td><td>0.0084 (7)</td><td>-0.0045 (7)</td><td>0.0041 (7)</td></tr><tr><td>N1</td><td>0.0425 (9)</td><td>0.0389 (9)</td><td>0.0426 (9)</td><td>-0.0019 (7)</td><td>-0.0033 (7)</td><td>-0.0008 (8)</td></tr><tr><td>N2</td><td>0.0373 (8)</td><td>0.0349 (9)</td><td>0.0492 (10)</td><td>0.0009 (7)</td><td>0.0014 (7)</td><td>-0.0011 (7)</td></tr><tr><td>C1</td><td>0.0361 (9)</td><td>0.0342 (9)</td><td>0.0432 (11)</td><td>0.0012 (8)</td><td>0.0035 (8)</td><td>0.0012 (8)</td></tr><tr><td>C2</td><td>0.0414 (10)</td><td>0.0385 (10)</td><td>0.0368 (10)</td><td>-0.0003 (8)</td><td>0.0070 (8)</td><td>0.0009 (8)</td></tr><tr><td>C3</td><td>0.0396 (10)</td><td>0.0403 (11)</td><td>0.0365 (10)</td><td>0.0013 (8)</td><td>0.0024 (8)</td><td>0.0058 (8)</td></tr><tr><td>C4</td><td>0.0349 (9)</td><td>0.0385 (11)</td><td>0.0423 (11)</td><td>0.0052 (8)</td><td>0.0055 (8)</td><td>0.0012 (8)</td></tr><tr><td>C5</td><td>0.0414 (11)</td><td>0.0468 (12)</td><td>0.0501 (12)</td><td>0.0006 (9)</td><td>0.0094 (9)</td><td>0.0032 (10)</td></tr><tr><td>C6</td><td>0.0574 (13)</td><td>0.0592 (15)</td><td>0.0556 (14)</td><td>0.0074 (12)</td><td>0.0183 (11)</td><td>0.0142 (12)</td></tr><tr><td>C7</td><td>0.0644 (15)</td><td>0.0677 (16)</td><td>0.0400 (12)</td><td>0.0230 (13)</td><td>0.0082 (10)</td><td>0.0047 (11)</td></tr><tr><td>C8</td><td>0.0531 (12)</td><td>0.0545 (14)</td><td>0.0476 (13)</td><td>0.0104 (11)</td><td>-0.0037 (10)</td><td>-0.0093 (11)</td></tr><tr><td>C9</td><td>0.0438 (11)</td><td>0.0440 (11)</td><td>0.0478 (12)</td><td>0.0016 (9)</td><td>0.0035 (9)</td><td>-0.0013 (9)</td></tr><tr><td>C10</td><td>0.0386 (9)</td><td>0.0391 (11)</td><td>0.0412 (10)</td><td>-0.0022 (8)</td><td>0.0060 (7)</td><td>0.0009 (8)</td></tr><tr><td>C11</td><td>0.0405 (10)</td><td>0.0450 (12)</td><td>0.0468 (12)</td><td>0.0014 (9)</td><td>0.0054 (9)</td><td>0.0040 (10)</td></tr><tr><td>C12</td><td>0.0419 (11)</td><td>0.0616 (15)</td><td>0.0605 (15)</td><td>0.0032 (11)</td><td>0.0105 (10)</td><td>0.0011 (12)</td></tr><tr><td>C13</td><td>0.0519 (13)</td><td>0.0735 (17)</td><td>0.0601 (14)</td><td>-0.0040 (12)</td><td>0.0219 (11)</td><td>0.0055 (13)</td></tr><tr><td>C14</td><td>0.0692 (16)</td><td>0.0698 (17)</td><td>0.0498 (14)</td><td>-0.0003 (13)</td><td>0.0166 (12)</td><td>0.0179 (13)</td></tr><tr><td>C15</td><td>0.0482 (12)</td><td>0.0622 (15)</td><td>0.0507 (13)</td><td>0.0044 (11)</td><td>0.0053 (10)</td><td>0.0129 (12)</td></tr><tr><td>C16</td><td>0.0540 (13)</td><td>0.0525 (14)</td><td>0.0520 (14)</td><td>-0.0059 (11)</td><td>-0.0086 (11)</td><td>-0.0047 (12)</td></tr><tr><td>C17</td><td>0.0463 (12)</td><td>0.0490 (14)</td><td>0.088 (2)</td><td>-0.0035 (10)</td><td>0.0067 (12)</td><td>-0.0068 (13)</td></tr><tr><td>C18</td><td>0.081 (2)</td><td>0.066 (2)</td><td>0.174 (4)</td><td>-0.0128 (18)</td><td>0.043 (2)</td><td>0.017 (2)</td></tr><tr><td>C19</td><td>0.0479 (13)</td><td>0.0358 (11)</td><td>0.0664 (15)</td><td>0.0013 (9)</td><td>0.0025 (11)</td><td>-0.0020 (11)</td></tr><tr><td>C20</td><td>0.0587 (15)</td><td>0.0758 (19)</td><td>0.0742 (19)</td><td>0.0032 (14)</td><td>0.0024 (13)</td><td>-0.0289 (16)</td></tr><tr><td>C21</td><td>0.103 (3)</td><td>0.214 (6)</td><td>0.094 (3)</td><td>0.001 (4)</td><td>0.026 (2)</td><td>-0.069 (4)</td></tr></tbody></table>

Geometric parameters (Å, °)

