# Synthesis and crystal structure of [( S p )-(2-phenylferrocenyl)methyl]trimethylammonium iodide dichloromethane monosolvate

Abdelhak Lachguar, Éric Deydier, Agnès Labande, Eric Manoury, Rinaldo Poli, Jean-Claude Daran

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Abdelhak Lachguar, Éric Deydier, Agnès Labande, Eric Manoury, Rinaldo Poli, et al.. Synthesis and crystal structure of [( S p )-(2-phenylferrocenyl)methyl]trimethylammonium iodide dichloromethane monosolvate. Acta crystallographica Section E: Crystallographic communications [2015-..], 2022, 78 (7), pp.722-726. 10.1107/s2056989022006053. hal-03737936

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# Synthesis and crystal structure of [(S<sub>p</sub>)-(2-phenyl-ferrocenyl)methyl]trimethylammonium iodide dichloromethane monosolvate

Abdelhak Lachguar,ᵃ,ᵇ Eric Deydier,ᵃ,ᵇ Agnès Labande,ª Eric Manoury,ª Rinaldo Poliª and Jean-Claude Daranª*

Received 24 January 2022

Accepted 7 June 2022

Edited by G. Diaz de Delgado, Universidad de Los Andes, Venezuela

**Keywords:** 1,2-disubstitued ferrocene; planar chirality; chiral ligands; asymmetric catalysis; disordered dichloromethane; crystal structure.

CCDC reference: 2177602

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

ªCNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, F-31077 Toulouse Cedex 4, France, and ᵇIUT A Paul Sabatier, de Chimie, Avenue Georges Pompidou, CS 20258, F-81104, Castres Cedex, France. *Correspondence e-mail: jean-claude.daran@lcc-toulouse.fr

As a follow-up to our research on the chemistry of disubstituted ferrocene derivatives, the synthesis and the structure of the title compound, [Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>15</sub>H<sub>19</sub>N)]I·CH<sub>2</sub>Cl<sub>2</sub>, is described. The cation molecule is built up from a ferrocene disubstituted by a trimethylammonium methyl group and a phenyl ring. The asymmetric unit contains the iodide to equilibrate the charge and a disordered dichloromethane solvate. The disordered model results from a roughly statistical exchange (0.6/0.4) between one Cl and one H. The packing of the structure is stabilized by weak C—H···X (X = I, Cl), C—H···π(Cp) and C—Cl···π(phenyl) interactions, building a three-dimensional network. The cation has planar chirality with S<sub>p</sub>(Fc) absolute configuration. The structure of the title compound is compared with related disubstituted (trimethylammonio)methyl ferrocenes.

## 1. Chemical context

Asymmetric catalysis by transition metals has received considerable attention over the last few decades and numerous chiral ligands and complexes allowing high activity and enantioselectivity have been reported (Jacobsen *et al.*, 1999; Börner, 2008). For this purpose, catalysts need a chiral ligand presenting at least a chiral center, a chiral axis or a planar chirality. Amongst the various chiral ligands that have been synthesized, ferrocenyl phosphines have proven to be particularly efficient for numerous asymmetric reactions (Buergler *et al.*, 2012; Gómez Arrayás *et al.*, 2006; Toma *et al.*, 2014).

Over the last few years, our team has developed the synthesis of various chiral ferrocenyl ligands for asymmetric catalysis (Audin *et al.*, 2010; Labande *et al.*, 2007; Bayda *et al.*, 2014; Daran *et al.*, 2010; Wei *et al.*, 2012, 2014; Loxq *et al.*, 2014). We mainly focused on a series of chiral bidentate PX ferrocenyl ligands (X = OR, SR, NHC) bearing planar chirality, which have been successfully used in different homogeneous asymmetric catalytic reactions: allylic substitution, methoxy-carbonylation, hydrogenation (Kozinets *et al.*, 2012; Le Roux *et al.*, 2007; Diab *et al.*, 2008; Routaboul *et al.*, 2005). All of these ligands present a planar chiral 1,2-disubstituted ferrocenyl group with coordination sites on both substituents. More recently, we wanted to extend the application of planar chiral 1,2-disubstituted ferrocenyl groups to the synthesis of ligands

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Published under a CC BY 4.0 licence
with only one substituent bearing a coordination site for fine
tuning of existing ligands. To this aim, we needed an enanti-
omerically pure planar chiral building block bearing a good
leaving group in order to introduce a planar chiral substituent
on nucleophilic atoms. In this context, we report here the two-
step synthesis of the title [(S<sub>p</sub>)-(2-phenylferrocenyl)meth-
yl]trimethylammonium iodide salt.

