Channels with ordered water and bipyridine molecules
in the porous coordination polymer [Cu(SiF 6 )(C 10 H
8 N 2 ) 2 ]×2C 10 N 2 H 8 ×5H 2 O n

Emmanuel Aubert, Abdelatif Doudouh, Paola Peluso, Victor Mamane

► To cite this version:

Emmanuel Aubert, Abdelatif Doudouh, Paola Peluso, Victor Mamane. Channels with ordered water and bipyridine molecules in the porous coordination polymer [Cu(SiF 6 )(C 10 H 8 N 2 ) 2 ]×2C 10 N 2 H 8 ×5H 2 O n. Acta crystallographica Section E: Crystallographic communications [2015-..], 2016, 72 (11), pp.1654-1658. 10.1107/S2056989016016686. hal-02266118

HAL Id: hal-02266118

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

Distributed under a Creative Commons Attribution 4.0 International License
Received 6 October 2016
Accepted 18 October 2016

Edited by A. Van der Lee, Université de
Montpellier II, France

**Keywords:** Porous coordination polymer; adsorption; hydrogen bonding; π-π stacking; copper(II); 4,4'-bipyridine; crystal structure.

CCDC reference: 1510381

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

# Channels with ordered water and bipyridine molecules in the porous coordination polymer {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}n

Emmanuel Aubert,ª* Abdelatif Doudouh,ª Paola Pelusoᵇ and Victor Mamaneᶜ

The coordination polymer {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}n, systematic name: poly[[bis(μ₂-4,4'-bipyridine)(μ₂-hexafluoridosilicato)copper(II)] 4,4'-bipyridine disolvate pentahydrate], contains pores which are filled with water and 4,4'-bipyridine molecules. As a result of the presence of these ordered species, the framework changes its symmetry from P4/mmm to P2₁/c. The 4,4'-bipyridine guest molecules form chains inside the 6.5 × 6.9 Å pores parallel to [100] in which the molecules interact through π-π stacking. Ordered water molecules form infinite hydrogen-bonded chains inside a second pore system (1.6 × 5.3 Å free aperture) perpendicular to the 4,4'-bipyridine channels.

## 1. Chemical context

The title compound was obtained in an attempt to reproduce the synthesis of [Cu(μ-4,4'-bipy)(H₂O)₂(BF₄)₂]·4,4'-bipy (Blake *et al.*, 1997). A contamination with SiF₆²⁻ is, however, at the origin of the formation of {[[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}n, whose framework was previously described by Noro *et al.* (2000, 2002). This framework has shown interesting gas adsorption properties in recent years (Burd *et al.*, 2012; Yu *et al.*, 2012; Fan *et al.*, 2013). Several structures based on this porous framework have been published since its discovery [CSD refcodes: GORWUF (Noro *et al.*, 2000), AFEKAX (Noro *et al.*, 2002), HAPKOA (Burd *et al.*, 2012)]. However, these structures which are reported in the tetragonal space group type P4/mmm are disordered: the framework bipyridines are disordered by symmetry whereas solvent molecules are not clearly identified within the pores. In this article, we show that this porous coordination polymer is capable of firmly stabilizing guest entities such as 4,4'-bipyridine and water molecules within its channels. The synthesis conditions thus seem a key factor in producing the ordering of guest molecules within this porous material.

## 2. Structural commentary

The asymmetric unit of the title compound (Fig. 1) contains two copper(II) atoms, both lying on inversion centers; each of these two atoms is coordinated by N atoms of four symmetrically related 4,4'-bipyridine molecules (with one independent bipyridine for each copper atom), forming slightly distorted two-dimensional square grids parallel to (100). The

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

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<footnote>ªCristallographie, Résonance Magnétique et Modélisations (CRM2), UMR CNRS, 7036, Université de Lorraine, BP 70239, Bd des Aiguillettes, 54506, Vandoeuvre-les-Nancy, France, ᵇIstituto di Chimica Biomolecolare ICB CNR - Sede Secondaria di Sassari, Traversa La Crucca 3, Regione Baldinca, I-07100 Li Punti - Sassari, Italy, and ᶜInstitut de Chimie de Strasbourg, UMR 7177, Equipe LASYROC, 1 rue Blaise Pascal, BP 296 R8, 67008 Strasbourg Cedex, France.</footnote>

<footnote>*Correspondence e-mail: emmanuel.aubert@univ-lorraine.fr</footnote>
copper(II) atoms are both at the center of elongated octahedra (Table 1).

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

The basal plane is composed of four nitrogen atoms coming from the 4,4'-bipyridine molecules, whereas the apical positions are occupied by fluorine atoms belonging to the SiF<sub>6</sub><sup>2-</sup> anions pillaring the structure (Fig. 2).

The 2D coordination grids are stacked along the [100] direction through the SiF<sub>6</sub><sup>2-</sup> anions, leading to a three-dimensional coordination polymer, which displays channels having a free aperture of 6.5 × 6.9 Å parallel to [100] and smaller pores of 1.6 × 5.3 Å along the [011] direction (as measured in projection in the plane perpendicular to the channels and using van der Waals radii). These interconnected pores are filled with two other 4,4'-bipyridine molecules and five water molecules (Figs. 3 and 4). In comparison, the

<figure><img src="image_5.png" /><figcaption>**Figure 1**
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.</figcaption></figure>

<table><caption>**Table 1**
Selected geometric parameters (Å, °).</caption><tr><td>Cu1—N1<sup>i</sup></td><td>2.0156 (11)</td><td>Cu2—N19<sup>vi</sup></td><td>2.0494 (11)</td></tr><tr><td>Cu1—N1</td><td>2.0156 (11)</td><td>Cu2—F2</td><td>2.4109 (9)</td></tr><tr><td>Cu1—N7<sup>ii</sup></td><td>2.0467 (11)</td><td>Cu2—F2<sup>iv</sup></td><td>2.4109 (9)</td></tr><tr><td>Cu1—N7<sup>iii</sup></td><td>2.0467 (11)</td><td>Si1—F6</td><td>1.6534 (11)</td></tr><tr><td>Cu1—F1<sup>i</sup></td><td>2.3585 (9)</td><td>Si1—F5</td><td>1.6806 (10)</td></tr><tr><td>Cu1—F1</td><td>2.3585 (9)</td><td>Si1—F3</td><td>1.6823 (10)</td></tr><tr><td>Cu2—N13<sup>iv</sup></td><td>2.0170 (11)</td><td>Si1—F4</td><td>1.6855 (11)</td></tr><tr><td>Cu2—N13</td><td>2.0170 (11)</td><td>Si1—F2</td><td>1.7120 (10)</td></tr><tr><td>Cu2—N19<sup>v</sup></td><td>2.0494 (11)</td><td>Si1—F1</td><td>1.7145 (10)</td></tr><tr><td>N1<sup>i</sup>—Cu1—N1</td><td>180.00 (6)</td><td>N19<sup>v</sup>—Cu2—F2</td><td>90.67 (4)</td></tr><tr><td>N1<sup>i</sup>—Cu1—N7<sup>ii</sup></td><td>91.58 (5)</td><td>N19<sup>vi</sup>—Cu2—F2</td><td>89.33 (4)</td></tr><tr><td>N1—Cu1—N7<sup>ii</sup></td><td>88.42 (5)</td><td>N13<sup>iv</sup>—Cu2—F2<sup>iv</sup></td><td>89.41 (4)</td></tr><tr><td>N1<sup>i</sup>—Cu1—N7<sup>iii</sup></td><td>88.42 (5)</td><td>N13—Cu2—F2<sup>iv</sup></td><td>90.59 (4)</td></tr><tr><td>N1—Cu1—N7<sup>iii</sup></td><td>91.58 (5)</td><td>N19<sup>v</sup>—Cu2—F2<sup>iv</sup></td><td>89.33 (4)</td></tr><tr><td>N7<sup>ii</sup>—Cu1—N7<sup>iii</sup></td><td>180.0</td><td>N19<sup>vi</sup>—Cu2—F2<sup>iv</sup></td><td>90.67 (4)</td></tr><tr><td>N1<sup>i</sup>—Cu1—F1<sup>i</sup></td><td>90.65 (4)</td><td>F2—Cu2—F2<sup>iv</sup></td><td>180.0</td></tr><tr><td>N1—Cu1—F1<sup>i</sup></td><td>89.35 (4)</td><td>F6—Si1—F5</td><td>90.80 (6)</td></tr><tr><td>N7<sup>ii</sup>—Cu1—F1<sup>i</sup></td><td>89.60 (4)</td><td>F6—Si1—F3</td><td>89.64 (6)</td></tr><tr><td>N7<sup>iii</sup>—Cu1—F1<sup>i</sup></td><td>90.40 (4)</td><td>F5—Si1—F3</td><td>179.55 (6)</td></tr><tr><td>N1<sup>i</sup>—Cu1—F1</td><td>89.35 (4)</td><td>F6—Si1—F4</td><td>178.87 (6)</td></tr><tr><td>N1—Cu1—F1</td><td>90.65 (4)</td><td>F5—Si1—F4</td><td>90.12 (6)</td></tr><tr><td>N7<sup>ii</sup>—Cu1—F1</td><td>90.40 (4)</td><td>F3—Si1—F4</td><td>89.44 (6)</td></tr><tr><td>N7<sup>iii</sup>—Cu1—F1</td><td>89.60 (4)</td><td>F6—Si1—F2</td><td>91.01 (4)</td></tr><tr><td>F1<sup>i</sup>—Cu1—F1</td><td>180.0</td><td>F5—Si1—F2</td><td>89.67 (5)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N13</td><td>180.0</td><td>F3—Si1—F2</td><td>90.41 (5)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N19<sup>v</sup></td><td>90.73 (5)</td><td>F4—Si1—F2</td><td>89.64 (4)</td></tr><tr><td>N13—Cu2—N19<sup>v</sup></td><td>89.27 (5)</td><td>F6—Si1—F1</td><td>90.89 (4)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N19<sup>vi</sup></td><td>89.27 (5)</td><td>F5—Si1—F1</td><td>90.35 (5)</td></tr><tr><td>N13—Cu2—N19<sup>vi</sup></td><td>90.73 (5)</td><td>F3—Si1—F1</td><td>89.56 (5)</td></tr><tr><td>N19<sup>v</sup>—Cu2—N19<sup>vi</sup></td><td>180.0</td><td>F4—Si1—F1</td><td>88.45 (4)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—F2</td><td>90.59 (4)</td><td>F2—Si1—F1</td><td>178.09 (4)</td></tr><tr><td>N13—Cu2—F2</td><td>89.41 (4)</td><td>Si1—F1—Cu1</td><td>178.36 (5)</td></tr></table>

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

<figure><img src="image_6.png" /><figcaption>**Figure 2**
View along [011]; the atoms belonging to the framework are shown as space-filling, whereas the molecules adsorbed inside the pores are shown as capped sticks.</figcaption></figure>
<figure><img src="image_7.png" /><figcaption>Figure 3</figcaption></figure>

View along [100]; the atoms belonging to the framework are shown as space-filling, whereas the molecules inside the pores are shown as capped sticks.

previously reported structures with this framework are described in the *P4/mmm* space group type, implying a squared Cu grid and channels; here, the Cu–Cu–Cu grid angle

<figure><img src="image_8.png" /><figcaption>Figure 4</figcaption></figure>

ORTEP-style plot of the title compound showing the coordination about the two inequivalent copper atoms. Hydrogen atoms, adsorbed 4,4'-bipyridine and water molecules are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.

<caption>Table 2</caption>

Hydrogen-bond geometry (Å, °).