<table><tr><td>O1—C2</td><td>1.203 (3)</td><td>C10—C11</td><td>1.388 (3)</td></tr><tr><td>O2—C3</td><td>1.208 (2)</td><td>C10—C15</td><td>1.390 (3)</td></tr><tr><td>N1—C2</td><td>1.360 (3)</td><td>C11—C12</td><td>1.391 (3)</td></tr><tr><td>N1—C3</td><td>1.399 (3)</td><td>C11—H11</td><td>1.00 (3)</td></tr><tr><td>N1—C16</td><td>1.453 (3)</td><td>C12—C13</td><td>1.377 (4)</td></tr><tr><td>N2—C1</td><td>1.472 (3)</td><td>C12—H12</td><td>0.94 (3)</td></tr><tr><td>N2—C3</td><td>1.346 (3)</td><td>C13—C14</td><td>1.366 (4)</td></tr><tr><td>N2—C19</td><td>1.454 (3)</td><td>C13—H13</td><td>1.01 (3)</td></tr><tr><td>C1—C10</td><td>1.534 (3)</td><td>C14—H14</td><td>1.00 (3)</td></tr><tr><td>C2—C1</td><td>1.545 (3)</td><td>C15—C14</td><td>1.390 (4)</td></tr></table>
<table><tr><td>H16A</td><td>-0.051 (3)</td><td>0.446 (4)</td><td>0.056 (3)</td><td>0.060 (8)*</td></tr><tr><td>H16B</td><td>0.053 (3)</td><td>0.332 (4)</td><td>0.014 (3)</td><td>0.070 (9)*</td></tr><tr><td>H18</td><td>-0.113 (6)</td><td>0.010 (8)</td><td>0.228 (6)</td><td>0.18 (2)*</td></tr><tr><td>H19A</td><td>0.315 (3)</td><td>0.879 (4)</td><td>0.328 (2)</td><td>0.061 (7)*</td></tr><tr><td>H19B</td><td>0.182 (3)</td><td>0.926 (4)</td><td>0.250 (3)</td><td>0.067 (8)*</td></tr><tr><td>H21</td><td>0.087 (5)</td><td>0.905 (8)</td><td>0.590 (5)</td><td>0.16 (2)*</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 (9)</td><td>0.0399 (8)</td><td>0.0585 (10)</td><td>0.0036 (7)</td><td>0.0088 (7)</td><td>-0.0076 (7)</td></tr><tr><td>O2</td><td>0.0430 (8)</td><td>0.0499 (9)</td><td>0.0606 (10)</td><td>0.0084 (7)</td><td>-0.0045 (7)</td><td>0.0041 (7)</td></tr><tr><td>N1</td><td>0.0425 (9)</td><td>0.0389 (9)</td><td>0.0426 (9)</td><td>-0.0019 (7)</td><td>-0.0033 (7)</td><td>-0.0008 (8)</td></tr><tr><td>N2</td><td>0.0373 (8)</td><td>0.0349 (9)</td><td>0.0492 (10)</td><td>0.0009 (7)</td><td>0.0014 (7)</td><td>-0.0011 (7)</td></tr><tr><td>C1</td><td>0.0361 (9)</td><td>0.0342 (9)</td><td>0.0432 (11)</td><td>0.0012 (8)</td><td>0.0035 (8)</td><td>0.0012 (8)</td></tr><tr><td>C2</td><td>0.0414 (10)</td><td>0.0385 (10)</td><td>0.0368 (10)</td><td>-0.0003 (8)</td><td>0.0070 (8)</td><td>0.0009 (8)</td></tr><tr><td>C3</td><td>0.0396 (10)</td><td>0.0403 (11)</td><td>0.0365 (10)</td><td>0.0013 (8)</td><td>0.0024 (8)</td><td>0.0058 (8)</td></tr><tr><td>C4</td><td>0.0349 (9)</td><td>0.0385 (11)</td><td>0.0423 (11)</td><td>0.0052 (8)</td><td>0.0055 (8)</td><td>0.0012 (8)</td></tr><tr><td>C5</td><td>0.0414 (11)</td><td>0.0468 (12)</td><td>0.0501 (12)</td><td>0.0006 (9)</td><td>0.0094 (9)</td><td>0.0032 (10)</td></tr><tr><td>C6</td><td>0.0574 (13)</td><td>0.0592 (15)</td><td>0.0556 (14)</td><td>0.0074 (12)</td><td>0.0183 (11)</td><td>0.0142 (12)</td></tr><tr><td>C7</td><td>0.0644 (15)</td><td>0.0677 (16)</td><td>0.0400 (12)</td><td>0.0230 (13)</td><td>0.0082 (10)</td><td>0.0047 (11)</td></tr><tr><td>C8</td><td>0.0531 (12)</td><td>0.0545 (14)</td><td>0.0476 (13)</td><td>0.0104 (11)</td><td>-0.0037 (10)</td><td>-0.0093 (11)</td></tr><tr><td>C9</td><td>0.0438 (11)</td><td>0.0440 (11)</td><td>0.0478 (12)</td><td>0.0016 (9)</td><td>0.0035 (9)</td><td>-0.0013 (9)</td></tr><tr><td>C10</td><td>0.0386 (9)</td><td>0.0391 (11)</td><td>0.0412 (10)</td><td>-0.0022 (8)</td><td>0.0060 (7)</td><td>0.0009 (8)</td></tr><tr><td>C11</td><td>0.0405 (10)</td><td>0.0450 (12)</td><td>0.0468 (12)</td><td>0.0014 (9)</td><td>0.0054 (9)</td><td>0.0040 (10)</td></tr><tr><td>C12</td><td>0.0419 (11)</td><td>0.0616 (15)</td><td>0.0605 (15)</td><td>0.0032 (11)</td><td>0.0105 (10)</td><td>0.0011 (12)</td></tr><tr><td>C13</td><td>0.0519 (13)</td><td>0.0735 (17)</td><td>0.0601 (14)</td><td>-0.0040 (12)</td><td>0.0219 (11)</td><td>0.0055 (13)</td></tr><tr><td>C14</td><td>0.0692 (16)</td><td>0.0698 (17)</td><td>0.0498 (14)</td><td>-0.0003 (13)</td><td>0.0166 (12)</td><td>0.0179 (13)</td></tr><tr><td>C15</td><td>0.0482 (12)</td><td>0.0622 (15)</td><td>0.0507 (13)</td><td>0.0044 (11)</td><td>0.0053 (10)</td><td>0.0129 (12)</td></tr><tr><td>C16</td><td>0.0540 (13)</td><td>0.0525 (14)</td><td>0.0520 (14)</td><td>-0.0059 (11)</td><td>-0.0086 (11)</td><td>-0.0047 (12)</td></tr><tr><td>C17</td><td>0.0463 (12)</td><td>0.0490 (14)</td><td>0.088 (2)</td><td>-0.0035 (10)</td><td>0.0067 (12)</td><td>-0.0068 (13)</td></tr><tr><td>C18</td><td>0.081 (2)</td><td>0.066 (2)</td><td>0.174 (4)</td><td>-0.0128 (18)</td><td>0.043 (2)</td><td>0.017 (2)</td></tr><tr><td>C19</td><td>0.0479 (13)</td><td>0.0358 (11)</td><td>0.0664 (15)</td><td>0.0013 (9)</td><td>0.0025 (11)</td><td>-0.0020 (11)</td></tr><tr><td>C20</td><td>0.0587 (15)</td><td>0.0758 (19)</td><td>0.0742 (19)</td><td>0.0032 (14)</td><td>0.0024 (13)</td><td>-0.0289 (16)</td></tr><tr><td>C21</td><td>0.103 (3)</td><td>0.214 (6)</td><td>0.094 (3)</td><td>0.001 (4)</td><td>0.026 (2)</td><td>-0.069 (4)</td></tr></tbody></table>