<figure><img src="image_7.png" /></figure>

The latter is synthesized in two steps, the first consists in the
enantioselective synthesis of (S<sub>p</sub>)-A following the procedure
developed by S.-L. You and co-workers (Gao *et al.*, 2013), the
second step is a quaternization of the tertiary amine to the
ammonium salt by reaction with an excess of iodo methane.
(Ferrocenylmethyl) ammoniums have been used successfully
as electrophiles because of the stabilization of carbocations in
an α position of ferrocene derivatives and because of the
presence of a good leaving group: trimethylamine. Nucleo-
philic[EM2] substitution (Lin *et al.*, 2020) on the methylene
carbon atom in the α position of the ferrocene moiety in
compound B, [(Sp)-(2-phenylferrocenyl)methyl]trimethyl-
ammonium iodide, should then be favoured and should
provide an efficient access to a wide range of various enanti-
omerically pure ferrocene derivatives of type C including

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

View of the asymmetric unit of the title compound with the atom-
labelling scheme. Ellipsoids are drawn at the 30% probability level and
the H atoms are represented as small circles of arbitrary radii. C—H···X
(X = I, Cl) interactions are represented as dashed lines.

<figure><img src="image_9.png" /><figcaption>**Figure 1**

Synthesis of the title (S<sub>p</sub>)-1-dimethylaminomethyl-2-phenylferrocenium iodide salt</figcaption></figure>
<figure><img src="image_10.png" /><figcaption>Figure 3</figcaption></figure>

ORTEP view of the disordered CH₂Cl₂ solvent molecule. Ellipsoids are drawn at the 20% probability level. H atoms are represented as small circles of arbitrary radii.

ligands, by reaction with various nucleophiles (amines, thiols, alcohols) (Fig. 1).

## 2. Structural commentary

The molecular structure is based on a ferrocene moiety in which one of the Cp rings is disubstituted in the 1,2 position by a tri-methylammonium-methyl and a phenyl substituent. The molecule has a positive charge, which is counterbalanced by an iodide (Fig. 2). Moreover, there is one disordered dichloromethane solvate molecule per asymmetric unit. The disordered model results from the exchange between one Cl and one H in the ratio 0.6/0.4 (Fig. 3). This disorder might be induced by the occurrence of weak C–Cl···I intramolecular and C–H···Cl intermolecular interactions. There are weak intramolecular C–H···I interactions within the asymmetric unit.

As a result of the presence of the two substituents on the Cp ring, the cation molecule has planar chirality and its absolute structure is *S*<sub>p</sub>, which is confirmed by the refinement of the Flack parameter (Parsons *et al.*, 2013). The phenyl ring is twisted with respect to the Cp ring by 48.74 (17)° and the C1–C11–N1 unit is roughly perpendicular to the Cp ring to which it is attached, making a dihedral angle of 89.7 (2)°.

## 3. Supramolecular features

The crystal packing is governed by the occurrence of weak C–H···*X* (*X* = Cl, I), C–H···π and C–Cl···π interactions (Table 1). The iodine atom is engaged in many weak C–H···I interactions involving some of the H atoms of the methyl groups, one H atom of the methylene group and the non-disordered H atoms of the dichloromethane solvate. These interactions build up a ribbon developing parallel to the *b* axis

<caption>Table 1</caption>

Hydrogen-bond geometry (Å, °).