<table><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>C17–H17···N31<sup>vii</sup></td><td>0.95</td><td>2.34</td><td>3.2849 (19)</td><td>170</td></tr><tr><td>C20–H20···F2<sup>ii</sup></td><td>0.95</td><td>2.32</td><td>3.0341 (16)</td><td>131</td></tr><tr><td>C20–H20···F5<sup>ii</sup></td><td>0.95</td><td>2.53</td><td>3.4305 (17)</td><td>159</td></tr><tr><td>C18–H18···F2<sup>iv</sup></td><td>0.95</td><td>2.52</td><td>3.1085 (16)</td><td>120</td></tr><tr><td>C9–H9···O52</td><td>0.95</td><td>2.50</td><td>3.4223 (18)</td><td>163</td></tr><tr><td>C3–H3···N37<sup>iii</sup></td><td>0.95</td><td>2.54</td><td>3.4803 (19)</td><td>173</td></tr><tr><td>C21–H21···O52<sup>ii</sup></td><td>0.95</td><td>2.56</td><td>3.4294 (18)</td><td>152</td></tr><tr><td>C14–H14···F2</td><td>0.95</td><td>2.43</td><td>3.0497 (16)</td><td>123</td></tr><tr><td>C14–H14···F4</td><td>0.95</td><td>2.55</td><td>3.4519 (17)</td><td>158</td></tr><tr><td>C8–H8···F1<sup>v</sup></td><td>0.95</td><td>2.33</td><td>3.0205 (16)</td><td>129</td></tr><tr><td>C8–H8···F4<sup>v</sup></td><td>0.95</td><td>2.51</td><td>3.3524 (18)</td><td>148</td></tr><tr><td>C5–H5···O52</td><td>0.95</td><td>2.43</td><td>3.2916 (18)</td><td>151</td></tr><tr><td>C24–H24···F2<sup>vii</sup></td><td>0.95</td><td>2.29</td><td>2.9997 (16)</td><td>131</td></tr><tr><td>C24–H24···F3<sup>vii</sup></td><td>0.95</td><td>2.55</td><td>3.4609 (17)</td><td>161</td></tr><tr><td>C11–H11···N37<sup>iii</sup></td><td>0.95</td><td>2.61</td><td>3.4358 (19)</td><td>145</td></tr><tr><td>C12–H12···F1<sup>viii</sup></td><td>0.95</td><td>2.26</td><td>2.9662 (16)</td><td>131</td></tr><tr><td>C12–H12···F6<sup>viii</sup></td><td>0.95</td><td>2.49</td><td>3.4040 (16)</td><td>161</td></tr><tr><td>C2–H2···F1<sup>i</sup></td><td>0.95</td><td>2.52</td><td>3.0708 (16)</td><td>117</td></tr><tr><td>C2–H2···F3<sup>i</sup></td><td>0.95</td><td>2.45</td><td>3.3364 (17)</td><td>156</td></tr><tr><td>C45–H45···O50<sup>ix</sup></td><td>0.95</td><td>2.44</td><td>3.376 (2)</td><td>167</td></tr><tr><td>C6–H6···F1</td><td>0.95</td><td>2.46</td><td>3.0691 (16)</td><td>122</td></tr><tr><td>C6–H6···F4</td><td>0.95</td><td>2.60</td><td>3.5313 (17)</td><td>166</td></tr><tr><td>C38–H38···F6</td><td>0.95</td><td>2.41</td><td>3.1240 (19)</td><td>132</td></tr><tr><td>C48–H48···O51<sup>iv</sup></td><td>0.95</td><td>2.50</td><td>3.330 (2)</td><td>146</td></tr><tr><td>O53–H53B···F3<sup>v</sup></td><td>0.78 (2)</td><td>1.96 (3)</td><td>2.7228 (17)</td><td>166 (2)</td></tr><tr><td>O52–H52B···O53</td><td>0.90 (3)</td><td>1.83 (3)</td><td>2.7227 (18)</td><td>170 (2)</td></tr><tr><td>O53–H53A···N43<sup>iv</sup></td><td>0.85 (3)</td><td>2.05 (3)</td><td>2.8666 (19)</td><td>161 (3)</td></tr><tr><td>O52–H52A···O51</td><td>0.90 (3)</td><td>1.84 (3)</td><td>2.726 (2)</td><td>172 (2)</td></tr><tr><td>O50–H50A···O49</td><td>1.05 (3)</td><td>1.72 (3)</td><td>2.741 (2)</td><td>163 (2)</td></tr><tr><td>O49–H49B···F5<sup>ii</sup></td><td>0.96 (3)</td><td>1.82 (3)</td><td>2.7716 (18)</td><td>173 (3)</td></tr><tr><td>O50–H50B···N25<sup>i</sup></td><td>0.96 (3)</td><td>1.86 (3)</td><td>2.816 (2)</td><td>173 (3)</td></tr><tr><td>O49–H49A···O52<sup>ii</sup></td><td>1.00 (4)</td><td>1.81 (4)</td><td>2.798 (2)</td><td>169 (3)</td></tr><tr><td>O51–H51B···F4</td><td>0.91 (3)</td><td>1.88 (3)</td><td>2.7029 (18)</td><td>149 (2)</td></tr><tr><td>O51–H51A···O50</td><td>1.00 (4)</td><td>1.76 (4)</td><td>2.719 (2)</td><td>158 (3)</td></tr></tbody></table>

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

significantly deviates from 90° (96.62°) and this may be related to the fact that, in the present compound, guest molecules fill the pores and interact significantly with the framework atoms (see below).

The Si–F bond lengths in SiF$_6^{2-}$ show some variations (Table 1), ranging from 1.6534 (11) to 1.7145 (10) Å. The two longest bond lengths are associated with opposite fluorine atoms bounded to a Cu$^{II}$ metal atom. Among the four remaining fluorine atoms, three of them form short hydrogen bonds with water molecules and display longer bond lengths than the last one, which only forms a weaker hydrogen-bonding interaction with a 4,4'-bipyridine molecule (Table 2). A search for SiF$_6^{2-}$ anions within the Cambridge Structural Database (CSD Version 5.36; Groom et al., 2016) leads to 241 hits (using options 'not disordered' and 'no errors'); the reported Si–F bond lengths range from 1.577 to 1.748 Å with a mean of 1.684 Å and a standard deviation of 0.022 Å.

### 3. Supramolecular features

Four of the five water molecules (O49 to O52) form infinite $C_4^4(2)$ chains running in the [001] direction throughout the pores (Fig. 5). The fifth water molecule (O53) interacts with
<figure><img src="image_9.png" /><figcaption>Figure 5</figcaption></figure>

Hydrogen-bonding pattern of solvate water molecules, forming infinite chains along the [001] direction. All other atoms apart from those of the water molecules are omitted for clarity.

these chains and several hydrogen bonds anchor these water molecules to the coordination polymer framework (Table 2). The 4,4'-bipyridine molecules filling the [100] channels form chains through π-π stacking (Fig. 6; Table 3), and are connected to three of the water molecules (O50, O51 and

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

π-π stacking pattern of the solvent 4,4'-bipyridine molecules in the [100] pores. All other atoms (except water molecules hydrogen-bonded to N atoms of these bipyridines) are omitted for clarity. Pyridyl centroids are displayed as green spheres.

<caption>Table 3</caption>

Geometrical parameters (Å, °) for the π-π stacking of the 4,4'-bipyridine molecules within the pores.

$Cg(I)$ is the centroid of the atoms defining plane I: $Cg(N25) = N25/C26-C30; Cg(N31) = N31/C32-C36; Cg(N43) = N43/C44-7-C48 and Cg(N37) = N37/C38-C42. $d_{Cg-Cg}$ is the distance between $Cg(I)$ and $Cg(J)$. $\alpha$ is the dihedral angle between planes I and J. $\beta$ is the angle between the $Cg(I) \rightarrow Cg(J)$ vector and the normal to plane I. $\gamma$ is the angle between the $Cg(I) \rightarrow Cg(J)$ vector and the normal to plane J.

<table><thead><tr><th>Cg(I)</th><th>Cg(J)</th><th>d<sub>Cg-Cg</sub></th><th>α</th><th>β</th><th>γ</th></tr></thead><tbody><tr><td>N25</td><td>N25<sup>i</sup></td><td>3.7374 (10)</td><td>0.02 (9)</td><td>9.2</td><td>9.2</td></tr><tr><td>N31</td><td>N37<sup>ii</sup></td><td>3.7358 (9)</td><td>20.79 (8)</td><td>21.4</td><td>13.1</td></tr><tr><td>N43</td><td>N43<sup>iii</sup></td><td>3.8576 (9)</td><td>0.00 (7)</td><td>23.8</td><td>23.8</td></tr></tbody></table>

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

O53) and framework fluorine and aromatic hydrogen atoms by hydrogen bonds (Table 2); these intermolecular interactions induce different dihedral angles within the two symmetry-independent 4,4'-bipyridine molecules [bipy(N25-N31): 45.29 (7)°; bipy(N37-N43): 30.31 (7)°]. Whereas the 4,4'-bipyridine molecules belonging to the coordination network are rather rigid between the metal atoms [average $U_{eq}$ = 0.014 (2) Å² as calculated on C,N atoms], the adsorbed 4,4'-bipyridine molecules display significantly larger atomic displacement parameters [$U_{eq}$ = 0.025 (5) Å²].

## 4. Database survey

A survey was performed in the Cambridge Structural Database (CSD Version 5.36; Groom et al., 2016). Beside the structures corresponding to the bare or hydrated $[Cu(SiF_6)(C_{10}H_8N_2)_2]_n$ coordination polymer framework [CSD refcodes: GORWUF (Noro et al., 2000), AFEKAX (Noro et al., 2002), HAPKOA (Burd et al., 2012)], several structures related to the title compound have been described. In particular, Noro et al. showed that the hydrated form of the title compound $[[Cu(SiF_6)(4,4'-bpy)_2]·8H_2O]_n$ undergoes a structural conversion when immersed in water, leading to an interpenetrated network where $SiF_6^{2-}$ anions are shifted out of the coordination sphere of copper ions and are replaced by water molecules [CSD refcodes: AFEHOI (Noro et al., 2002); JEZRUB (Gable et al., 1990)]. When copper is replaced by zinc, an isostructural compound is obtained [CSD refcodes: WONZIJ (Lin et al., 2009); ZESFUY (Subramanian & Zaworotko, 1995)].

## 5. Synthesis and crystallization

An aqueous solution (5 cm³) of hydrated copper(II) tetra-fluoridoborate (47.43 mg, 0.2 mmol) was added to a refluxing acetonitrile solution (5 cm³) of 4,4'-bipyridine (62.48 mg, 0.4 mmol). After filtration, $Et_2O$ vapor was diffused into the mother liquor for seven days, and then the solvent was allowed to evaporate very slowly. A mixture of blue and violet crystals was obtained; whereas the diffraction spots of the blue crystals could not be properly indexed, the violet crystals were of very good quality and led to the structure reported on herein.
## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All hydrogen atoms of water molecules were freely refined in an isotropic approximation. Aromatic hydrogen atoms were refined with riding coordinates and $U_{iso}(H) = 1.2U_{iso}(C)$.

## Acknowledgements

The Service Commun de Diffraction des Rayons X – Lorraine University is thanked for providing access to crystallographic facilities.

## References

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Burd, S. D., Ma, S., Perman, J. A., Sikora, B. J., Snurr, R. Q., Thallapally, P. K., Tian, J., Wojtas, L. & Zaworotko, M. J. (2012). *J. Am. Chem. Soc.* **134**, 3663–3666.

Clark, R. C. & Reid, J. S. (1995). *Acta Cryst.* **A51**, 887–897.

Fan, S., Sun, F., Xie, J., Guo, J., Zhang, L., Wang, C., Pan, Q. & Zhu, G. (2013). *J. Mater. Chem. A*, **1**, 11438–11442.

Gable, R. W., Hoskins, B. F. & Robson, R. (1990). *J. Chem. Soc. Chem. Commun.* pp. 1677–1678.

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

Lin, M.-J., Jouaiti, A., Kyritsakas, N. & Hosseini, M. W. (2009). *CrystEngComm*, **11**, 189–191.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). *J. Appl. Cryst.* **39**, 453–457.

Noro, S., Kitagawa, S., Kondo, M. & Seki, K. (2000). *Angew. Chem. Int. Ed.* **39**, 2081–2084.

Noro, S., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. & Yamashita, M. (2002). *J. Am. Chem. Soc.* **124**, 2568–2583.

Rigaku Oxford Diffraction (2015). *CrysAlis PRO*. Rigaku Corporation, Tokyo, Japan.

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

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

Subramanian, S. & Zaworotko, M. J. (1995). *Angew. Chem. Int. Ed.* **34**, 2127–2129.

<table><caption>**Table 4**
Experimental details.</caption><tr><td>Crystal data</td><td></td></tr><tr><td>Chemical formula</td><td>[Cu(SiF<sub>6</sub>)(C<sub>10</sub>H<sub>8</sub>N<sub>2</sub>)<sub>2</sub>]-2C<sub>10</sub>H<sub>8</sub>N<sub>2</sub>·5H<sub>2</sub>O</td></tr><tr><td>M<sub>r</sub></td><td>920.44</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, P2<sub>1</sub>/c</td></tr><tr><td>Temperature (K)</td><td>110</td></tr><tr><td>a, b, c (Å)</td><td>16.3875 (2), 16.6136 (2), 14.7959 (2)</td></tr><tr><td>β (°)</td><td>90.654 (1)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>4028.00 (9)</td></tr><tr><td>Z</td><td>4</td></tr><tr><td>Radiation type</td><td>Cu Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>1.78</td></tr><tr><td>Crystal size (mm)</td><td>0.25 × 0.16 × 0.14</td></tr><tr><td>Data collection</td><td></td></tr><tr><td>Diffractometer</td><td>Rigaku Oxford Diffraction Super-Nova (Cu) X-ray Source</td></tr><tr><td>Absorption correction</td><td>Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015) based on expressions derived by Clark & Reid (1995)]</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.708, 0.824</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>68271, 8435, 7846</td></tr><tr><td>R<sub>int</sub></td><td>0.029</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.630</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>0.036, 0.110, 1.06</td></tr><tr><td>No. of reflections</td><td>8435</td></tr><tr><td>No. of parameters</td><td>593</td></tr><tr><td>H-atom treatment</td><td>H atoms treated by a mixture of independent and constrained refinement</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>0.47, -0.50</td></tr></table>

Computer programs: *CrysAlis PRO* (Rigaku Oxford Diffraction, 2015), *SHELXT* (Sheldrick, 2015a), *SHELXL* (Sheldrick, 2015b), *Mercury* (Macrae *et al.*, 2006) and *publCIF* (Westrip, 2010).