Geometric parameters (Å, °)

<table><tr><td>O1—C2</td><td>1.203 (3)</td><td>C10—C11</td><td>1.388 (3)</td></tr><tr><td>O2—C3</td><td>1.208 (2)</td><td>C10—C15</td><td>1.390 (3)</td></tr><tr><td>N1—C2</td><td>1.360 (3)</td><td>C11—C12</td><td>1.391 (3)</td></tr><tr><td>N1—C3</td><td>1.399 (3)</td><td>C11—H11</td><td>1.00 (3)</td></tr><tr><td>N1—C16</td><td>1.453 (3)</td><td>C12—C13</td><td>1.377 (4)</td></tr><tr><td>N2—C1</td><td>1.472 (3)</td><td>C12—H12</td><td>0.94 (3)</td></tr><tr><td>N2—C3</td><td>1.346 (3)</td><td>C13—C14</td><td>1.366 (4)</td></tr><tr><td>N2—C19</td><td>1.454 (3)</td><td>C13—H13</td><td>1.01 (3)</td></tr><tr><td>C1—C10</td><td>1.534 (3)</td><td>C14—H14</td><td>1.00 (3)</td></tr><tr><td>C2—C1</td><td>1.545 (3)</td><td>C15—C14</td><td>1.390 (4)</td></tr></table>
<table>
  <tbody>
    <tr>
      <td>C4—C1</td>
      <td>1.529 (3)</td>
      <td>C15—H15</td>
      <td>0.99 (3)</td>
    </tr>
    <tr>
      <td>C4—C5</td>
      <td>1.390 (3)</td>
      <td>C16—H16A</td>
      <td>0.89 (3)</td>
    </tr>
    <tr>
      <td>C4—C9</td>
      <td>1.390 (3)</td>
      <td>C16—H16B</td>
      <td>0.98 (3)</td>
    </tr>
    <tr>
      <td>C5—C6</td>
      <td>1.389 (3)</td>
      <td>C17—C16</td>
      <td>1.447 (4)</td>
    </tr>
    <tr>
      <td>C5—H5</td>
      <td>1.02 (3)</td>
      <td>C17—C18</td>
      <td>1.162 (5)</td>
    </tr>
    <tr>
      <td>C6—C7</td>
      <td>1.370 (4)</td>
      <td>C18—H18</td>
      <td>0.97 (6)</td>
    </tr>
    <tr>
      <td>C6—H6</td>
      <td>0.90 (3)</td>
      <td>C19—C20</td>
      <td>1.462 (4)</td>
    </tr>
    <tr>
      <td>C7—H7</td>
      <td>1.01 (3)</td>
      <td>C19—H19A</td>
      <td>0.94 (3)</td>
    </tr>
    <tr>
      <td>C8—C7</td>
      <td>1.384 (4)</td>
      <td>C19—H19B</td>
      <td>0.95 (3)</td>
    </tr>
    <tr>
      <td>C8—H8</td>
      <td>0.98 (3)</td>
      <td>C20—C21</td>
      <td>1.148 (5)</td>
    </tr>
    <tr>
      <td>C9—C8</td>
      <td>1.380 (3)</td>
      <td>C21—H21</td>
      <td>0.90 (5)</td>
    </tr>
    <tr>
      <td>C9—H9</td>
      <td>0.93 (3)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>O1···H16B</td>
      <td>2.84 (2)</td>
      <td>C20···C4</td>
      <td>3.372 (3)</td>
    </tr>
    <tr>
      <td>O1···H13<sup>i</sup></td>
      <td>2.61 (2)</td>
      <td>C20···C9</td>
      <td>3.472 (3)</td>
    </tr>
    <tr>
      <td>O1···H5</td>
      <td>2.767 (18)</td>
      <td>C2···H5</td>
      <td>2.476 (18)</td>
    </tr>
    <tr>
      <td>O1···H8<sup>ii</sup></td>
      <td>2.62 (2)</td>
      <td>C4···H11</td>
      <td>2.679 (18)</td>
    </tr>
    <tr>
      <td>O2···H18<sup>iii</sup></td>
      <td>2.68 (5)</td>
      <td>C6···H9<sup>ii</sup></td>
      <td>2.97 (2)</td>
    </tr>
    <tr>
      <td>O2···H19B</td>
      <td>2.65 (2)</td>
      <td>C6···H18<sup>v</sup></td>
      <td>2.90 (4)</td>
    </tr>
    <tr>
      <td>O2···H16A</td>
      <td>2.50 (2)</td>
      <td>C8···H11<sup>vi</sup></td>
      <td>2.94 (2)</td>
    </tr>
    <tr>
      <td>O2···H16B<sup>iv</sup></td>
      <td>2.33 (2)</td>
      <td>C8···H19A<sup>ii</sup></td>
      <td>2.83 (2)</td>
    </tr>
    <tr>
      <td>N2···H15</td>
      <td>2.53 (2)</td>
      <td>C9···H11</td>
      <td>2.73 (2)</td>
    </tr>
    <tr>
      <td>C4···C20</td>
      <td>3.372 (3)</td>
      <td>C10···H9</td>
      <td>2.75 (2)</td>
    </tr>
    <tr>
      <td>C9···C19</td>
      <td>3.378 (3)</td>
      <td>C10···H19A</td>
      <td>2.96 (2)</td>
    </tr>
    <tr>
      <td>C9···C11</td>
      <td>3.138 (3)</td>
      <td>C11···H14<sup>i</sup></td>
      <td>2.94 (2)</td>
    </tr>
    <tr>
      <td>C9···C20</td>
      <td>3.472 (3)</td>
      <td>C11···H9</td>
      <td>2.79 (2)</td>
    </tr>
    <tr>
      <td>C11···C9</td>
      <td>3.138 (3)</td>
      <td>C12···H14<sup>i</sup></td>
      <td>2.91 (2)</td>
    </tr>
    <tr>
      <td>C15···C19</td>
      <td>3.450 (3)</td>
      <td>C14···H7<sup>vi</sup></td>
      <td>2.97 (2)</td>
    </tr>
    <tr>
      <td>C19···C15</td>
      <td>3.450 (3)</td>
      <td>H8···H11<sup>vi</sup></td>
      <td>2.53 (3)</td>
    </tr>
    <tr>
      <td>C19···C9</td>
      <td>3.378 (3)</td>
      <td>H9···H11</td>
      <td>2.58 (3)</td>
    </tr>
    <tr>
      <td>C2—N1—C3</td>
      <td>112.60 (17)</td>
      <td>C8—C9—H9</td>
      <td>121.2 (19)</td>
    </tr>
    <tr>
      <td>C2—N1—C16</td>
      <td>124.3 (2)</td>
      <td>C11—C10—C1</td>
      <td>120.65 (18)</td>
    </tr>
    <tr>
      <td>C3—N1—C16</td>
      <td>122.9 (2)</td>
      <td>C11—C10—C15</td>
      <td>118.4 (2)</td>
    </tr>
    <tr>
      <td>C3—N2—C1</td>
      <td>112.90 (16)</td>
      <td>C15—C10—C1</td>
      <td>120.64 (18)</td>
    </tr>
    <tr>
      <td>C3—N2—C19</td>
      <td>121.81 (18)</td>
      <td>C10—C11—C12</td>
      <td>120.2 (2)</td>
    </tr>
    <tr>
      <td>C19—N2—C1</td>
      <td>124.78 (17)</td>
      <td>C10—C11—H11</td>
      <td>120.6 (14)</td>
    </tr>
    <tr>
      <td>N2—C1—C2</td>
      <td>100.41 (15)</td>
      <td>C12—C11—H11</td>
      <td>119.3 (14)</td>
    </tr>
    <tr>
      <td>N2—C1—C4</td>
      <td>109.84 (16)</td>
      <td>C11—C12—H12</td>
      <td>119.8 (18)</td>
    </tr>
    <tr>
      <td>N2—C1—C10</td>
      <td>112.27 (16)</td>
      <td>C13—C12—C11</td>
      <td>120.9 (2)</td>
    </tr>
    <tr>
      <td>C4—C1—C2</td>
      <td>111.07 (16)</td>
      <td>C13—C12—H12</td>
      <td>119.3 (18)</td>
    </tr>
    <tr>
      <td>C4—C1—C10</td>
      <td>116.25 (15)</td>
      <td>C12—C13—H13</td>
      <td>119.5 (17)</td>
    </tr>
    <tr>
      <td>C10—C1—C2</td>
      <td>105.76 (16)</td>
      <td>C14—C13—C12</td>
      <td>119.3 (2)</td>
    </tr>
    <tr>
      <td>O1—C2—N1</td>
      <td>126.3 (2)</td>
      <td>C14—C13—H13</td>
      <td>121.2 (17)</td>
    </tr>
    <tr>
      <td>O1—C2—C1</td>
      <td>126.93 (19)</td>
      <td>C13—C14—C15</td>
      <td>120.6 (2)</td>
    </tr>
    <tr>
      <td>N1—C2—C1</td>
      <td>106.74 (16)</td>
      <td>C13—C14—H14</td>
      <td>121.1 (17)</td>
    </tr>
    <tr>
      <td>O2—C3—N1</td>
      <td>125.0 (2)</td>
      <td>C15—C14—H14</td>
      <td>118.2 (17)</td>
    </tr>
    <tr>
      <td>O2—C3—N2</td>
      <td>128.0 (2)</td>
      <td>C10—C15—C14</td>
      <td>120.7 (2)</td>
    </tr>
  </tbody>
</table>
<table>
  <tbody>