<table><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>C11–H11A···I1<sup>i</sup></td><td>0.99</td><td>3.17</td><td>3.988 (4)</td><td>140</td></tr><tr><td>C12–H12C···I1</td><td>0.98</td><td>3.21</td><td>4.117 (5)</td><td>154</td></tr><tr><td>C12–H12B···Cl2C</td><td>0.98</td><td>3.51</td><td>3.787 (7)</td><td>99</td></tr><tr><td>C13–H13A···I1</td><td>0.98</td><td>3.27</td><td>4.158 (5)</td><td>151</td></tr><tr><td>C14–H14A···I1</td><td>0.98</td><td>3.14</td><td>4.057 (5)</td><td>157</td></tr><tr><td>C14–H14B···I1<sup>i</sup></td><td>0.98</td><td>3.25</td><td>4.077 (5)</td><td>143</td></tr><tr><td>C30A–H30A···I1<sup>ii</sup></td><td>1.00</td><td>2.89</td><td>3.867 (7)</td><td>166</td></tr><tr><td>C13–H13B···CT2<sup>iii</sup></td><td>0.98</td><td>2.98</td><td>3.901 (6)</td><td>158</td></tr><tr><td>C23–H23···CT1<sup>iv</sup></td><td>0.95</td><td>2.69</td><td>3.600 (7)</td><td>160</td></tr></tbody></table>

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

(Fig. 4). Then the Cl2 atom of the chloroform solvate interacts with the C12–H12C methyl group, thus building a link between the strips, resulting in a layer parallel to the (101) plane (Fig. 4). Moreover, there are two weak C–H···π interactions involving atom H13B of the C13 methyl group with the centroid of the Cp ring (C6–C10; C12) and atom C23 of the phenyl group with the centroid of the substituted Cp ring (C1–C5; C11). Finally, there is also a C–Cl···π interaction involving the Cl1 atom of the solvate [C30–Cl1···C13 (C21–C26), 1.757 (8), 3.4096 (2) and 4.7694 (3) Å, 132.13 (1)°]. All these interactions build up a three-dimensional network.

## 4. Database survey

A search in the Cambridge Structural Database (version 5.36; Groom *et al.*, 2016) using a fragment containing a ferrocenyl disubstituted by a trimethylamoniummethyl and at least a C atom gave six hits that could be compared with the title compound. A comparison of C1–C11, C11–N1 distances and dihedral angles between the Cp ring and the C1–C11–N1 plane is shown in Table 2. In all these compounds, the bulky

<figure><img src="image_11.png" /><figcaption>Figure 4</figcaption></figure>

Partial packing view showing the C–H···*X* (*X* = I, Cl) intermolecular interactions resulting in the formation of ribbons parallel to the *b* axis and C–H···Cl interactions linking the ribbons to form a layer parallel to (101) plane. The dichloromethane solvate builds the link between the layers.
<table><caption>**Table 2**
Comparison of the geometry (Å, °) within the methylamine C–CH₂–N fragment for the title compound with related structures.</caption><thead><tr><th></th><th>C1–C11</th><th>C11–N1</th><th>Cp1/C1>N1</th></tr></thead><tbody><tr><td>Title compound</td><td>1.493 (5)</td><td>1.531 (4)</td><td>89.7 (2)</td></tr><tr><td>BECKUQ</td><td>1.509</td><td>1.534</td><td>85.6</td></tr><tr><td>LIFWUS</td><td>1.465</td><td>1.544</td><td>69.8</td></tr><tr><td>LIFWUS</td><td>1.509</td><td>1.536</td><td>78.6</td></tr><tr><td>LIFXAZ</td><td>1.494</td><td>1.525</td><td>70.4</td></tr><tr><td>PIJLEB</td><td>1.494</td><td>1.519</td><td>86.9</td></tr><tr><td>VIKZIA</td><td>1.485</td><td>1.538</td><td>86.0</td></tr><tr><td>XEQKIN</td><td>1.497</td><td>1.531</td><td>84.2</td></tr></tbody></table>

References: BECKUQ (Hitchcock *et al.*, 2002); LIFWUS (Malezieux *et al.*, 1994); LIFXAZ (Malezieux *et al.*, 1994); PIJLEB (Butler *et al.*, 2002); VIKZIA (Butler *et al.*, 2002); XEKQIN (Deck *et al.*, 2000).

N(CH₃)₃ group is always above the Cp ring to which it is attached. The dihedral angles between the Cp and the C–C–N plane range from 69.8 to 89.7° for the title compound.