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

Yu, Q., Yang, J., Zhao, Q., Dong, J. & Li, J. (2012). *J. Coord. Chem.* **65**, 1645–1654.
supporting information

Acta Cryst. (2016). E72, 1654-1658 [https://doi.org/10.1107/S2056989016016686]

Channels with ordered water and bipyridine molecules in the porous
coordination polymer {[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀N₂H₈·5H₂O}n

Emmanuel Aubert, Abdelatif Doudouh, Paola Peluso and Victor Mamane

Computing details

Data collection: *CrysAlis PRO* (Rigaku Oxford Diffraction, 2015); cell refinement: *CrysAlis PRO* (Rigaku Oxford

Diffraction, 2015); data reduction: *CrysAlis PRO* (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure:

SHELXT (Sheldrick, 2015a); program(s) used to refine structure: *SHELXL* (Sheldrick, 2015b); molecular graphics:

*Mercury* (Macrae *et al.*, 2006); software used to prepare material for publication: *publCIF* (Westrip, 2010).

Poly[[bis(µ₂-4,4'-bipyridine)(µ₂-hexafluoridosilicato)copper(II)] 4,4'-bipyridine disolvate pentahydrate]

Crystal data

[Cu(SiF₆)(C₁₀H₈N₂)₂]·2C₁₀H₈N₂·5H₂O

$M_r = 920.44$

Monoclinic, P2₁/c

$a = 16.3875 (2) Å$

$b = 16.6136 (2) Å$

$c = 14.7959 (2) Å$

$\beta = 90.654 (1)°$

$V = 4028.00 (9) Å³$

$Z = 4$

$F(000) = 1900$

$D_x = 1.518 \text{ Mg m}^{-3}$

Cu Kα radiation, λ = 1.54184 Å

Cell parameters from 32121 reflections

$\theta = 3.7-76.5°$

$\mu = 1.78 \text{ mm}^{-1}$

$T = 110 K$

Prism, violet

$0.25 \times 0.16 \times 0.14 \text{ mm}$

Data collection

Rigaku Oxford Diffraction SuperNova (Cu) X-
ray Source
diffractometer

Radiation source: micro-focus sealed X-ray tube
ω scans

Absorption correction: analytical
[CrysAlis PRO (Rigaku Oxford Diffraction,
2015)]; analytical numeric absorption correction
using a multi-faceted crystal model based on
expressions derived by Clark & Reid (1995)

$T_{\text{min}} = 0.708, T_{\text{max}} = 0.824$

68271 measured reflections

8435 independent reflections

7846 reflections with *I* > 2σ(*I*)

$R_{\text{int}} = 0.029$

$\theta_{\text{max}} = 76.2^{\circ}, \theta_{\text{min}} = 3.8^{\circ}$

$h = -20 \rightarrow 20$

$k = 0 \rightarrow 20$

$l = 0 \rightarrow 18$

Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.036$

$wR(F^2) = 0.110$

$S = 1.06$

8435 reflections

593 parameters

0 restraints

Primary atom site location: iterative

Hydrogen site location: difference Fourier map

H atoms treated by a mixture of independent
and constrained refinement

$w = 1/[\sigma^2(F_o^2) + (0.0562P)^2 + 2.6502P]$

where $P = (F_o^2 + 2F_c^2)/3$
$$ (\Delta/\sigma)_{\text{max}} = 0.002 \\ \Delta\rho_{\text{max}} = 0.47 \text{ e Å}^{-3} $$