    <tr>
      <td>C4—C1</td>
      <td>1.529 (3)</td>
      <td>C15—H15</td>
      <td>0.99 (3)</td>
    </tr>
    <tr>
      <td>C4—C5</td>
      <td>1.390 (3)</td>
      <td>C16—H16A</td>
      <td>0.89 (3)</td>
    </tr>
    <tr>
      <td>C4—C9</td>
      <td>1.390 (3)</td>
      <td>C16—H16B</td>
      <td>0.98 (3)</td>
    </tr>
    <tr>
      <td>C5—C6</td>
      <td>1.389 (3)</td>
      <td>C17—C16</td>
      <td>1.447 (4)</td>
    </tr>
    <tr>
      <td>C5—H5</td>
      <td>1.02 (3)</td>
      <td>C17—C18</td>
      <td>1.162 (5)</td>
    </tr>
    <tr>
      <td>C6—C7</td>
      <td>1.370 (4)</td>
      <td>C18—H18</td>
      <td>0.97 (6)</td>
    </tr>
    <tr>
      <td>C6—H6</td>
      <td>0.90 (3)</td>
      <td>C19—C20</td>
      <td>1.462 (4)</td>
    </tr>
    <tr>
      <td>C7—H7</td>
      <td>1.01 (3)</td>
      <td>C19—H19A</td>
      <td>0.94 (3)</td>
    </tr>
    <tr>
      <td>C8—C7</td>
      <td>1.384 (4)</td>
      <td>C19—H19B</td>
      <td>0.95 (3)</td>
    </tr>
    <tr>
      <td>C8—H8</td>
      <td>0.98 (3)</td>
      <td>C20—C21</td>
      <td>1.148 (5)</td>
    </tr>
    <tr>
      <td>C9—C8</td>
      <td>1.380 (3)</td>
      <td>C21—H21</td>
      <td>0.90 (5)</td>
    </tr>
    <tr>
      <td>C9—H9</td>
      <td>0.93 (3)</td>
      <td></td>
      <td></td>
    </tr>
    <tr>
      <td>O1···H16B</td>
      <td>2.84 (2)</td>
      <td>C20···C4</td>
      <td>3.372 (3)</td>
    </tr>
    <tr>
      <td>O1···H13<sup>i</sup></td>
      <td>2.61 (2)</td>
      <td>C20···C9</td>
      <td>3.472 (3)</td>
    </tr>
    <tr>
      <td>O1···H5</td>
      <td>2.767 (18)</td>
      <td>C2···H5</td>
      <td>2.476 (18)</td>
    </tr>
    <tr>
      <td>O1···H8<sup>ii</sup></td>
      <td>2.62 (2)</td>
      <td>C4···H11</td>
      <td>2.679 (18)</td>
    </tr>
    <tr>
      <td>O2···H18<sup>iii</sup></td>
      <td>2.68 (5)</td>
      <td>C6···H9<sup>ii</sup></td>
      <td>2.97 (2)</td>
    </tr>
    <tr>
      <td>O2···H19B</td>
      <td>2.65 (2)</td>
      <td>C6···H18<sup>v</sup></td>
      <td>2.90 (4)</td>
    </tr>
    <tr>
      <td>O2···H16A</td>
      <td>2.50 (2)</td>
      <td>C8···H11<sup>vi</sup></td>
      <td>2.94 (2)</td>
    </tr>
    <tr>
      <td>O2···H16B<sup>iv</sup></td>
      <td>2.33 (2)</td>
      <td>C8···H19A<sup>ii</sup></td>
      <td>2.83 (2)</td>
    </tr>
    <tr>
      <td>N2···H15</td>
      <td>2.53 (2)</td>
      <td>C9···H11</td>
      <td>2.73 (2)</td>
    </tr>
    <tr>
      <td>C4···C20</td>
      <td>3.372 (3)</td>
      <td>C10···H9</td>
      <td>2.75 (2)</td>
    </tr>
    <tr>
      <td>C9···C19</td>
      <td>3.378 (3)</td>
      <td>C10···H19A</td>
      <td>2.96 (2)</td>
    </tr>
    <tr>
      <td>C9···C11</td>
      <td>3.138 (3)</td>
      <td>C11···H14<sup>i</sup></td>
      <td>2.94 (2)</td>
    </tr>
    <tr>
      <td>C9···C20</td>
      <td>3.472 (3)</td>
      <td>C11···H9</td>
      <td>2.79 (2)</td>
    </tr>
    <tr>
      <td>C11···C9</td>
      <td>3.138 (3)</td>
      <td>C12···H14<sup>i</sup></td>
      <td>2.91 (2)</td>
    </tr>
    <tr>
      <td>C15···C19</td>
      <td>3.450 (3)</td>
      <td>C14···H7<sup>vi</sup></td>
      <td>2.97 (2)</td>
    </tr>
    <tr>
      <td>C19···C15</td>
      <td>3.450 (3)</td>
      <td>H8···H11<sup>vi</sup></td>
      <td>2.53 (3)</td>
    </tr>
    <tr>
      <td>C19···C9</td>
      <td>3.378 (3)</td>
      <td>H9···H11</td>
      <td>2.58 (3)</td>
    </tr>
    <tr>
      <td>C2—N1—C3</td>
      <td>112.60 (17)</td>
      <td>C8—C9—H9</td>
      <td>121.2 (19)</td>
    </tr>
    <tr>
      <td>C2—N1—C16</td>
      <td>124.3 (2)</td>
      <td>C11—C10—C1</td>
      <td>120.65 (18)</td>
    </tr>
    <tr>
      <td>C3—N1—C16</td>
      <td>122.9 (2)</td>
      <td>C11—C10—C15</td>
      <td>118.4 (2)</td>
    </tr>
    <tr>
      <td>C3—N2—C1</td>
      <td>112.90 (16)</td>
      <td>C15—C10—C1</td>
      <td>120.64 (18)</td>
    </tr>
    <tr>
      <td>C3—N2—C19</td>
      <td>121.81 (18)</td>
      <td>C10—C11—C12</td>
      <td>120.2 (2)</td>
    </tr>
    <tr>
      <td>C19—N2—C1</td>
      <td>124.78 (17)</td>
      <td>C10—C11—H11</td>
      <td>120.6 (14)</td>
    </tr>
    <tr>
      <td>N2—C1—C2</td>
      <td>100.41 (15)</td>
      <td>C12—C11—H11</td>
      <td>119.3 (14)</td>
    </tr>
    <tr>
      <td>N2—C1—C4</td>
      <td>109.84 (16)</td>
      <td>C11—C12—H12</td>
      <td>119.8 (18)</td>
    </tr>
    <tr>
      <td>N2—C1—C10</td>
      <td>112.27 (16)</td>
      <td>C13—C12—C11</td>
      <td>120.9 (2)</td>
    </tr>
    <tr>
      <td>C4—C1—C2</td>
      <td>111.07 (16)</td>
      <td>C13—C12—H12</td>
      <td>119.3 (18)</td>
    </tr>
    <tr>
      <td>C4—C1—C10</td>
      <td>116.25 (15)</td>
      <td>C12—C13—H13</td>
      <td>119.5 (17)</td>
    </tr>
    <tr>
      <td>C10—C1—C2</td>
      <td>105.76 (16)</td>
      <td>C14—C13—C12</td>
      <td>119.3 (2)</td>
    </tr>
    <tr>
      <td>O1—C2—N1</td>
      <td>126.3 (2)</td>
      <td>C14—C13—H13</td>
      <td>121.2 (17)</td>
    </tr>
    <tr>
      <td>O1—C2—C1</td>
      <td>126.93 (19)</td>
      <td>C13—C14—C15</td>
      <td>120.6 (2)</td>
    </tr>
    <tr>
      <td>N1—C2—C1</td>
      <td>106.74 (16)</td>
      <td>C13—C14—H14</td>
      <td>121.1 (17)</td>
    </tr>
    <tr>
      <td>O2—C3—N1</td>
      <td>125.0 (2)</td>
      <td>C15—C14—H14</td>
      <td>118.2 (17)</td>
    </tr>
    <tr>
      <td>O2—C3—N2</td>
      <td>128.0 (2)</td>
      <td>C10—C15—C14</td>
      <td>120.7 (2)</td>
    </tr>
  </tbody>
</table>
<table><tr><td>N2—C3—N1</td><td>107.02 (17)</td></tr><tr><td>C5—C4—C1</td><td>120.41 (18)</td></tr><tr><td>C9—C4—C1</td><td>120.74 (18)</td></tr><tr><td>C9—C4—C5</td><td>118.6 (2)</td></tr><tr><td>C4—C5—H5</td><td>121.0 (14)</td></tr><tr><td>C6—C5—C4</td><td>120.7 (2)</td></tr><tr><td>C6—C5—H5</td><td>118.4 (14)</td></tr><tr><td>C5—C6—H6</td><td>119 (2)</td></tr><tr><td>C7—C6—C5</td><td>120.0 (2)</td></tr><tr><td>C7—C6—H6</td><td>120.8 (19)</td></tr><tr><td>C6—C7—C8</td><td>119.8 (2)</td></tr><tr><td>C6—C7—H7</td><td>121.8 (18)</td></tr><tr><td>C8—C7—H7</td><td>118.3 (18)</td></tr><tr><td>C7—C8—H8</td><td>120.2 (16)</td></tr><tr><td>C9—C8—C7</td><td>120.4 (2)</td></tr><tr><td>C9—C8—H8</td><td>119.3 (16)</td></tr><tr><td>C4—C9—H9</td><td>118.4 (19)</td></tr><tr><td>C8—C9—C4</td><td>120.4 (2)</td></tr></table>