## 5. Synthesis and crystallization

**Synthesis of (Sₚ)-1-dimethylaminomethyl-2-phenylferrocene [(Sₚ)-A]:** To a solution of phenylboronic acid (110 mg, 1 mmol) in DMA (8 mL) were added Boc-L-Val-OH (43.5 mg, 0.2 mmol), Pd(OAc)₂ (22.5 mg, 0.1 mmol), K₂CO₃ (138.21 mg, 1 mmol), TBAB (tetrabutyl ammonium bromide; 80 mg, 0.25 mmol) and N,N-dimethylferrocenylmethylamine (243 mg, 1 mmol) successively. The mixture was stirred at 333 K under air (open flask). When the reaction was complete (TLC monitoring), the mixture was quenched with saturated aqueous NaHCO₃ and the organic phase was extracted three times with EtOAc. The combined organic layers were washed with H₂O and brine successively, dried (Na₂SO₄) and filtered. The solvent was removed under reduced pressure and the residue purified by column chromatography (ethyl acetate/ petroleum ether = 1/10, v/v, 2% Et₃N) to afford the desired product A as a yellow oil (205 mg, 64% yield). The results are in agreement with published analytical data (Gao *et al.*, 2013).

¹H NMR (400 MHz, CDCl₃) δ ppm 7.79–7.71 (m, 2H, CH Ph), 7.41–7.31 (m, 2H, CH Ph), 7.30–7.21 (m, 1H, CH Ph), 4.53–4.47 (m, 1H, CH subst Cp), 4.33 (dd, *J* = 2.5, 1.5 Hz, 1H, CH subst Cp), 4.26 (*t*, *J* = 2.5 Hz, 1H, CH subst Cp), 4.08 (s, 5H, CH Cₚ), 3.67 (*d*, *J* = 12.8 Hz, 1H, CH₂), 3.18 (*d*, *J* = 12.8 Hz, 1H, CH₂), 2.21 (s, 6H, CH₃). ¹³C NMR (101 MHz, CDCl₃) δ ppm 138.91 (Cq, Ph), 129.36 (CH Ph), 127.93 (CH Ph), 126.06 (CH Ph), 88.17 (Cq subst Cp), 82.24 (Cq subst Cp), 71.56 (CH subst Cp), 70.06 (CH Cp), 69.94 (CH subst Cp), 67.10 (CH subst Cp), 57.93 (CH₂), 45.08 (CH₃).

**Synthesis of [(Sₚ)-(2-phenylferrocenyl)methyl]trimethylammonium iodide salt [(Sₚ)-B]:** An excess of MeI (1 mL, 1.62 mmol) was added to a solution of A (250 mg, 0.78 mmol) in Et₂O (3 mL). The reaction mixture was stirred for 4 h at RT. An abundant yellow solid precipitated. The yellow solid was filtered, washed with Et₂O and dried to yield B as a yellow solid (332 mg, 92% yield), which was crystallized in dichloromethane.

<table><caption>**Table 3**
Experimental details.</caption><tbody><tr><td colspan="2"><strong>Crystal data</strong></td></tr><tr><td>Chemical formula</td><td>[Fe(C₅H₅)(C₁₅H₁₉N)]·I·CH₂Cl₂</td></tr><tr><td>M<sub>r</sub></td><td>546.08</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, P2<sub>1</sub></td></tr><tr><td>Temperature (K)</td><td>110</td></tr><tr><td>a, b, c (Å)</td><td>10.7919 (7), 10.2128 (5),<br>11.2941 (7)</td></tr><tr><td>β (°)</td><td>113.031 (3)</td></tr><tr><td>V (Å³)</td><td>1145.57 (12)</td></tr><tr><td>Z</td><td>2</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm⁻¹)</td><td>2.24</td></tr><tr><td>Crystal size (mm)</td><td>0.30 × 0.10 × 0.10</td></tr><tr><td colspan="2"><strong>Data collection</strong></td></tr><tr><td>Diffractometer</td><td>Bruker APEXII CCD</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Krause et al., 2015)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.520, 0.746</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>58547, 6993, 6822</td></tr><tr><td>R<sub>int</sub></td><td>0.052</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å⁻¹)</td><td>0.715</td></tr><tr><td colspan="2"><strong>Refinement</strong></td></tr><tr><td>R[F² > 2σ(F²)], wR(F²), S</td><td>0.033, 0.092, 1.06</td></tr><tr><td>No. of reflections</td><td>6993</td></tr><tr><td>No. of parameters</td><td>247</td></tr><tr><td>No. of restraints</td><td>1</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å⁻³)</td><td>1.50, -0.69</td></tr><tr><td>Absolute structure</td><td>Flack x determined using 3144 quotients [(I⁺)-(I⁻)][(I⁺)+(I⁻)] (Parsons *et al.*, 2013)</td></tr><tr><td>Absolute structure parameter</td><td>0.018 (6)</td></tr></tbody></table>

Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a), SHELXL2018 (Sheldrick, 2015b), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae *et al.*, 2020).

¹H NMR (400 MHz, CDCl₃) δ ppm 7.58–7.50 (m, 2H, CH Ph), 7.46–7.37 (m, 2H, CH Ph), 7.37–7.26 (m, 1H, CH Ph), 5.33 (d, *J* = 13.4 Hz, 1H, CH₂), 4.91 (dd, *J* = 2.5, 1.5 Hz, 1H, CH subst Cp), 4.83 (d, *J* = 13.4 Hz, 1H, CH₂), 4.56 (dd, *J* = 2.5, 1.5 Hz, 1H, CH subst Cp), 4.52 (*t*, *J* = 2.5 Hz, 1H, CH subst Cp), 4.34 (s, 5H, CH Cₚ), 3.02 (s, 9H, CH₃). ¹³C NMR (101 MHz, CDCl₃) δ ppm 136.54 (Cq, Ph), 129.86 (CH Ph), 129.05 (CH Ph), 127.72 (CH Ph), 90.61 (Cq subst Cp), 73.44 (CH subst Cp), 72.15 (Cq subst Cp), 70.96 (CH Cp), 70.44 (Cq subst Cp), 70.04 (Cq subst Cp), 65.21 (CH₂), 52.76 (CH₃).

## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms attached to C atoms were fixed geometrically and treated as riding with C–H = 1.0 Å (methine), 0.95 Å (aromatic), 0.99 Å (methylene) and 0.98 Å (methyl) with *U*<sub>iso</sub>(H) = 1.2*U*<sub>eq</sub>(CH aromatic, methylene) or *U*<sub>iso</sub>(H) = 1.5*U*<sub>eq</sub>(CH₃).

The occurrence of three large residual densities around the C atom of the solvate with distances around 1.76 Å initially suggested the presence of a chloroform solvate molecule. However, if one of the Cl atoms (Cl1) could be refined
correctly with full occupancy, the two others display large and
elongated ellipsoids. Refining their occupancy factors using
the restraints available in *SHELXL* gave a ratio of 0.6/0.4. So
the disordered model is based on an exchange between one H
and one Cl (Fig. 3). The model has been refined using the
PART instruction to model two CH<sub>2</sub>Cl<sub>2</sub> models. The non-
disordered atoms C30, H30 and Cl1 were split with occupancy
factor 0.5 and introduced in the two models (C30A, C30B,
H30A, H30B, Cl1A, Cl1B). Their coordinates and thermal
parameters were constrained to be identical using the EXYZ
and EADP commands available in *SHELXL*. This disordered
model is not perfect, as suggested by a large residual electron
density in the vicinity of the atom H30B.

Acknowledgements

The authors thank the Centre National de la Recherche
Scientifique (CNRS), the Institut Universitaire de Techno-
logie (IUT) Paul Sabatier and the Chemistry Department of
the IUT Castres for offering access to laboratories and
analytical equipment.

Funding information

Funding for this research was provided by: Centre National de
la Recherche Scientifique (CNRS), Midi-Pyrénées region,
Institut Universitaire de Technologie (IUT) Paul Sabatier and
the Syndicat Mixte de Castres Mazamet (PhD grant
ALDOCT000431.