$$ \Delta\rho_{\text{min}} = -0.50 \text{ e Å}^{-3} $$

Special details

**Geometry.** All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

<table><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>Cu1</td><td>0.0000</td><td>0.5000</td><td>0.5000</td><td>0.00740 (9)</td></tr><tr><td>Cu2</td><td>0.5000</td><td>0.5000</td><td>0.5000</td><td>0.00808 (9)</td></tr><tr><td>Si1</td><td>0.24851 (2)</td><td>0.50181 (2)</td><td>0.49951 (2)</td><td>0.01085 (11)</td></tr><tr><td>F1</td><td>0.14392 (6)</td><td>0.50149 (4)</td><td>0.50157 (6)</td><td>0.01423 (19)</td></tr><tr><td>F2</td><td>0.35288 (6)</td><td>0.49872 (4)</td><td>0.49705 (6)</td><td>0.01514 (19)</td></tr><tr><td>F5</td><td>0.25214 (6)</td><td>0.49217 (7)</td><td>0.61255 (7)</td><td>0.0327 (3)</td></tr><tr><td>F6</td><td>0.25001 (5)</td><td>0.60099 (6)</td><td>0.50857 (8)</td><td>0.0313 (3)</td></tr><tr><td>F3</td><td>0.24470 (6)</td><td>0.51068 (7)</td><td>0.38628 (7)</td><td>0.0305 (2)</td></tr><tr><td>F4</td><td>0.24575 (5)</td><td>0.40086 (6)</td><td>0.48849 (9)</td><td>0.0356 (3)</td></tr><tr><td>N1</td><td>-0.00035 (7)</td><td>0.41543 (7)</td><td>0.59766 (8)</td><td>0.0104 (2)</td></tr><tr><td>O52</td><td>0.24669 (7)</td><td>0.22533 (8)</td><td>0.69796 (10)</td><td>0.0304 (3)</td></tr><tr><td>N7</td><td>-0.00003 (7)</td><td>0.09067 (7)</td><td>0.90635 (7)</td><td>0.0104 (2)</td></tr><tr><td>N19</td><td>0.50157 (7)</td><td>0.08206 (7)</td><td>0.10342 (7)</td><td>0.0103 (2)</td></tr><tr><td>N13</td><td>0.50009 (7)</td><td>0.40834 (7)</td><td>0.41061 (7)</td><td>0.0102 (2)</td></tr><tr><td>O53</td><td>0.29213 (8)</td><td>0.07136 (8)</td><td>0.73649 (9)</td><td>0.0319 (3)</td></tr><tr><td>O50</td><td>0.27901 (8)</td><td>0.11159 (8)</td><td>0.42810 (9)</td><td>0.0326 (3)</td></tr><tr><td>O51</td><td>0.29696 (9)</td><td>0.24956 (9)</td><td>0.52512 (10)</td><td>0.0374 (3)</td></tr><tr><td>N43</td><td>0.55301 (8)</td><td>0.94138 (8)</td><td>0.35053 (9)</td><td>0.0224 (3)</td></tr><tr><td>O49</td><td>0.22422 (9)</td><td>0.11500 (9)</td><td>0.25239 (9)</td><td>0.0375 (3)</td></tr><tr><td>N37</td><td>0.23466 (8)</td><td>0.82015 (8)</td><td>0.64527 (10)</td><td>0.0244 (3)</td></tr><tr><td>N31</td><td>0.26526 (8)</td><td>0.82439 (10)</td><td>0.32164 (10)</td><td>0.0281 (3)</td></tr><tr><td>C16</td><td>0.50172 (8)</td><td>0.27683 (8)</td><td>0.29304 (9)</td><td>0.0117 (3)</td></tr><tr><td>C17</td><td>0.56598 (8)</td><td>0.33166 (8)</td><td>0.29579 (9)</td><td>0.0136 (3)</td></tr><tr><td>H17</td><td>0.6114</td><td>0.3250</td><td>0.2572</td><td>0.016*</td></tr><tr><td>C22</td><td>0.50242 (8)</td><td>0.20746 (8)</td><td>0.23027 (9)</td><td>0.0113 (3)</td></tr><tr><td>C4</td><td>-0.00106 (8)</td><td>0.28967 (8)</td><td>0.72282 (9)</td><td>0.0131 (3)</td></tr><tr><td>C20</td><td>0.43162 (8)</td><td>0.11255 (8)</td><td>0.13529 (9)</td><td>0.0141 (3)</td></tr><tr><td>H20</td><td>0.3814</td><td>0.0907</td><td>0.1139</td><td>0.017*</td></tr><tr><td>C10</td><td>-0.00090 (8)</td><td>0.22170 (8)</td><td>0.78738 (9)</td><td>0.0132 (3)</td></tr><tr><td>C15</td><td>0.43615 (8)</td><td>0.29027 (8)</td><td>0.35038 (9)</td><td>0.0146 (3)</td></tr><tr><td>H15</td><td>0.3911</td><td>0.2543</td><td>0.3504</td><td>0.018*</td></tr><tr><td>C18</td><td>0.56320 (8)</td><td>0.39594 (8)</td><td>0.35523 (9)</td><td>0.0125 (3)</td></tr><tr><td>H18</td><td>0.6076</td><td>0.4327</td><td>0.3569</td><td>0.015*</td></tr><tr><td>C9</td><td>0.07202 (8)</td><td>0.18464 (9)</td><td>0.81404 (10)</td><td>0.0164 (3)</td></tr><tr><td>H9</td><td>0.1227</td><td>0.2038</td><td>0.7920</td><td>0.020*</td></tr><tr><td>C3</td><td>-0.06460 (8)</td><td>0.34570 (8)</td><td>0.71891 (9)</td><td>0.0144 (3)</td></tr><tr><td>H3</td><td>-0.1089</td><td>0.3418</td><td>0.7595</td><td>0.017*</td></tr></tbody></table>
<table>
  <tr>
    <td>C21</td>
    <td>0.42956 (8)</td>
    <td>0.17432 (9)</td>
    <td>0.19781 (9)</td>
    <td>0.0145 (3)</td>
  </tr>
  <tr>
    <td>H21</td>
    <td>0.3787</td>
    <td>0.1941</td>
    <td>0.2186</td>
    <td>0.017*</td>
  </tr>
  <tr>
    <td>C14</td>
    <td>0.43721 (8)</td>
    <td>0.35642 (8)</td>
    <td>0.40738 (9)</td>
    <td>0.0147 (3)</td>
  </tr>
  <tr>
    <td>H14</td>
    <td>0.3919</td>
    <td>0.3654</td>
    <td>0.4455</td>
    <td>0.018*</td>
  </tr>
  <tr>
    <td>C8</td>
    <td>0.06999 (8)</td>
    <td>0.11997 (9)</td>
    <td>0.87270 (10)</td>
    <td>0.0155 (3)</td>
  </tr>
  <tr>
    <td>H8</td>
    <td>0.1200</td>
    <td>0.0952</td>
    <td>0.8900</td>
    <td>0.019*</td>
  </tr>
  <tr>
    <td>C5</td>
    <td>0.06262 (8)</td>
    <td>0.29879 (9)</td>
    <td>0.66202 (10)</td>
    <td>0.0162 (3)</td>
  </tr>
  <tr>
    <td>H5</td>
    <td>0.1066</td>
    <td>0.2616</td>
    <td>0.6620</td>
    <td>0.019*</td>
  </tr>
  <tr>
    <td>C24</td>
    <td>0.57206 (8)</td>
    <td>0.11186 (9)</td>
    <td>0.13636 (10)</td>
    <td>0.0156 (3)</td>
  </tr>
  <tr>
    <td>H24</td>
    <td>0.6220</td>
    <td>0.0897</td>
    <td>0.1158</td>
    <td>0.019*</td>
  </tr>
  <tr>
    <td>C23</td>
    <td>0.57484 (8)</td>
    <td>0.17385 (9)</td>
    <td>0.19922 (10)</td>
    <td>0.0160 (3)</td>
  </tr>
  <tr>
    <td>H23</td>
    <td>0.6259</td>
    <td>0.1933</td>
    <td>0.2210</td>
    <td>0.019*</td>
  </tr>
  <tr>
    <td>C11</td>
    <td>-0.07321 (8)</td>
    <td>0.19167 (9)</td>
    <td>0.82304 (9)</td>
    <td>0.0147 (3)</td>
  </tr>
  <tr>
    <td>H11</td>
    <td>-0.1240</td>
    <td>0.2156</td>
    <td>0.8072</td>
    <td>0.018*</td>
  </tr>
  <tr>
    <td>C12</td>
    <td>-0.07035 (8)</td>
    <td>0.12663 (9)</td>
    <td>0.88184 (9)</td>
    <td>0.0142 (3)</td>
  </tr>
  <tr>
    <td>H12</td>
    <td>-0.1200</td>
    <td>0.1068</td>
    <td>0.9057</td>
    <td>0.017*</td>
  </tr>
  <tr>
    <td>C2</td>
    <td>-0.06252 (8)</td>
    <td>0.40681 (8)</td>
    <td>0.65549 (9)</td>
    <td>0.0130 (3)</td>
  </tr>
  <tr>
    <td>H2</td>
    <td>-0.1065</td>
    <td>0.4440</td>
    <td>0.6527</td>
    <td>0.016*</td>
  </tr>
  <tr>
    <td>C45</td>
    <td>0.42153 (9)</td>
    <td>0.96535 (9)</td>
    <td>0.41679 (11)</td>
    <td>0.0208 (3)</td>
  </tr>
  <tr>
    <td>H45</td>
    <td>0.3752</td>
    <td>0.9994</td>
    <td>0.4215</td>
    <td>0.025*</td>
  </tr>
  <tr>
    <td>C6</td>
    <td>0.06131 (8)</td>
    <td>0.36237 (9)</td>
    <td>0.60178 (10)</td>
    <td>0.0152 (3)</td>
  </tr>
  <tr>
    <td>H6</td>
    <td>0.1058</td>
    <td>0.3687</td>
    <td>0.5618</td>
    <td>0.018*</td>
  </tr>
  <tr>
    <td>C46</td>
    <td>0.42614 (9)</td>
    <td>0.89392 (9)</td>
    <td>0.46622 (10)</td>
    <td>0.0173 (3)</td>
  </tr>
  <tr>
    <td>C44</td>
    <td>0.48547 (10)</td>
    <td>0.98589 (10)</td>
    <td>0.36069 (11)</td>
    <td>0.0226 (3)</td>
  </tr>
  <tr>
    <td>H44</td>
    <td>0.4811</td>
    <td>1.0346</td>
    <td>0.3273</td>
    <td>0.027*</td>
  </tr>
  <tr>
    <td>C47</td>
    <td>0.49637 (9)</td>
    <td>0.84765 (9)</td>
    <td>0.45646 (10)</td>
    <td>0.0201 (3)</td>
  </tr>
  <tr>
    <td>H47</td>
    <td>0.5025</td>
    <td>0.7986</td>
    <td>0.4889</td>
    <td>0.024*</td>
  </tr>
  <tr>
    <td>C38</td>
    <td>0.28158 (9)</td>
    <td>0.76657 (9)</td>
    <td>0.60272 (10)</td>
    <td>0.0208 (3)</td>
  </tr>
  <tr>
    <td>H38</td>
    <td>0.2714</td>
    <td>0.7110</td>
    <td>0.6125</td>
    <td>0.025*</td>
  </tr>
  <tr>
    <td>N25</td>
    <td>-0.12407 (9)</td>
    <td>0.91210 (10)</td>
    <td>0.49597 (11)</td>
    <td>0.0340 (4)</td>
  </tr>
  <tr>
    <td>C39</td>
    <td>0.34424 (9)</td>
    <td>0.78762 (9)</td>
    <td>0.54526 (10)</td>
    <td>0.0195 (3)</td>
  </tr>
  <tr>
    <td>H39</td>
    <td>0.3764</td>
    <td>0.7470</td>
    <td>0.5179</td>
    <td>0.023*</td>
  </tr>
  <tr>
    <td>C40</td>
    <td>0.36000 (9)</td>
    <td>0.86869 (9)</td>
    <td>0.52772 (10)</td>
    <td>0.0180 (3)</td>
  </tr>
  <tr>
    <td>C36</td>
    <td>0.22422 (10)</td>
    <td>0.77389 (11)</td>
    <td>0.37480 (11)</td>
    <td>0.0253 (3)</td>
  </tr>
  <tr>
    <td>H36</td>
    <td>0.2459</td>
    <td>0.7215</td>
    <td>0.3846</td>
    <td>0.030*</td>
  </tr>
  <tr>
    <td>C48</td>
    <td>0.55719 (9)</td>
    <td>0.87357 (10)</td>
    <td>0.39917 (11)</td>
    <td>0.0222 (3)</td>
  </tr>
  <tr>
    <td>H48</td>
    <td>0.6047</td>
    <td>0.8413</td>
    <td>0.3941</td>
    <td>0.027*</td>
  </tr>
  <tr>
    <td>C34</td>
    <td>0.11765 (9)</td>
    <td>0.86961 (10)</td>
    <td>0.40037 (10)</td>
    <td>0.0224 (3)</td>
  </tr>
  <tr>
    <td>C35</td>
    <td>0.15162 (9)</td>
    <td>0.79402 (10)</td>
    <td>0.41632 (11)</td>
    <td>0.0231 (3)</td>
  </tr>
  <tr>
    <td>H35</td>
    <td>0.1254</td>
    <td>0.7568</td>
    <td>0.4551</td>
    <td>0.028*</td>
  </tr>
  <tr>
    <td>C33</td>
    <td>0.16047 (10)</td>
    <td>0.92295 (10)</td>
    <td>0.34582 (11)</td>
    <td>0.0266 (3)</td>
  </tr>
  <tr>
    <td>H33</td>
    <td>0.1399</td>
    <td>0.9754</td>
    <td>0.3338</td>
    <td>0.032*</td>
  </tr>
  <tr>
    <td>C28</td>
    <td>0.03559 (10)</td>
    <td>0.88875 (10)</td>
    <td>0.43575 (11)</td>
    <td>0.0232 (3)</td>
  </tr>
  <tr>
    <td>C41</td>
    <td>0.31092 (10)</td>
    <td>0.92455 (10)</td>
    <td>0.57120 (12)</td>
    <td>0.0254 (3)</td>
  </tr>
  <tr>
    <td>H41</td>
    <td>0.3184</td>
    <td>0.9805</td>
    <td>0.5613</td>
    <td>0.030*</td>
  </tr>
  <tr>
    <td>C27</td>
    <td>0.01285 (10)</td>
    <td>0.86650 (11)</td>
    <td>0.52287 (12)</td>
    <td>0.0286 (4)</td>
  </tr>
  <tr>
    <td>H27</td>
    <td>0.0513</td>
    <td>0.8423</td>
    <td>0.5630</td>
    <td>0.034*</td>
  </tr>
  <tr>
    <td>C32</td>
    <td>0.23375 (10)</td>
    <td>0.89772 (11)</td>
    <td>0.30952 (12)</td>
    <td>0.0286 (4)</td>
  </tr>
</table>
<table><tr><td>H32</td><td>0.2634</td><td>0.9349</td><td>0.2738</td><td>0.034*</td></tr><tr><td>C42</td><td>0.25108 (10)</td><td>0.89764 (10)</td><td>0.62910 (13)</td><td>0.0299 (4)</td></tr><tr><td>H42</td><td>0.2195</td><td>0.9370</td><td>0.6595</td><td>0.036*</td></tr><tr><td>C26</td><td>-0.06647 (11)</td><td>0.88027 (12)</td><td>0.54980 (13)</td><td>0.0335 (4)</td></tr><tr><td>H26</td><td>-0.0808</td><td>0.8663</td><td>0.6098</td><td>0.040*</td></tr><tr><td>C29</td><td>-0.02335 (11)</td><td>0.92411 (11)</td><td>0.38086 (12)</td><td>0.0302 (4)</td></tr><tr><td>H29</td><td>-0.0100</td><td>0.9422</td><td>0.3219</td><td>0.036*</td></tr><tr><td>C30</td><td>-0.10216 (12)</td><td>0.93284 (12)</td><td>0.41284 (14)</td><td>0.0367 (4)</td></tr><tr><td>H30</td><td>-0.1425</td><td>0.9547</td><td>0.3734</td><td>0.044*</td></tr><tr><td>H53B</td><td>0.2849 (14)</td><td>0.0514 (14)</td><td>0.7835 (17)</td><td>0.034 (6)*</td></tr><tr><td>H52B</td><td>0.2595 (15)</td><td>0.1754 (16)</td><td>0.7175 (17)</td><td>0.046 (7)*</td></tr><tr><td>H53A</td><td>0.3396 (18)</td><td>0.0590 (18)</td><td>0.720 (2)</td><td>0.066 (9)*</td></tr><tr><td>H52A</td><td>0.2588 (15)</td><td>0.2311 (15)</td><td>0.6395 (18)</td><td>0.046 (7)*</td></tr><tr><td>H50A</td><td>0.2641 (16)</td><td>0.1230 (17)</td><td>0.360 (2)</td><td>0.060 (8)*</td></tr><tr><td>H49B</td><td>0.2334 (18)</td><td>0.0814 (19)</td><td>0.201 (2)</td><td>0.069 (9)*</td></tr><tr><td>H50B</td><td>0.2281 (19)</td><td>0.0997 (19)</td><td>0.457 (2)</td><td>0.072 (9)*</td></tr><tr><td>H49A</td><td>0.234 (2)</td><td>0.174 (2)</td><td>0.241 (2)</td><td>0.100 (12)*</td></tr><tr><td>H51B</td><td>0.2650 (13)</td><td>0.2899 (15)</td><td>0.5027 (14)</td><td>0.034 (6)*</td></tr><tr><td>H51A</td><td>0.281 (2)</td><td>0.207 (2)</td><td>0.480 (2)</td><td>0.093 (11)*</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>Cu1</td><td>0.01176 (16)</td><td>0.00446 (15)</td><td>0.00599 (15)</td><td>-0.00002 (9)</td><td>0.00097 (11)</td><td>0.00010 (8)</td></tr><tr><td>Cu2</td><td>0.01341 (16)</td><td>0.00456 (15)</td><td>0.00628 (15)</td><td>0.00000 (9)</td><td>0.00100 (11)</td><td>-0.00001 (8)</td></tr><tr><td>Si1</td><td>0.0105 (2)</td><td>0.0103 (2)</td><td>0.0118 (2)</td><td>0.00012 (11)</td><td>0.00098 (16)</td><td>-0.00039 (12)</td></tr><tr><td>F1</td><td>0.0130 (4)</td><td>0.0140 (5)</td><td>0.0157 (4)</td><td>-0.0002 (3)</td><td>0.0016 (3)</td><td>-0.0021 (3)</td></tr><tr><td>F2</td><td>0.0138 (4)</td><td>0.0154 (5)</td><td>0.0162 (5)</td><td>0.0010 (3)</td><td>0.0015 (3)</td><td>0.0020 (3)</td></tr><tr><td>F5</td><td>0.0194 (5)</td><td>0.0653 (8)</td><td>0.0135 (5)</td><td>-0.0001 (4)</td><td>0.0007 (4)</td><td>0.0059 (4)</td></tr><tr><td>F6</td><td>0.0196 (5)</td><td>0.0126 (5)</td><td>0.0616 (7)</td><td>-0.0008 (3)</td><td>0.0034 (5)</td><td>-0.0057 (4)</td></tr><tr><td>F3</td><td>0.0187 (5)</td><td>0.0589 (7)</td><td>0.0139 (5)</td><td>0.0055 (4)</td><td>0.0012 (4)</td><td>-0.0002 (4)</td></tr><tr><td>F4</td><td>0.0198 (5)</td><td>0.0123 (5)</td><td>0.0746 (8)</td><td>0.0007 (3)</td><td>0.0011 (5)</td><td>-0.0033 (4)</td></tr><tr><td>N1</td><td>0.0130 (5)</td><td>0.0087 (5)</td><td>0.0096 (5)</td><td>-0.0006 (4)</td><td>0.0001 (4)</td><td>0.0019 (4)</td></tr><tr><td>O52</td><td>0.0243 (6)</td><td>0.0258 (6)</td><td>0.0412 (8)</td><td>0.0045 (5)</td><td>0.0085 (5)</td><td>0.0034 (5)</td></tr><tr><td>N7</td><td>0.0137 (5)</td><td>0.0086 (5)</td><td>0.0088 (5)</td><td>-0.0003 (4)</td><td>0.0007 (4)</td><td>0.0019 (4)</td></tr><tr><td>N19</td><td>0.0145 (5)</td><td>0.0079 (5)</td><td>0.0085 (5)</td><td>0.0004 (4)</td><td>0.0004 (4)</td><td>-0.0010 (4)</td></tr><tr><td>N13</td><td>0.0139 (5)</td><td>0.0072 (5)</td><td>0.0094 (5)</td><td>0.0003 (4)</td><td>0.0005 (4)</td><td>-0.0011 (4)</td></tr><tr><td>O53</td><td>0.0346 (7)</td><td>0.0311 (7)</td><td>0.0302 (7)</td><td>0.0059 (5)</td><td>0.0124 (5)</td><td>0.0096 (5)</td></tr><tr><td>O50</td><td>0.0271 (6)</td><td>0.0342 (7)</td><td>0.0366 (7)</td><td>0.0047 (5)</td><td>0.0013 (5)</td><td>-0.0021 (5)</td></tr><tr><td>O51</td><td>0.0474 (8)</td><td>0.0258 (7)</td><td>0.0389 (7)</td><td>0.0018 (6)</td><td>-0.0021 (6)</td><td>0.0054 (6)</td></tr><tr><td>N43</td><td>0.0228 (6)</td><td>0.0233 (7)</td><td>0.0212 (6)</td><td>-0.0028 (5)</td><td>0.0009 (5)</td><td>-0.0016 (5)</td></tr><tr><td>O49</td><td>0.0472 (8)</td><td>0.0342 (7)</td><td>0.0310 (7)</td><td>0.0016 (6)</td><td>0.0001 (6)</td><td>0.0007 (6)</td></tr><tr><td>N37</td><td>0.0198 (6)</td><td>0.0231 (7)</td><td>0.0305 (7)</td><td>-0.0016 (5)</td><td>0.0044 (5)</td><td>-0.0003 (6)</td></tr><tr><td>N31</td><td>0.0206 (6)</td><td>0.0401 (8)</td><td>0.0238 (7)</td><td>-0.0031 (6)</td><td>0.0021 (5)</td><td>-0.0034 (6)</td></tr><tr><td>C16</td><td>0.0136 (6)</td><td>0.0099 (6)</td><td>0.0118 (6)</td><td>0.0007 (5)</td><td>-0.0003 (5)</td><td>-0.0022 (5)</td></tr><tr><td>C17</td><td>0.0134 (6)</td><td>0.0136 (6)</td><td>0.0138 (6)</td><td>-0.0008 (5)</td><td>0.0031 (5)</td><td>-0.0031 (5)</td></tr><tr><td>C22</td><td>0.0142 (6)</td><td>0.0089 (6)</td><td>0.0109 (6)</td><td>-0.0007 (5)</td><td>0.0007 (5)</td><td>-0.0015 (5)</td></tr><tr><td>C4</td><td>0.0139 (6)</td><td>0.0118 (6)</td><td>0.0137 (6)</td><td>-0.0001 (5)</td><td>0.0003 (5)</td><td>0.0042 (5)</td></tr></tbody></table>