<table><tr><td>C3—N2—C1—C4</td><td>-112.10 (13)</td></tr><tr><td>C19—N2—C1—C4</td><td>59.82 (18)</td></tr><tr><td>C3—N2—C1—C10</td><td>116.91 (13)</td></tr><tr><td>C19—N2—C1—C10</td><td>-71.17 (19)</td></tr><tr><td>C3—N2—C1—C2</td><td>4.97 (15)</td></tr><tr><td>C19—N2—C1—C2</td><td>176.88 (13)</td></tr><tr><td>C9—C4—C1—N2</td><td>-87.33 (15)</td></tr><tr><td>C5—C4—C1—N2</td><td>86.52 (16)</td></tr><tr><td>C9—C4—C1—C10</td><td>41.52 (19)</td></tr><tr><td>C5—C4—C1—C10</td><td>-144.63 (14)</td></tr><tr><td>C9—C4—C1—C2</td><td>162.49 (13)</td></tr><tr><td>C5—C4—C1—C2</td><td>-23.66 (18)</td></tr><tr><td>O1—C2—C1—N2</td><td>177.04 (14)</td></tr><tr><td>N1—C2—C1—N2</td><td>-1.91 (14)</td></tr><tr><td>O1—C2—C1—C4</td><td>-66.81 (19)</td></tr><tr><td>N1—C2—C1—C4</td><td>114.23 (13)</td></tr><tr><td>O1—C2—C1—C10</td><td>60.15 (19)</td></tr><tr><td>N1—C2—C1—C10</td><td>-118.80 (12)</td></tr><tr><td>C3—N1—C2—O1</td><td>179.51 (14)</td></tr><tr><td>C16—N1—C2—O1</td><td>-5.2 (2)</td></tr><tr><td>C3—N1—C2—C1</td><td>-1.52 (16)</td></tr><tr><td>C16—N1—C2—C1</td><td>173.78 (14)</td></tr><tr><td>C19—N2—C3—O2</td><td>2.4 (2)</td></tr><tr><td>C1—N2—C3—O2</td><td>174.63 (14)</td></tr><tr><td>C19—N2—C3—N1</td><td>-178.28 (14)</td></tr><tr><td>C1—N2—C3—N1</td><td>-6.09 (16)</td></tr></table>