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Wei, M.-M., Audin, C., Manoury, E., Deydier, E. & Daran, J.-C. (2014). *Acta Cryst.* **C70**, 281–284.

Wei, M.-M., García-Melchor, M., Daran, J.-C., Audin, C., Lledós, A., Poli, R., Deydier, E. & Manoury, E. (2012). *Organometallics*, **31**, 6669–6680.
supporting information

*Acta Cryst.* (2022). **E78**, 722-726 [https://doi.org/10.1107/S2056989022006053]

# Synthesis and crystal structure of [(S<sub>p</sub>)-(2-phenylferrocenyl)methyl]trimethylammonium iodide dichloromethane monosolvate

Abdelhak Lachguar, Eric Deydier, Agnès Labande, Eric Manoury, Rinaldo Poli and Jean-Claude Daran

## Computing details

Data collection: *APEX2* (Bruker, 2015); cell refinement: *SAINT* (Bruker, 2015); data reduction: *SAINT* (Bruker, 2015); program(s) used to solve structure: *SHELXT* (Sheldrick, 2015a); program(s) used to refine structure: *SHELXL2018* (Sheldrick, 2015b); molecular graphics: *ORTEP*III (Burnett & Johnson, 1996), *ORTEP-3 for Windows* (Farrugia, 2012) and *Mercury* (Macrae *et al.*, 2020); software used to prepare material for publication: *SHELXL2018* (Sheldrick, 2015b).

## [(S<sub>p</sub>)-(2-Phenylferrocenyl)methyl]trimethylammonium iodide dichloromethane monosolvate

### Crystal data

[Fe(C<sub>5</sub>H<sub>5</sub>)(C<sub>15</sub>H<sub>19</sub>N)]I·CH<sub>2</sub>Cl<sub>2</sub>

M<sub>r</sub> = 546.08

Monoclinic, P2<sub>1</sub>

a = 10.7919 (7) Å

b = 10.2128 (5) Å

c = 11.2941 (7) Å

β = 113.031 (3)°

V = 1145.57 (12) Å<sup>3</sup>

Z = 2

F(000) = 544

D<sub>x</sub> = 1.583 Mg m<sup>-3</sup>

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 9989 reflections

θ = 2.8–28.3°

μ = 2.24 mm<sup>-1</sup>

T = 110 K

Stick, yellow

0.30 × 0.10 × 0.10 mm

### Data collection

Bruker APEXII CCD
diffractometer

Radiation source: micro-focus sealed tube

Graphite monochromator

φ and ω scans

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

T<sub>min</sub> = 0.520, T<sub>max</sub> = 0.746

58547 measured reflections

6993 independent reflections

6822 reflections with *I* > 2σ(*I*)

R<sub>int</sub> = 0.052

θ<sub>max</sub> = 30.5°, θ<sub>min</sub> = 2.1°

h = -15→15

k = -14→14

l = -16→16

### Refinement

Refinement on *F*<sup>2</sup>

Least-squares matrix: full

R[F<sup>2</sup> > 2σ(F<sup>2</sup>)] = 0.033

wR(F<sup>2</sup>) = 0.092

S = 1.06

6993 reflections

247 parameters

1 restraint

Primary atom site location: structure-invariant
direct methods

Secondary atom site location: difference Fourier
map

Hydrogen site location: inferred from
neighbouring sites

H-atom parameters constrained
$$w = 1/[\sigma^2(F_o^2) + (0.0507P)^2 + 0.9038P]$$

where $P = (F_o^2 + 2F_c^2)/3$

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

$$\Delta\rho_{\max} = 1.50 \text{ e Å}^{-3}$$

$$\Delta\rho_{\min} = -0.68 \text{ e Å}^{-3}$$

Absolute structure: Flack *x* determined using

3144 quotients [(I')-(I)]/[(I')+(I)] (Parsons *et al.*, 2013)

Absolute structure parameter: 0.018 (6)