<table><tr><td>C20</td><td>0.0133 (6)</td><td>0.0127 (6)</td><td>0.0162 (7)</td><td>-0.0014 (5)</td><td>0.0012 (5)</td><td>-0.0040 (5)</td></tr><tr><td>C10</td><td>0.0148 (6)</td><td>0.0116 (6)</td><td>0.0132 (6)</td><td>0.0004 (5)</td><td>0.0016 (5)</td><td>0.0047 (5)</td></tr><tr><td>C15</td><td>0.0143 (6)</td><td>0.0126 (6)</td><td>0.0171 (7)</td><td>-0.0030 (5)</td><td>0.0032 (5)</td><td>-0.0043 (5)</td></tr><tr><td>C18</td><td>0.0140 (6)</td><td>0.0113 (6)</td><td>0.0122 (6)</td><td>-0.0010 (5)</td><td>0.0006 (5)</td><td>-0.0018 (5)</td></tr><tr><td>C9</td><td>0.0121 (6)</td><td>0.0179 (7)</td><td>0.0193 (7)</td><td>-0.0003 (5)</td><td>0.0022 (5)</td><td>0.0080 (6)</td></tr><tr><td>C3</td><td>0.0141 (6)</td><td>0.0155 (7)</td><td>0.0136 (6)</td><td>0.0015 (5)</td><td>0.0032 (5)</td><td>0.0042 (5)</td></tr><tr><td>C21</td><td>0.0126 (6)</td><td>0.0145 (7)</td><td>0.0164 (7)</td><td>0.0000 (5)</td><td>0.0022 (5)</td><td>-0.0045 (5)</td></tr><tr><td>C14</td><td>0.0159 (6)</td><td>0.0126 (6)</td><td>0.0157 (6)</td><td>-0.0011 (5)</td><td>0.0037 (5)</td><td>-0.0035 (5)</td></tr><tr><td>C8</td><td>0.0139 (6)</td><td>0.0148 (7)</td><td>0.0179 (7)</td><td>0.0016 (5)</td><td>0.0015 (5)</td><td>0.0058 (5)</td></tr><tr><td>C5</td><td>0.0131 (6)</td><td>0.0151 (7)</td><td>0.0205 (7)</td><td>0.0028 (5)</td><td>0.0032 (5)</td><td>0.0071 (5)</td></tr><tr><td>C24</td><td>0.0136 (6)</td><td>0.0154 (7)</td><td>0.0177 (7)</td><td>0.0016 (5)</td><td>0.0009 (5)</td><td>-0.0061 (5)</td></tr><tr><td>C23</td><td>0.0125 (6)</td><td>0.0175 (7)</td><td>0.0179 (7)</td><td>-0.0002 (5)</td><td>-0.0012 (5)</td><td>-0.0067 (5)</td></tr><tr><td>C11</td><td>0.0119 (6)</td><td>0.0153 (7)</td><td>0.0168 (6)</td><td>0.0016 (5)</td><td>0.0009 (5)</td><td>0.0057 (5)</td></tr><tr><td>C12</td><td>0.0132 (6)</td><td>0.0148 (7)</td><td>0.0147 (6)</td><td>-0.0005 (5)</td><td>0.0008 (5)</td><td>0.0044 (5)</td></tr><tr><td>C2</td><td>0.0145 (6)</td><td>0.0128 (6)</td><td>0.0118 (6)</td><td>0.0018 (5)</td><td>0.0005 (5)</td><td>0.0018 (5)</td></tr><tr><td>C45</td><td>0.0192 (7)</td><td>0.0177 (7)</td><td>0.0255 (8)</td><td>0.0006 (6)</td><td>-0.0016 (6)</td><td>-0.0001 (6)</td></tr><tr><td>C6</td><td>0.0139 (6)</td><td>0.0145 (7)</td><td>0.0174 (7)</td><td>0.0014 (5)</td><td>0.0032 (5)</td><td>0.0058 (5)</td></tr><tr><td>C46</td><td>0.0176 (7)</td><td>0.0174 (7)</td><td>0.0169 (7)</td><td>-0.0015 (5)</td><td>-0.0028 (5)</td><td>-0.0021 (5)</td></tr><tr><td>C44</td><td>0.0252 (8)</td><td>0.0187 (7)</td><td>0.0237 (8)</td><td>-0.0015 (6)</td><td>-0.0007 (6)</td><td>0.0022 (6)</td></tr><tr><td>C47</td><td>0.0205 (7)</td><td>0.0192 (7)</td><td>0.0205 (7)</td><td>0.0017 (6)</td><td>-0.0016 (6)</td><td>0.0003 (6)</td></tr><tr><td>C38</td><td>0.0222 (7)</td><td>0.0182 (7)</td><td>0.0219 (7)</td><td>-0.0019 (6)</td><td>-0.0013 (6)</td><td>0.0005 (6)</td></tr><tr><td>N25</td><td>0.0270 (7)</td><td>0.0306 (8)</td><td>0.0446 (9)</td><td>0.0051 (6)</td><td>0.0069 (7)</td><td>-0.0021 (7)</td></tr><tr><td>C39</td><td>0.0228 (7)</td><td>0.0171 (7)</td><td>0.0186 (7)</td><td>0.0014 (6)</td><td>-0.0001 (6)</td><td>-0.0008 (6)</td></tr><tr><td>C40</td><td>0.0158 (6)</td><td>0.0190 (7)</td><td>0.0193 (7)</td><td>-0.0011 (5)</td><td>-0.0024 (5)</td><td>0.0000 (6)</td></tr><tr><td>C36</td><td>0.0198 (7)</td><td>0.0319 (9)</td><td>0.0241 (8)</td><td>0.0008 (6)</td><td>-0.0012 (6)</td><td>-0.0023 (7)</td></tr><tr><td>C48</td><td>0.0194 (7)</td><td>0.0242 (8)</td><td>0.0230 (8)</td><td>0.0018 (6)</td><td>0.0002 (6)</td><td>-0.0020 (6)</td></tr><tr><td>C34</td><td>0.0214 (7)</td><td>0.0263 (8)</td><td>0.0194 (7)</td><td>-0.0025 (6)</td><td>0.0009 (6)</td><td>-0.0037 (6)</td></tr><tr><td>C35</td><td>0.0203 (7)</td><td>0.0283 (8)</td><td>0.0205 (7)</td><td>-0.0026 (6)</td><td>-0.0004 (6)</td><td>0.0006 (6)</td></tr><tr><td>C33</td><td>0.0294 (8)</td><td>0.0249 (8)</td><td>0.0255 (8)</td><td>-0.0039 (6)</td><td>0.0021 (6)</td><td>-0.0007 (6)</td></tr><tr><td>C28</td><td>0.0239 (8)</td><td>0.0210 (8)</td><td>0.0247 (8)</td><td>-0.0023 (6)</td><td>0.0024 (6)</td><td>-0.0037 (6)</td></tr><tr><td>C41</td><td>0.0216 (7)</td><td>0.0160 (7)</td><td>0.0387 (9)</td><td>-0.0005 (6)</td><td>0.0060 (7)</td><td>-0.0003 (6)</td></tr><tr><td>C27</td><td>0.0259 (8)</td><td>0.0352 (9)</td><td>0.0246 (8)</td><td>0.0020 (7)</td><td>0.0019 (6)</td><td>0.0002 (7)</td></tr><tr><td>C32</td><td>0.0260 (8)</td><td>0.0347 (9)</td><td>0.0253 (8)</td><td>-0.0092 (7)</td><td>0.0043 (6)</td><td>-0.0018 (7)</td></tr><tr><td>C42</td><td>0.0239 (8)</td><td>0.0204 (8)</td><td>0.0455 (10)</td><td>0.0011 (6)</td><td>0.0122 (7)</td><td>-0.0028 (7)</td></tr><tr><td>C26</td><td>0.0317 (9)</td><td>0.0346 (10)</td><td>0.0343 (10)</td><td>0.0012 (7)</td><td>0.0113 (7)</td><td>0.0000 (8)</td></tr><tr><td>C29</td><td>0.0334 (9)</td><td>0.0264 (9)</td><td>0.0308 (9)</td><td>0.0047 (7)</td><td>0.0041 (7)</td><td>0.0029 (7)</td></tr><tr><td>C30</td><td>0.0318 (9)</td><td>0.0341 (10)</td><td>0.0442 (11)</td><td>0.0112 (8)</td><td>0.0010 (8)</td><td>0.0038 (8)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>Cu1—N1<sup>i</sup></td><td>2.0156 (11)</td><td>C10—C9</td><td>1.3971 (19)</td></tr><tr><td>Cu1—N1</td><td>2.0156 (11)</td><td>C15—C14</td><td>1.3852 (19)</td></tr><tr><td>Cu1—N7<sup>ii</sup></td><td>2.0467 (11)</td><td>C15—H15</td><td>0.9500</td></tr><tr><td>Cu1—N7<sup>iii</sup></td><td>2.0467 (11)</td><td>C18—H18</td><td>0.9500</td></tr><tr><td>Cu1—F1<sup>i</sup></td><td>2.3585 (9)</td><td>C9—C8</td><td>1.3818 (19)</td></tr><tr><td>Cu1—F1</td><td>2.3585 (9)</td><td>C9—H9</td><td>0.9500</td></tr><tr><td>Cu2—N13<sup>iv</sup></td><td>2.0170 (11)</td><td>C3—C2</td><td>1.3832 (19)</td></tr><tr><td>Cu2—N13</td><td>2.0170 (11)</td><td>C3—H3</td><td>0.9500</td></tr></table>
<table>
  <tr>
    <td>Cu2—N19<sup>v</sup></td>
    <td>2.0494 (11)</td>
    <td>C21—H21</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Cu2—N19<sup>vi</sup></td>
    <td>2.0494 (11)</td>
    <td>C14—H14</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Cu2—F2</td>
    <td>2.4109 (9)</td>
    <td>C8—H8</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Cu2—F2<sup>iv</sup></td>
    <td>2.4109 (9)</td>
    <td>C5—C6</td>
    <td>1.3821 (19)</td>
  </tr>
  <tr>
    <td>Si1—F6</td>
    <td>1.6534 (11)</td>
    <td>C5—H5</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Si1—F5</td>
    <td>1.6806 (10)</td>
    <td>C24—C23</td>
    <td>1.3882 (19)</td>
  </tr>
  <tr>
    <td>Si1—F3</td>
    <td>1.6823 (10)</td>
    <td>C24—H24</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Si1—F4</td>
    <td>1.6855 (11)</td>
    <td>C23—H23</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>Si1—F2</td>
    <td>1.7120 (10)</td>
    <td>C11—C12</td>
    <td>1.3877 (19)</td>
  </tr>
  <tr>
    <td>Si1—F1</td>
    <td>1.7145 (10)</td>
    <td>C11—H11</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N1—C6</td>
    <td>1.3418 (18)</td>
    <td>C12—H12</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N1—C2</td>
    <td>1.3455 (17)</td>
    <td>C2—H2</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>O52—H52B</td>
    <td>0.90 (3)</td>
    <td>C45—C44</td>
    <td>1.387 (2)</td>
  </tr>
  <tr>
    <td>O52—H52A</td>
    <td>0.90 (3)</td>
    <td>C45—C46</td>
    <td>1.396 (2)</td>
  </tr>
  <tr>
    <td>N7—C12</td>
    <td>1.3442 (18)</td>
    <td>C45—H45</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N7—C8</td>
    <td>1.3470 (18)</td>
    <td>C6—H6</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N7—Cu1<sup>vii</sup></td>
    <td>2.0467 (11)</td>
    <td>C46—C47</td>
    <td>1.393 (2)</td>
  </tr>
  <tr>
    <td>N19—C24</td>
    <td>1.3432 (18)</td>
    <td>C46—C40</td>
    <td>1.484 (2)</td>
  </tr>
  <tr>
    <td>N19—C20</td>
    <td>1.3436 (18)</td>
    <td>C44—H44</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N19—Cu2<sup>viii</sup></td>
    <td>2.0494 (11)</td>
    <td>C47—C48</td>
    <td>1.384 (2)</td>
  </tr>
  <tr>
    <td>N13—C18</td>
    <td>1.3426 (17)</td>
    <td>C47—H47</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N13—C14</td>
    <td>1.3443 (18)</td>
    <td>C38—C39</td>
    <td>1.385 (2)</td>
  </tr>
  <tr>
    <td>O53—H53B</td>
    <td>0.78 (2)</td>
    <td>C38—H38</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>O53—H53A</td>
    <td>0.85 (3)</td>
    <td>N25—C30</td>
    <td>1.331 (3)</td>
  </tr>
  <tr>
    <td>O50—H50A</td>
    <td>1.05 (3)</td>
    <td>N25—C26</td>
    <td>1.337 (3)</td>
  </tr>
  <tr>
    <td>O50—H50B</td>
    <td>0.96 (3)</td>
    <td>C39—C40</td>
    <td>1.396 (2)</td>
  </tr>
  <tr>
    <td>O51—H51B</td>
    <td>0.91 (3)</td>
    <td>C39—H39</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>O51—H51A</td>
    <td>1.00 (4)</td>
    <td>C40—C41</td>
    <td>1.391 (2)</td>
  </tr>
  <tr>
    <td>N43—C48</td>
    <td>1.338 (2)</td>
    <td>C36—C35</td>
    <td>1.386 (2)</td>
  </tr>
  <tr>
    <td>N43—C44</td>
    <td>1.341 (2)</td>
    <td>C36—H36</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>O49—H49B</td>
    <td>0.96 (3)</td>
    <td>C48—H48</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>O49—H49A</td>
    <td>1.00 (4)</td>
    <td>C34—C35</td>
    <td>1.393 (2)</td>
  </tr>
  <tr>
    <td>N37—C42</td>
    <td>1.337 (2)</td>
    <td>C34—C33</td>
    <td>1.394 (2)</td>
  </tr>
  <tr>
    <td>N37—C38</td>
    <td>1.338 (2)</td>
    <td>C34—C28</td>
    <td>1.483 (2)</td>
  </tr>
  <tr>
    <td>N31—C32</td>
    <td>1.334 (2)</td>
    <td>C35—H35</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>N31—C36</td>
    <td>1.337 (2)</td>
    <td>C33—C32</td>
    <td>1.386 (2)</td>
  </tr>
  <tr>
    <td>C16—C17</td>
    <td>1.3927 (19)</td>
    <td>C33—H33</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C16—C15</td>
    <td>1.3947 (18)</td>
    <td>C28—C29</td>
    <td>1.386 (2)</td>
  </tr>
  <tr>
    <td>C16—C22</td>
    <td>1.4803 (19)</td>
    <td>C28—C27</td>
    <td>1.396 (2)</td>
  </tr>
  <tr>
    <td>C17—C18</td>
    <td>1.3845 (19)</td>
    <td>C41—C42</td>
    <td>1.384 (2)</td>
  </tr>
  <tr>
    <td>C17—H17</td>
    <td>0.9500</td>
    <td>C41—H41</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C22—C23</td>
    <td>1.3942 (19)</td>
    <td>C27—C26</td>
    <td>1.383 (2)</td>
  </tr>
  <tr>
    <td>C22—C21</td>
    <td>1.3950 (19)</td>
    <td>C27—H27</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C4—C5</td>
    <td>1.3938 (19)</td>
    <td>C32—H32</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C4—C3</td>
    <td>1.3974 (19)</td>
    <td>C42—H42</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C4—C10</td>
    <td>1.4791 (19)</td>
    <td>C26—H26</td>
    <td>0.9500</td>
  </tr>
  <tr>
    <td>C20—C21</td>
    <td>1.3823 (19)</td>
    <td>C29—C30</td>
    <td>1.388 (3)</td>
  </tr>
  <tr>
    <td>C20—H20</td>
    <td>0.9500</td>
    <td>C29—H29</td>
    <td>0.9500</td>
  </tr>
</table>
<table><thead><tr><th>C10—C11</th><th>1.3948 (19)</th><th>C30—H30</th><th>0.9500</th></tr></thead><tbody><tr><td>N1<sup>i</sup>—Cu1—N1</td><td>180.00 (6)</td><td>C2—C3—C4</td><td>119.53 (12)</td></tr><tr><td>N1<sup>i</sup>—Cu1—N7<sup>ii</sup></td><td>91.58 (5)</td><td>C2—C3—H3</td><td>120.2</td></tr><tr><td>N1—Cu1—N7<sup>ii</sup></td><td>88.42 (5)</td><td>C4—C3—H3</td><td>120.2</td></tr><tr><td>N1<sup>i</sup>—Cu1—N7<sup>iii</sup></td><td>88.42 (5)</td><td>C20—C21—C22</td><td>119.74 (12)</td></tr><tr><td>N1—Cu1—N7<sup>iii</sup></td><td>91.58 (5)</td><td>C20—C21—H21</td><td>120.1</td></tr><tr><td>N7<sup>ii</sup>—Cu1—N7<sup>iii</sup></td><td>180.0</td><td>C22—C21—H21</td><td>120.1</td></tr><tr><td>N1<sup>i</sup>—Cu1—F1<sup>i</sup></td><td>90.65 (4)</td><td>N13—C14—C15</td><td>122.35 (12)</td></tr><tr><td>N1—Cu1—F1<sup>i</sup></td><td>89.35 (4)</td><td>N13—C14—H14</td><td>118.8</td></tr><tr><td>N7<sup>ii</sup>—Cu1—F1<sup>i</sup></td><td>89.60 (4)</td><td>C15—C14—H14</td><td>118.8</td></tr><tr><td>N7<sup>iii</sup>—Cu1—F1<sup>i</sup></td><td>90.40 (4)</td><td>N7—C8—C9</td><td>122.68 (13)</td></tr><tr><td>N1<sup>i</sup>—Cu1—F1</td><td>89.35 (4)</td><td>N7—C8—H8</td><td>118.7</td></tr><tr><td>N1—Cu1—F1</td><td>90.65 (4)</td><td>C9—C8—H8</td><td>118.7</td></tr><tr><td>N7<sup>ii</sup>—Cu1—F1</td><td>90.40 (4)</td><td>C6—C5—C4</td><td>119.54 (13)</td></tr><tr><td>N7<sup>iii</sup>—Cu1—F1</td><td>89.60 (4)</td><td>C6—C5—H5</td><td>120.2</td></tr><tr><td>F1<sup>i</sup>—Cu1—F1</td><td>180.0</td><td>C4—C5—H5</td><td>120.2</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N13</td><td>180.0</td><td>N19—C24—C23</td><td>122.55 (12)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N19<sup>v</sup></td><td>90.73 (5)</td><td>N19—C24—H24</td><td>118.7</td></tr><tr><td>N13—Cu2—N19<sup>v</sup></td><td>89.27 (5)</td><td>C23—C24—H24</td><td>118.7</td></tr><tr><td>N13<sup>iv</sup>—Cu2—N19<sup>vi</sup></td><td>89.27 (5)</td><td>C24—C23—C22</td><td>119.76 (12)</td></tr><tr><td>N13—Cu2—N19<sup>vi</sup></td><td>90.73 (5)</td><td>C24—C23—H23</td><td>120.1</td></tr><tr><td>N19<sup>v</sup>—Cu2—N19<sup>vi</sup></td><td>180.0</td><td>C22—C23—H23</td><td>120.1</td></tr><tr><td>N13<sup>iv</sup>—Cu2—F2</td><td>90.59 (4)</td><td>C12—C11—C10</td><td>119.54 (12)</td></tr><tr><td>N13—Cu2—F2</td><td>89.41 (4)</td><td>C12—C11—H11</td><td>120.2</td></tr><tr><td>N19<sup>v</sup>—Cu2—F2</td><td>90.67 (4)</td><td>C10—C11—H11</td><td>120.2</td></tr><tr><td>N19<sup>vi</sup>—Cu2—F2</td><td>89.33 (4)</td><td>N7—C12—C11</td><td>122.54 (12)</td></tr><tr><td>N13<sup>iv</sup>—Cu2—F2<sup>iv</sup></td><td>89.41 (4)</td><td>N7—C12—H12</td><td>118.7</td></tr><tr><td>N13—Cu2—F2<sup>iv</sup></td><td>90.59 (4)</td><td>C11—C12—H12</td><td>118.7</td></tr><tr><td>N19<sup>v</sup>—Cu2—F2<sup>iv</sup></td><td>89.33 (4)</td><td>N1—C2—C3</td><td>122.29 (12)</td></tr><tr><td>N19<sup>vi</sup>—Cu2—F2<sup>iv</sup></td><td>90.67 (4)</td><td>N1—C2—H2</td><td>118.9</td></tr><tr><td>F2—Cu2—F2<sup>iv</sup></td><td>180.0</td><td>C3—C2—H2</td><td>118.9</td></tr><tr><td>F6—Si1—F5</td><td>90.80 (6)</td><td>C44—C45—C46</td><td>119.09 (14)</td></tr><tr><td>F6—Si1—F3</td><td>89.64 (6)</td><td>C44—C45—H45</td><td>120.5</td></tr><tr><td>F5—Si1—F3</td><td>179.55 (6)</td><td>C46—C45—H45</td><td>120.5</td></tr><tr><td>F6—Si1—F4</td><td>178.87 (6)</td><td>N1—C6—C5</td><td>122.51 (12)</td></tr><tr><td>F5—Si1—F4</td><td>90.12 (6)</td><td>N1—C6—H6</td><td>118.7</td></tr><tr><td>F3—Si1—F4</td><td>89.44 (6)</td><td>C5—C6—H6</td><td>118.7</td></tr><tr><td>F6—Si1—F2</td><td>91.01 (4)</td><td>C47—C46—C45</td><td>117.06 (14)</td></tr><tr><td>F5—Si1—F2</td><td>89.67 (5)</td><td>C47—C46—C40</td><td>121.19 (14)</td></tr><tr><td>F3—Si1—F2</td><td>90.41 (5)</td><td>C45—C46—C40</td><td>121.74 (13)</td></tr><tr><td>F4—Si1—F2</td><td>89.64 (4)</td><td>N43—C44—C45</td><td>124.17 (15)</td></tr><tr><td>F6—Si1—F1</td><td>90.89 (4)</td><td>N43—C44—H44</td><td>117.9</td></tr><tr><td>F5—Si1—F1</td><td>90.35 (5)</td><td>C45—C44—H44</td><td>117.9</td></tr><tr><td>F3—Si1—F1</td><td>89.56 (5)</td><td>C48—C47—C46</td><td>119.55 (14)</td></tr><tr><td>F4—Si1—F1</td><td>88.45 (4)</td><td>C48—C47—H47</td><td>120.2</td></tr><tr><td>F2—Si1—F1</td><td>178.09 (4)</td><td>C46—C47—H47</td><td>120.2</td></tr><tr><td>Si1—F1—Cu1</td><td>178.36 (5)</td><td>N37—C38—C39</td><td>123.69 (14)</td></tr></tbody></table>
<table>
  <tr>
    <td>Si1—F2—Cu2</td>
    <td>176.83 (5)</td>
  </tr>
  <tr>
    <td>C6—N1—C2</td>
    <td>118.46 (12)</td>
  </tr>
  <tr>
    <td>C6—N1—Cu1</td>
    <td>118.82 (9)</td>
  </tr>
  <tr>
    <td>C2—N1—Cu1</td>
    <td>122.58 (9)</td>
  </tr>
  <tr>
    <td>H52B—O52—H52A</td>
    <td>111 (2)</td>
  </tr>
  <tr>
    <td>C12—N7—C8</td>
    <td>118.09 (12)</td>
  </tr>
  <tr>
    <td>C12—N7—Cu1<sup>vii</sup></td>
    <td>120.22 (9)</td>
  </tr>
  <tr>
    <td>C8—N7—Cu1<sup>vii</sup></td>
    <td>121.50 (9)</td>
  </tr>
  <tr>
    <td>C24—N19—C20</td>
    <td>117.86 (12)</td>
  </tr>
  <tr>
    <td>C24—N19—Cu2<sup>viii</sup></td>
    <td>121.30 (9)</td>
  </tr>
  <tr>
    <td>C20—N19—Cu2<sup>viii</sup></td>
    <td>120.62 (9)</td>
  </tr>
  <tr>
    <td>C18—N13—C14</td>
    <td>118.38 (12)</td>
  </tr>
  <tr>
    <td>C18—N13—Cu2</td>
    <td>121.49 (9)</td>
  </tr>
  <tr>
    <td>C14—N13—Cu2</td>
    <td>120.10 (9)</td>
  </tr>
  <tr>
    <td>H53B—O53—H53A</td>
    <td>108 (3)</td>
  </tr>
  <tr>
    <td>H50A—O50—H50B</td>
    <td>105 (2)</td>
  </tr>
  <tr>
    <td>H51B—O51—H51A</td>
    <td>98 (2)</td>
  </tr>
  <tr>
    <td>C48—N43—C44</td>
    <td>116.18 (14)</td>
  </tr>
  <tr>
    <td>H49B—O49—H49A</td>
    <td>114 (3)</td>
  </tr>
  <tr>
    <td>C42—N37—C38</td>
    <td>115.99 (14)</td>
  </tr>
  <tr>
    <td>C32—N31—C36</td>
    <td>117.09 (14)</td>
  </tr>
  <tr>
    <td>C17—C16—C15</td>
    <td>117.72 (12)</td>
  </tr>
  <tr>
    <td>C17—C16—C22</td>
    <td>121.09 (12)</td>
  </tr>
  <tr>
    <td>C15—C16—C22</td>
    <td>121.19 (12)</td>
  </tr>
  <tr>
    <td>C18—C17—C16</td>
    <td>119.51 (12)</td>
  </tr>
  <tr>
    <td>C18—C17—H17</td>
    <td>120.2</td>
  </tr>
  <tr>
    <td>C16—C17—H17</td>
    <td>120.2</td>
  </tr>
  <tr>
    <td>C23—C22—C21</td>
    <td>117.19 (12)</td>
  </tr>
  <tr>
    <td>C23—C22—C16</td>
    <td>122.08 (12)</td>
  </tr>
  <tr>
    <td>C21—C22—C16</td>
    <td>120.70 (12)</td>
  </tr>
  <tr>
    <td>C5—C4—C3</td>
    <td>117.65 (12)</td>
  </tr>
  <tr>
    <td>C5—C4—C10</td>
    <td>120.26 (13)</td>
  </tr>
  <tr>
    <td>C3—C4—C10</td>
    <td>122.08 (12)</td>
  </tr>
  <tr>
    <td>N19—C20—C21</td>
    <td>122.84 (13)</td>
  </tr>
  <tr>
    <td>N19—C20—H20</td>
    <td>118.6</td>
  </tr>
  <tr>
    <td>C21—C20—H20</td>
    <td>118.6</td>
  </tr>
  <tr>
    <td>C11—C10—C9</td>
    <td>117.59 (12)</td>
  </tr>
  <tr>
    <td>C11—C10—C4</td>
    <td>121.48 (13)</td>
  </tr>
  <tr>
    <td>C9—C10—C4</td>
    <td>120.93 (12)</td>
  </tr>
  <tr>
    <td>C14—C15—C16</td>
    <td>119.54 (13)</td>
  </tr>
  <tr>
    <td>C14—C15—H15</td>
    <td>120.2</td>
  </tr>
  <tr>
    <td>C16—C15—H15</td>
    <td>120.2</td>
  </tr>
  <tr>
    <td>N13—C18—C17</td>
    <td>122.50 (12)</td>
  </tr>
  <tr>
    <td>N13—C18—H18</td>
    <td>118.8</td>
  </tr>
  <tr>
    <td>C17—C18—H18</td>
    <td>118.8</td>
  </tr>
  <tr>
    <td>C8—C9—C10</td>
    <td>119.56 (13)</td>
  </tr>
  <tr>
    <td>C8—C9—H9</td>
    <td>120.2</td>
  </tr>
  <tr>
    <td>C10—C9—H9</td>
    <td>120.2</td>
  </tr>
</table>