<table><tr><td>C10—C15—H15</td><td>119.9 (16)</td></tr><tr><td>C14—C15—H15</td><td>119.3 (16)</td></tr><tr><td>N1—C16—H16A</td><td>107.0 (19)</td></tr><tr><td>N1—C16—H16B</td><td>108.8 (17)</td></tr><tr><td>C17—C16—N1</td><td>113.0 (2)</td></tr><tr><td>C17—C16—H16A</td><td>112.0 (18)</td></tr><tr><td>C17—C16—H16B</td><td>108.8 (18)</td></tr><tr><td>H16A—C16—H16B</td><td>107 (2)</td></tr><tr><td>C18—C17—C16</td><td>177.3 (4)</td></tr><tr><td>C17—C18—H18</td><td>176 (3)</td></tr><tr><td>N2—C19—C20</td><td>114.0 (2)</td></tr><tr><td>N2—C19—H19A</td><td>108.9 (18)</td></tr><tr><td>N2—C19—H19B</td><td>104.8 (18)</td></tr><tr><td>C20—C19—H19A</td><td>107.8 (16)</td></tr><tr><td>C20—C19—H19B</td><td>112.0 (17)</td></tr><tr><td>H19A—C19—H19B</td><td>109 (2)</td></tr><tr><td>C21—C20—C19</td><td>178.8 (5)</td></tr><tr><td>C20—C21—H21</td><td>179 (4)</td></tr></table>

<table><tr><td>C2—N1—C3—N2</td><td>4.70 (16)</td></tr><tr><td>C16—N1—C3—N2</td><td>-170.68 (14)</td></tr><tr><td>C9—C4—C5—C6</td><td>0.3 (2)</td></tr><tr><td>C1—C4—C5—C6</td><td>-173.66 (14)</td></tr><tr><td>C4—C5—C6—C7</td><td>-0.3 (3)</td></tr><tr><td>C5—C6—C7—C8</td><td>0.0 (3)</td></tr><tr><td>C9—C8—C7—C6</td><td>0.3 (3)</td></tr><tr><td>C4—C9—C8—C7</td><td>-0.3 (3)</td></tr><tr><td>C5—C4—C9—C8</td><td>0.0 (2)</td></tr><tr><td>C1—C4—C9—C8</td><td>173.96 (14)</td></tr><tr><td>N2—C1—C10—C11</td><td>159.40 (13)</td></tr><tr><td>C4—C1—C10—C11</td><td>31.74 (19)</td></tr><tr><td>C2—C1—C10—C11</td><td>-92.03 (15)</td></tr><tr><td>N2—C1—C10—C15</td><td>-27.33 (19)</td></tr><tr><td>C4—C1—C10—C15</td><td>-154.99 (14)</td></tr><tr><td>C2—C1—C10—C15</td><td>81.25 (17)</td></tr><tr><td>C15—C10—C11—C12</td><td>0.6 (2)</td></tr><tr><td>C1—C10—C11—C12</td><td>174.00 (15)</td></tr><tr><td>C10—C11—C12—C13</td><td>-0.2 (3)</td></tr><tr><td>C11—C12—C13—C14</td><td>-0.1 (3)</td></tr><tr><td>C12—C13—C14—C15</td><td>0.0 (3)</td></tr><tr><td>C10—C15—C14—C13</td><td>0.4 (3)</td></tr><tr><td>C11—C10—C15—C14</td><td>-0.7 (3)</td></tr><tr><td>C1—C10—C15—C14</td><td>-174.13 (17)</td></tr><tr><td>C2—N1—C16—C17</td><td>69.8 (2)</td></tr><tr><td>C3—N1—C16—C17</td><td>-115.34 (18)</td></tr></table>
<table><tr><td>N2—C3—N1</td><td>107.02 (17)</td></tr><tr><td>C5—C4—C1</td><td>120.41 (18)</td></tr><tr><td>C9—C4—C1</td><td>120.74 (18)</td></tr><tr><td>C9—C4—C5</td><td>118.6 (2)</td></tr><tr><td>C4—C5—H5</td><td>121.0 (14)</td></tr><tr><td>C6—C5—C4</td><td>120.7 (2)</td></tr><tr><td>C6—C5—H5</td><td>118.4 (14)</td></tr><tr><td>C5—C6—H6</td><td>119 (2)</td></tr><tr><td>C7—C6—C5</td><td>120.0 (2)</td></tr><tr><td>C7—C6—H6</td><td>120.8 (19)</td></tr><tr><td>C6—C7—C8</td><td>119.8 (2)</td></tr><tr><td>C6—C7—H7</td><td>121.8 (18)</td></tr><tr><td>C8—C7—H7</td><td>118.3 (18)</td></tr><tr><td>C7—C8—H8</td><td>120.2 (16)</td></tr><tr><td>C9—C8—C7</td><td>120.4 (2)</td></tr><tr><td>C9—C8—H8</td><td>119.3 (16)</td></tr><tr><td>C4—C9—H9</td><td>118.4 (19)</td></tr><tr><td>C8—C9—C4</td><td>120.4 (2)</td></tr></table>

<table><tr><td>C3—N2—C1—C4</td><td>-112.10 (13)</td></tr><tr><td>C19—N2—C1—C4</td><td>59.82 (18)</td></tr><tr><td>C3—N2—C1—C10</td><td>116.91 (13)</td></tr><tr><td>C19—N2—C1—C10</td><td>-71.17 (19)</td></tr><tr><td>C3—N2—C1—C2</td><td>4.97 (15)</td></tr><tr><td>C19—N2—C1—C2</td><td>176.88 (13)</td></tr><tr><td>C9—C4—C1—N2</td><td>-87.33 (15)</td></tr><tr><td>C5—C4—C1—N2</td><td>86.52 (16)</td></tr><tr><td>C9—C4—C1—C10</td><td>41.52 (19)</td></tr><tr><td>C5—C4—C1—C10</td><td>-144.63 (14)</td></tr><tr><td>C9—C4—C1—C2</td><td>162.49 (13)</td></tr><tr><td>C5—C4—C1—C2</td><td>-23.66 (18)</td></tr><tr><td>O1—C2—C1—N2</td><td>177.04 (14)</td></tr><tr><td>N1—C2—C1—N2</td><td>-1.91 (14)</td></tr><tr><td>O1—C2—C1—C4</td><td>-66.81 (19)</td></tr><tr><td>N1—C2—C1—C4</td><td>114.23 (13)</td></tr><tr><td>O1—C2—C1—C10</td><td>60.15 (19)</td></tr><tr><td>N1—C2—C1—C10</td><td>-118.80 (12)</td></tr><tr><td>C3—N1—C2—O1</td><td>179.51 (14)</td></tr><tr><td>C16—N1—C2—O1</td><td>-5.2 (2)</td></tr><tr><td>C3—N1—C2—C1</td><td>-1.52 (16)</td></tr><tr><td>C16—N1—C2—C1</td><td>173.78 (14)</td></tr><tr><td>C19—N2—C3—O2</td><td>2.4 (2)</td></tr><tr><td>C1—N2—C3—O2</td><td>174.63 (14)</td></tr><tr><td>C19—N2—C3—N1</td><td>-178.28 (14)</td></tr><tr><td>C1—N2—C3—N1</td><td>-6.09 (16)</td></tr></table>