<table>
  <tr>
    <td>N37—C38—H38</td>
    <td>118.2</td>
  </tr>
  <tr>
    <td>C39—C38—H38</td>
    <td>118.2</td>
  </tr>
  <tr>
    <td>C30—N25—C26</td>
    <td>117.18 (15)</td>
  </tr>
  <tr>
    <td>C38—C39—C40</td>
    <td>119.83 (14)</td>
  </tr>
  <tr>
    <td>C38—C39—H39</td>
    <td>120.1</td>
  </tr>
  <tr>
    <td>C40—C39—H39</td>
    <td>120.1</td>
  </tr>
  <tr>
    <td>C41—C40—C39</td>
    <td>116.65 (14)</td>
  </tr>
  <tr>
    <td>C41—C40—C46</td>
    <td>121.72 (14)</td>
  </tr>
  <tr>
    <td>C39—C40—C46</td>
    <td>121.64 (13)</td>
  </tr>
  <tr>
    <td>N31—C36—C35</td>
    <td>123.33 (16)</td>
  </tr>
  <tr>
    <td>N31—C36—H36</td>
    <td>118.3</td>
  </tr>
  <tr>
    <td>C35—C36—H36</td>
    <td>118.3</td>
  </tr>
  <tr>
    <td>N43—C48—C47</td>
    <td>123.95 (14)</td>
  </tr>
  <tr>
    <td>N43—C48—H48</td>
    <td>118.0</td>
  </tr>
  <tr>
    <td>C47—C48—H48</td>
    <td>118.0</td>
  </tr>
  <tr>
    <td>C35—C34—C33</td>
    <td>117.94 (15)</td>
  </tr>
  <tr>
    <td>C35—C34—C28</td>
    <td>119.72 (14)</td>
  </tr>
  <tr>
    <td>C33—C34—C28</td>
    <td>122.19 (15)</td>
  </tr>
  <tr>
    <td>C36—C35—C34</td>
    <td>119.07 (15)</td>
  </tr>
  <tr>
    <td>C36—C35—H35</td>
    <td>120.5</td>
  </tr>
  <tr>
    <td>C34—C35—H35</td>
    <td>120.5</td>
  </tr>
  <tr>
    <td>C32—C33—C34</td>
    <td>118.45 (16)</td>
  </tr>
  <tr>
    <td>C32—C33—H33</td>
    <td>120.8</td>
  </tr>
  <tr>
    <td>C34—C33—H33</td>
    <td>120.8</td>
  </tr>
  <tr>
    <td>C29—C28—C27</td>
    <td>117.51 (15)</td>
  </tr>
  <tr>
    <td>C29—C28—C34</td>
    <td>120.85 (15)</td>
  </tr>
  <tr>
    <td>C27—C28—C34</td>
    <td>121.46 (15)</td>
  </tr>
  <tr>
    <td>C42—C41—C40</td>
    <td>119.25 (15)</td>
  </tr>
  <tr>
    <td>C42—C41—H41</td>
    <td>120.4</td>
  </tr>
  <tr>
    <td>C40—C41—H41</td>
    <td>120.4</td>
  </tr>
  <tr>
    <td>C26—C27—C28</td>
    <td>118.95 (17)</td>
  </tr>
  <tr>
    <td>C26—C27—H27</td>
    <td>120.5</td>
  </tr>
  <tr>
    <td>C28—C27—H27</td>
    <td>120.5</td>
  </tr>
  <tr>
    <td>N31—C32—C33</td>
    <td>124.04 (16)</td>
  </tr>
  <tr>
    <td>N31—C32—H32</td>
    <td>118.0</td>
  </tr>
  <tr>
    <td>C33—C32—H32</td>
    <td>118.0</td>
  </tr>
  <tr>
    <td>N37—C42—C41</td>
    <td>124.56 (15)</td>
  </tr>
  <tr>
    <td>N37—C42—H42</td>
    <td>117.7</td>
  </tr>
  <tr>
    <td>C41—C42—H42</td>
    <td>117.7</td>
  </tr>
  <tr>
    <td>N25—C26—C27</td>
    <td>123.59 (17)</td>
  </tr>
  <tr>
    <td>N25—C26—H26</td>
    <td>118.2</td>
  </tr>
  <tr>
    <td>C27—C26—H26</td>
    <td>118.2</td>
  </tr>
  <tr>
    <td>C28—C29—C30</td>
    <td>119.30 (17)</td>
  </tr>
  <tr>
    <td>C28—C29—H29</td>
    <td>120.3</td>
  </tr>
  <tr>
    <td>C30—C29—H29</td>
    <td>120.3</td>
  </tr>
  <tr>
    <td>N25—C30—C29</td>
    <td>123.38 (18)</td>
  </tr>
  <tr>
    <td>N25—C30—H30</td>
    <td>118.3</td>
  </tr>
  <tr>
    <td>C29—C30—H30</td>
    <td>118.3</td>
  </tr>
</table>
<table>
  <tr>
    <td>C15—C16—C17—C18</td>
    <td>0.9 (2)</td>
  </tr>
  <tr>
    <td>C22—C16—C17—C18</td>
    <td>179.87 (12)</td>
  </tr>
  <tr>
    <td>C17—C16—C22—C23</td>
    <td>26.6 (2)</td>
  </tr>
  <tr>
    <td>C15—C16—C22—C23</td>
    <td>-154.49 (14)</td>
  </tr>
  <tr>
    <td>C17—C16—C22—C21</td>
    <td>-151.72 (14)</td>
  </tr>
  <tr>
    <td>C15—C16—C22—C21</td>
    <td>27.22 (19)</td>
  </tr>
  <tr>
    <td>C24—N19—C20—C21</td>
    <td>2.0 (2)</td>
  </tr>
  <tr>
    <td>Cu2<sup>viii</sup>—N19—C20—C21</td>
    <td>-172.69 (11)</td>
  </tr>
  <tr>
    <td>C5—C4—C10—C11</td>
    <td>-154.60 (14)</td>
  </tr>
  <tr>
    <td>C3—C4—C10—C11</td>
    <td>24.2 (2)</td>
  </tr>
  <tr>
    <td>C5—C4—C10—C9</td>
    <td>24.7 (2)</td>
  </tr>
  <tr>
    <td>C3—C4—C10—C9</td>
    <td>-156.55 (14)</td>
  </tr>
  <tr>
    <td>C17—C16—C15—C14</td>
    <td>-0.2 (2)</td>
  </tr>
  <tr>
    <td>C22—C16—C15—C14</td>
    <td>-179.17 (13)</td>
  </tr>
  <tr>
    <td>C14—N13—C18—C17</td>
    <td>-0.5 (2)</td>
  </tr>
  <tr>
    <td>Cu2—N13—C18—C17</td>
    <td>177.47 (10)</td>
  </tr>
  <tr>
    <td>C16—C17—C18—N13</td>
    <td>-0.6 (2)</td>
  </tr>
  <tr>
    <td>C11—C10—C9—C8</td>
    <td>0.9 (2)</td>
  </tr>
  <tr>
    <td>C4—C10—C9—C8</td>
    <td>-178.38 (14)</td>
  </tr>
  <tr>
    <td>C5—C4—C3—C2</td>
    <td>0.5 (2)</td>
  </tr>
  <tr>
    <td>C10—C4—C3—C2</td>
    <td>-178.27 (13)</td>
  </tr>
  <tr>
    <td>N19—C20—C21—C22</td>
    <td>0.0 (2)</td>
  </tr>
  <tr>
    <td>C23—C22—C21—C20</td>
    <td>-2.0 (2)</td>
  </tr>
  <tr>
    <td>C16—C22—C21—C20</td>
    <td>176.33 (13)</td>
  </tr>
  <tr>
    <td>C18—N13—C14—C15</td>
    <td>1.2 (2)</td>
  </tr>
  <tr>
    <td>Cu2—N13—C14—C15</td>
    <td>-176.76 (11)</td>
  </tr>
  <tr>
    <td>C16—C15—C14—N13</td>
    <td>-0.9 (2)</td>
  </tr>
  <tr>
    <td>C12—N7—C8—C9</td>
    <td>-0.4 (2)</td>
  </tr>
  <tr>
    <td>Cu1<sup>vii</sup>—N7—C8—C9</td>
    <td>-175.57 (11)</td>
  </tr>
  <tr>
    <td>C10—C9—C8—N7</td>
    <td>-0.4 (2)</td>
  </tr>
  <tr>
    <td>C3—C4—C5—C6</td>
    <td>0.8 (2)</td>
  </tr>
  <tr>
    <td>C10—C4—C5—C6</td>
    <td>179.62 (13)</td>
  </tr>
  <tr>
    <td>C20—N19—C24—C23</td>
    <td>-2.0 (2)</td>
  </tr>
  <tr>
    <td>Cu2<sup>viii</sup>—N19—C24—C23</td>
    <td>172.69 (11)</td>
  </tr>
  <tr>
    <td>N19—C24—C23—C22</td>
    <td>-0.1 (2)</td>
  </tr>
  <tr>
    <td>C21—C22—C23—C24</td>
    <td>2.1 (2)</td>
  </tr>
  <tr>
    <td>C16—C22—C23—C24</td>
    <td>-176.27 (13)</td>
  </tr>
  <tr>
    <td>C9—C10—C11—C12</td>
    <td>-0.8 (2)</td>
  </tr>
  <tr>
    <td>C4—C10—C11—C12</td>
    <td>178.56 (13)</td>
  </tr>
  <tr>
    <td>C8—N7—C12—C11</td>
    <td>0.6 (2)</td>
  </tr>
  <tr>
    <td>Cu1<sup>vii</sup>—N7—C12—C11</td>
    <td>175.83 (11)</td>
  </tr>
  <tr>
    <td>C10—C11—C12—N7</td>
    <td>0.0 (2)</td>
  </tr>
  <tr>
    <td>C6—N1—C2—C3</td>
    <td>0.4 (2)</td>
  </tr>
  <tr>
    <td>Cu1—N1—C2—C3</td>
    <td>176.11 (10)</td>
  </tr>
</table>