<table><tr><td>C10—C15—H15</td><td>119.9 (16)</td></tr><tr><td>C14—C15—H15</td><td>119.3 (16)</td></tr><tr><td>N1—C16—H16A</td><td>107.0 (19)</td></tr><tr><td>N1—C16—H16B</td><td>108.8 (17)</td></tr><tr><td>C17—C16—N1</td><td>113.0 (2)</td></tr><tr><td>C17—C16—H16A</td><td>112.0 (18)</td></tr><tr><td>C17—C16—H16B</td><td>108.8 (18)</td></tr><tr><td>H16A—C16—H16B</td><td>107 (2)</td></tr><tr><td>C18—C17—C16</td><td>177.3 (4)</td></tr><tr><td>C17—C18—H18</td><td>176 (3)</td></tr><tr><td>N2—C19—C20</td><td>114.0 (2)</td></tr><tr><td>N2—C19—H19A</td><td>108.9 (18)</td></tr><tr><td>N2—C19—H19B</td><td>104.8 (18)</td></tr><tr><td>C20—C19—H19A</td><td>107.8 (16)</td></tr><tr><td>C20—C19—H19B</td><td>112.0 (17)</td></tr><tr><td>H19A—C19—H19B</td><td>109 (2)</td></tr><tr><td>C21—C20—C19</td><td>178.8 (5)</td></tr><tr><td>C20—C21—H21</td><td>179 (4)</td></tr></table>

<table><tr><td>C2—N1—C3—N2</td><td>4.70 (16)</td></tr><tr><td>C16—N1—C3—N2</td><td>-170.68 (14)</td></tr><tr><td>C9—C4—C5—C6</td><td>0.3 (2)</td></tr><tr><td>C1—C4—C5—C6</td><td>-173.66 (14)</td></tr><tr><td>C4—C5—C6—C7</td><td>-0.3 (3)</td></tr><tr><td>C5—C6—C7—C8</td><td>0.0 (3)</td></tr><tr><td>C9—C8—C7—C6</td><td>0.3 (3)</td></tr><tr><td>C4—C9—C8—C7</td><td>-0.3 (3)</td></tr><tr><td>C5—C4—C9—C8</td><td>0.0 (2)</td></tr><tr><td>C1—C4—C9—C8</td><td>173.96 (14)</td></tr><tr><td>N2—C1—C10—C11</td><td>159.40 (13)</td></tr><tr><td>C4—C1—C10—C11</td><td>31.74 (19)</td></tr><tr><td>C2—C1—C10—C11</td><td>-92.03 (15)</td></tr><tr><td>N2—C1—C10—C15</td><td>-27.33 (19)</td></tr><tr><td>C4—C1—C10—C15</td><td>-154.99 (14)</td></tr><tr><td>C2—C1—C10—C15</td><td>81.25 (17)</td></tr><tr><td>C15—C10—C11—C12</td><td>0.6 (2)</td></tr><tr><td>C1—C10—C11—C12</td><td>174.00 (15)</td></tr><tr><td>C10—C11—C12—C13</td><td>-0.2 (3)</td></tr><tr><td>C11—C12—C13—C14</td><td>-0.1 (3)</td></tr><tr><td>C12—C13—C14—C15</td><td>0.0 (3)</td></tr><tr><td>C10—C15—C14—C13</td><td>0.4 (3)</td></tr><tr><td>C11—C10—C15—C14</td><td>-0.7 (3)</td></tr><tr><td>C1—C10—C15—C14</td><td>-174.13 (17)</td></tr><tr><td>C2—N1—C16—C17</td><td>69.8 (2)</td></tr><tr><td>C3—N1—C16—C17</td><td>-115.34 (18)</td></tr></table>
<table><tr><td>C2—N1—C3—O2</td><td>-175.99 (14)</td><td>C3—N2—C19—C20</td><td>76.6 (2)</td></tr><tr><td>C16—N1—C3—O2</td><td>8.6 (2)</td><td>C1—N2—C19—C20</td><td>-94.61 (19)</td></tr></table>

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

### Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C4–C9 and C10–C15 rings, respectively.

<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>C16—H16B···O2<sup>vii</sup></td><td>0.98 (3)</td><td>2.33 (3)</td><td>3.178 (3)</td><td>144 (2)</td></tr><tr><td>C9—H9···Cg1<sup>vi</sup></td><td>0.93 (3)</td><td>2.93 (2)</td><td>3.778 (2)</td><td>152.7 (17)</td></tr><tr><td>C14—H14···Cg2<sup>viii</sup></td><td>1.00 (3)</td><td>2.87 (2)</td><td>3.762 (3)</td><td>149.6 (17)</td></tr></tbody></table>

Symmetry codes: (vi) $-x+1, y+1/2, -z+1$; (vii) $-x, y-1/2, -z$; (viii) $-x+1, y+1/2, -z$.
<table><tr><td>C2—N1—C3—O2</td><td>-175.99 (14)</td><td>C3—N2—C19—C20</td><td>76.6 (2)</td></tr><tr><td>C16—N1—C3—O2</td><td>8.6 (2)</td><td>C1—N2—C19—C20</td><td>-94.61 (19)</td></tr></table>

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

### Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C4–C9 and C10–C15 rings, respectively.

<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>C16—H16B···O2<sup>vii</sup></td><td>0.98 (3)</td><td>2.33 (3)</td><td>3.178 (3)</td><td>144 (2)</td></tr><tr><td>C9—H9···Cg1<sup>vi</sup></td><td>0.93 (3)</td><td>2.93 (2)</td><td>3.778 (2)</td><td>152.7 (17)</td></tr><tr><td>C14—H14···Cg2<sup>viii</sup></td><td>1.00 (3)</td><td>2.87 (2)</td><td>3.762 (3)</td><td>149.6 (17)</td></tr></tbody></table>

Symmetry codes: (vi) $-x+1, y+1/2, -z+1$; (vii) $-x, y-1/2, -z$; (viii) $-x+1, y+1/2, -z$.