<table>
  <tr>
    <td>C4—C3—C2—N1</td>
    <td>-1.1 (2)</td>
  </tr>
  <tr>
    <td>C2—N1—C6—C5</td>
    <td>1.0 (2)</td>
  </tr>
  <tr>
    <td>Cu1—N1—C6—C5</td>
    <td>-174.86 (11)</td>
  </tr>
  <tr>
    <td>C4—C5—C6—N1</td>
    <td>-1.6 (2)</td>
  </tr>
  <tr>
    <td>C44—C45—C46—C47</td>
    <td>0.7 (2)</td>
  </tr>
  <tr>
    <td>C44—C45—C46—C40</td>
    <td>179.73 (14)</td>
  </tr>
  <tr>
    <td>C48—N43—C44—C45</td>
    <td>-0.5 (2)</td>
  </tr>
  <tr>
    <td>C46—C45—C44—N43</td>
    <td>-0.3 (2)</td>
  </tr>
  <tr>
    <td>C45—C46—C47—C48</td>
    <td>-0.3 (2)</td>
  </tr>
  <tr>
    <td>C40—C46—C47—C48</td>
    <td>-179.31 (14)</td>
  </tr>
  <tr>
    <td>C42—N37—C38—C39</td>
    <td>0.3 (2)</td>
  </tr>
  <tr>
    <td>N37—C38—C39—C40</td>
    <td>-1.4 (2)</td>
  </tr>
  <tr>
    <td>C38—C39—C40—C41</td>
    <td>0.7 (2)</td>
  </tr>
  <tr>
    <td>C38—C39—C40—C46</td>
    <td>-179.63 (13)</td>
  </tr>
  <tr>
    <td>C47—C46—C40—C41</td>
    <td>149.49 (16)</td>
  </tr>
  <tr>
    <td>C45—C46—C40—C41</td>
    <td>-29.5 (2)</td>
  </tr>
  <tr>
    <td>C47—C46—C40—C39</td>
    <td>-30.1 (2)</td>
  </tr>
  <tr>
    <td>C45—C46—C40—C39</td>
    <td>150.90 (15)</td>
  </tr>
  <tr>
    <td>C32—N31—C36—C35</td>
    <td>0.5 (2)</td>
  </tr>
  <tr>
    <td>C44—N43—C48—C47</td>
    <td>1.0 (2)</td>
  </tr>
  <tr>
    <td>C46—C47—C48—N43</td>
    <td>-0.6 (2)</td>
  </tr>
  <tr>
    <td>N31—C36—C35—C34</td>
    <td>2.0 (2)</td>
  </tr>
  <tr>
    <td>C33—C34—C35—C36</td>
    <td>-2.6 (2)</td>
  </tr>
  <tr>
    <td>C28—C34—C35—C36</td>
    <td>173.10 (15)</td>
  </tr>
  <tr>
    <td>C35—C34—C33—C32</td>
    <td>0.8 (2)</td>
  </tr>
  <tr>
    <td>C28—C34—C33—C32</td>
    <td>-174.74 (15)</td>
  </tr>
  <tr>
    <td>C35—C34—C28—C29</td>
    <td>-132.33 (17)</td>
  </tr>
  <tr>
    <td>C33—C34—C28—C29</td>
    <td>43.2 (2)</td>
  </tr>
  <tr>
    <td>C35—C34—C28—C27</td>
    <td>42.8 (2)</td>
  </tr>
  <tr>
    <td>C33—C34—C28—C27</td>
    <td>-141.73 (17)</td>
  </tr>
  <tr>
    <td>C39—C40—C41—C42</td>
    <td>0.8 (2)</td>
  </tr>
  <tr>
    <td>C46—C40—C41—C42</td>
    <td>-178.85 (15)</td>
  </tr>
  <tr>
    <td>C29—C28—C27—C26</td>
    <td>0.3 (3)</td>
  </tr>
  <tr>
    <td>C34—C28—C27—C26</td>
    <td>-174.98 (16)</td>
  </tr>
  <tr>
    <td>C36—N31—C32—C33</td>
    <td>-2.4 (3)</td>
  </tr>
  <tr>
    <td>C34—C33—C32—N31</td>
    <td>1.8 (3)</td>
  </tr>
  <tr>
    <td>C38—N37—C42—C41</td>
    <td>1.3 (3)</td>
  </tr>
  <tr>
    <td>C40—C41—C42—N37</td>
    <td>-1.9 (3)</td>
  </tr>
  <tr>
    <td>C30—N25—C26—C27</td>
    <td>-1.5 (3)</td>
  </tr>
  <tr>
    <td>C28—C27—C26—N25</td>
    <td>1.8 (3)</td>
  </tr>
  <tr>
    <td>C27—C28—C29—C30</td>
    <td>-2.6 (3)</td>
  </tr>
  <tr>
    <td>C34—C28—C29—C30</td>
    <td>172.72 (17)</td>
  </tr>
  <tr>
    <td>C26—N25—C30—C29</td>
    <td>-1.0 (3)</td>
  </tr>
  <tr>
    <td>C28—C29—C30—N25</td>
    <td>3.1 (3)</td>
  </tr>
</table>

Symmetry codes: (i) $-x, -y+1, -z+1$; (ii) $x, -y+1/2, z-1/2$; (iii) $-x, y+1/2, -z+3/2$; (iv) $-x+1, -y+1, -z+1$; (v) $x, -y+1/2, z+1/2$; (vi) $-x+1, y+1/2, -z+1/2$; (vii) $-x, y-1/2, -z+3/2$; (viii) $-x+1, y-1/2, -z+1/2$.
<table><caption>Hydrogen-bond geometry (Å, °)</caption><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>C17—H17···N31<sup>viii</sup></td><td>0.95</td><td>2.34</td><td>3.2849 (19)</td><td>170</td></tr><tr><td>C20—H20···F2<sup>ii</sup></td><td>0.95</td><td>2.32</td><td>3.0341 (16)</td><td>131</td></tr><tr><td>C20—H20···F5<sup>ii</sup></td><td>0.95</td><td>2.53</td><td>3.4305 (17)</td><td>159</td></tr><tr><td>C18—H18···F2<sup>iv</sup></td><td>0.95</td><td>2.52</td><td>3.1085 (16)</td><td>120</td></tr><tr><td>C9—H9···O52</td><td>0.95</td><td>2.50</td><td>3.4223 (18)</td><td>163</td></tr><tr><td>C3—H3···N37<sup>vii</sup></td><td>0.95</td><td>2.54</td><td>3.4803 (19)</td><td>173</td></tr><tr><td>C21—H21···O52<sup>ii</sup></td><td>0.95</td><td>2.56</td><td>3.4294 (18)</td><td>152</td></tr><tr><td>C14—H14···F2</td><td>0.95</td><td>2.43</td><td>3.0497 (16)</td><td>123</td></tr><tr><td>C14—H14···F4</td><td>0.95</td><td>2.55</td><td>3.4519 (17)</td><td>158</td></tr><tr><td>C8—H8···F1<sup>v</sup></td><td>0.95</td><td>2.33</td><td>3.0205 (16)</td><td>129</td></tr><tr><td>C8—H8···F4<sup>v</sup></td><td>0.95</td><td>2.51</td><td>3.3524 (18)</td><td>148</td></tr><tr><td>C5—H5···O52</td><td>0.95</td><td>2.43</td><td>3.2916 (18)</td><td>151</td></tr><tr><td>C24—H24···F2<sup>viii</sup></td><td>0.95</td><td>2.29</td><td>2.9997 (16)</td><td>131</td></tr><tr><td>C24—H24···F3<sup>viii</sup></td><td>0.95</td><td>2.55</td><td>3.4609 (17)</td><td>161</td></tr><tr><td>C11—H11···N37<sup>vii</sup></td><td>0.95</td><td>2.61</td><td>3.4358 (19)</td><td>145</td></tr><tr><td>C12—H12···F1<sup>vii</sup></td><td>0.95</td><td>2.26</td><td>2.9662 (16)</td><td>131</td></tr><tr><td>C12—H12···F6<sup>vii</sup></td><td>0.95</td><td>2.49</td><td>3.4040 (16)</td><td>161</td></tr><tr><td>C2—H2···F1<sup>i</sup></td><td>0.95</td><td>2.52</td><td>3.0708 (16)</td><td>117</td></tr><tr><td>C2—H2···F3<sup>i</sup></td><td>0.95</td><td>2.45</td><td>3.3364 (17)</td><td>156</td></tr><tr><td>C45—H45···O50<sup>ix</sup></td><td>0.95</td><td>2.44</td><td>3.376 (2)</td><td>167</td></tr><tr><td>C6—H6···F1</td><td>0.95</td><td>2.46</td><td>3.0691 (16)</td><td>122</td></tr><tr><td>C6—H6···F4</td><td>0.95</td><td>2.60</td><td>3.5313 (17)</td><td>166</td></tr><tr><td>C38—H38···F6</td><td>0.95</td><td>2.41</td><td>3.1240 (19)</td><td>132</td></tr><tr><td>C48—H48···O51<sup>iv</sup></td><td>0.95</td><td>2.50</td><td>3.330 (2)</td><td>146</td></tr><tr><td>O53—H53B···F3<sup>v</sup></td><td>0.78 (2)</td><td>1.96 (3)</td><td>2.7228 (17)</td><td>166 (2)</td></tr><tr><td>O52—H52B···O53</td><td>0.90 (3)</td><td>1.83 (3)</td><td>2.7227 (18)</td><td>170 (2)</td></tr><tr><td>O53—H53A···N43<sup>iv</sup></td><td>0.85 (3)</td><td>2.05 (3)</td><td>2.8666 (19)</td><td>161 (3)</td></tr><tr><td>O52—H52A···O51</td><td>0.90 (3)</td><td>1.84 (3)</td><td>2.726 (2)</td><td>172 (2)</td></tr><tr><td>O50—H50A···O49</td><td>1.05 (3)</td><td>1.72 (3)</td><td>2.741 (2)</td><td>163 (2)</td></tr><tr><td>O49—H49B···F5<sup>ii</sup></td><td>0.96 (3)</td><td>1.82 (3)</td><td>2.7716 (18)</td><td>173 (3)</td></tr><tr><td>O50—H50B···N25<sup>i</sup></td><td>0.96 (3)</td><td>1.86 (3)</td><td>2.816 (2)</td><td>173 (3)</td></tr><tr><td>O49—H49A···O52<sup>ii</sup></td><td>1.00 (4)</td><td>1.81 (4)</td><td>2.798 (2)</td><td>169 (3)</td></tr><tr><td>O51—H51B···F4</td><td>0.91 (3)</td><td>1.88 (3)</td><td>2.7029 (18)</td><td>149 (2)</td></tr><tr><td>O51—H51A···O50</td><td>1.00 (4)</td><td>1.76 (4)</td><td>2.719 (2)</td><td>158 (3)</td></tr></tbody></table>

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