### Special details

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

<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th><th>Occ. (&lt;1)</th></tr></thead><tbody><tr><td>Fe1</td><td>0.94060 (5)</td><td>0.53142 (6)</td><td>0.79508 (5)</td><td>0.02716 (11)</td><td></td></tr><tr><td>I1</td><td>0.22433 (3)</td><td>0.13532 (3)</td><td>0.79999 (3)</td><td>0.04532 (10)</td><td></td></tr><tr><td>N1</td><td>0.5997 (3)</td><td>0.3408 (3)</td><td>0.8610 (3)</td><td>0.0281 (6)</td><td></td></tr><tr><td>C1</td><td>0.7697 (3)</td><td>0.4388 (3)</td><td>0.7817 (3)</td><td>0.0243 (6)</td><td></td></tr><tr><td>C2</td><td>0.7375 (3)</td><td>0.5512 (4)</td><td>0.6967 (3)</td><td>0.0248 (6)</td><td></td></tr><tr><td>C3</td><td>0.8016 (4)</td><td>0.5304 (5)</td><td>0.6083 (4)</td><td>0.0323 (7)</td><td></td></tr><tr><td>H3</td><td>0.797426</td><td>0.587679</td><td>0.540618</td><td>0.039*</td><td></td></tr><tr><td>C4</td><td>0.8728 (4)</td><td>0.4085 (5)</td><td>0.6395 (4)</td><td>0.0361 (8)</td><td></td></tr><tr><td>H4</td><td>0.924513</td><td>0.371724</td><td>0.596435</td><td>0.043*</td><td></td></tr><tr><td>C5</td><td>0.8532 (4)</td><td>0.3521 (4)</td><td>0.7450 (4)</td><td>0.0316 (7)</td><td></td></tr><tr><td>H5</td><td>0.888964</td><td>0.270870</td><td>0.784766</td><td>0.038*</td><td></td></tr><tr><td>C6</td><td>1.0323 (5)</td><td>0.6035 (7)</td><td>0.9762 (5)</td><td>0.0588 (18)</td><td></td></tr><tr><td>H6</td><td>0.996901</td><td>0.602449</td><td>1.041048</td><td>0.071*</td><td></td></tr><tr><td>C7</td><td>1.1125 (5)</td><td>0.5035 (6)</td><td>0.9540 (6)</td><td>0.0546 (14)</td><td></td></tr><tr><td>H7</td><td>1.139685</td><td>0.424007</td><td>1.000841</td><td>0.065*</td><td></td></tr><tr><td>C8</td><td>1.1439 (4)</td><td>0.5440 (6)</td><td>0.8501 (6)</td><td>0.0482 (11)</td><td></td></tr><tr><td>H8</td><td>1.196503</td><td>0.496477</td><td>0.814202</td><td>0.058*</td><td></td></tr><tr><td>C9</td><td>1.0835 (5)</td><td>0.6679 (6)</td><td>0.8081 (6)</td><td>0.0517 (13)</td><td></td></tr><tr><td>H9</td><td>1.088663</td><td>0.717959</td><td>0.739283</td><td>0.062*</td><td></td></tr><tr><td>C10</td><td>1.0143 (5)</td><td>0.7038 (6)</td><td>0.8864 (7)</td><td>0.0542 (14)</td><td></td></tr><tr><td>H10</td><td>0.964387</td><td>0.782051</td><td>0.879465</td><td>0.065*</td><td></td></tr><tr><td>C11</td><td>0.7314 (3)</td><td>0.4163 (4)</td><td>0.8937 (3)</td><td>0.0262 (6)</td><td></td></tr><tr><td>H11A</td><td>0.723121</td><td>0.502191</td><td>0.930581</td><td>0.031*</td><td></td></tr><tr><td>H11B</td><td>0.804794</td><td>0.367396</td><td>0.960681</td><td>0.031*</td><td></td></tr><tr><td>C12</td><td>0.4841 (4)</td><td>0.4146 (5)</td><td>0.7671 (6)</td><td>0.0463 (11)</td><td></td></tr><tr><td>H12A</td><td>0.496041</td><td>0.423269</td><td>0.685738</td><td>0.069*</td><td></td></tr><tr><td>H12B</td><td>0.479920</td><td>0.501808</td><td>0.801502</td><td>0.069*</td><td></td></tr><tr><td>H12C</td><td>0.400292</td><td>0.367326</td><td>0.752068</td><td>0.069*</td><td></td></tr><tr><td>C13</td><td>0.6057 (5)</td><td>0.2094 (4)</td><td>0.8064 (5)</td><td>0.0389 (9)</td><td></td></tr><tr><td>H13A</td><td>0.518810</td><td>0.165131</td><td>0.783295</td><td>0.058*</td><td></td></tr><tr><td>H13B</td><td>0.676498</td><td>0.156995</td><td>0.870448</td><td>0.058*</td><td></td></tr><tr><td>H13C</td><td>0.625814</td><td>0.219443</td><td>0.729424</td><td>0.058*</td><td></td></tr><tr><td>C14</td><td>0.5803 (6)</td><td>0.3216 (6)</td><td>0.9844 (5)</td><td>0.0501 (13)</td><td></td></tr><tr><td>H14A</td><td>0.494379</td><td>0.277179</td><td>0.966431</td><td>0.075*</td><td></td></tr></tbody></table>
<table><caption>Atomic displacement parameters (Å²)</caption><tr><td>H14B</td><td>0.579953</td><td>0.406942</td><td>1.023851</td><td>0.075*</td><td></td></tr><tr><td>H14C</td><td>0.654042</td><td>0.268085</td><td>1.043360</td><td>0.075*</td><td></td></tr><tr><td>C21</td><td>0.6496 (4)</td><td>0.6618 (3)</td><td>0.6930 (3)</td><td>0.0279 (7)</td><td></td></tr><tr><td>C22</td><td>0.5483 (5)</td><td>0.6960 (5)</td><td>0.5744 (4)</td><td>0.0425 (10)</td><td></td></tr><tr><td>H22</td><td>0.539718</td><td>0.649794</td><td>0.498588</td><td>0.051*</td><td></td></tr><tr><td>C23</td><td>0.4595 (6)</td><td>0.7987 (7)</td><td>0.5682 (6)</td><td>0.0594 (16)</td><td></td></tr><tr><td>H23</td><td>0.390870</td><td>0.820909</td><td>0.487518</td><td>0.071*</td><td></td></tr><tr><td>C24</td><td>0.4694 (5)</td><td>0.8671 (5)</td><td>0.6747 (6)</td><td>0.0469 (11)</td><td></td></tr><tr><td>H24</td><td>0.408025</td><td>0.935960</td><td>0.668760</td><td>0.056*</td><td></td></tr><tr><td>C25</td><td>0.5712 (5)</td><td>0.8348 (5)</td><td>0.7930 (5)</td><td>0.0372 (8)</td><td></td></tr><tr><td>H25</td><td>0.579600</td><td>0.882142</td><td>0.868150</td><td>0.045*</td><td></td></tr><tr><td>C26</td><td>0.6603 (4)</td><td>0.7334 (4)</td><td>0.8012 (4)</td><td>0.0308 (7)</td><td></td></tr><tr><td>H26</td><td>0.729624</td><td>0.712896</td><td>0.882019</td><td>0.037*</td><td></td></tr><tr><td>C30A</td><td>0.1255 (9)</td><td>0.5103 (11)</td><td>0.4280 (8)</td><td>0.086 (3)</td><td>0.5</td></tr><tr><td>H30C</td><td>0.160640</td><td>0.586709</td><td>0.485441</td><td>0.103*</td><td>0.5</td></tr><tr><td>H30A</td><td>0.029108</td><td>0.526078</td><td>0.374882</td><td>0.103*</td><td>0.5</td></tr><tr><td>Cl1A</td><td>0.2146 (3)</td><td>0.4929 (2)</td><td>0.3278 (2)</td><td>0.0790 (6)</td><td>0.5</td></tr><tr><td>Cl2B</td><td>0.1425 (3)</td><td>0.3690 (3)</td><td>0.5204 (3)</td><td>0.0674 (8)</td><td>0.6</td></tr><tr><td>C30B</td><td>0.1255 (9)</td><td>0.5103 (11)</td><td>0.4280 (8)</td><td>0.086 (3)</td><td>0.5</td></tr><tr><td>H30D</td><td>0.032076</td><td>0.537089</td><td>0.374507</td><td>0.103*</td><td>0.5</td></tr><tr><td>H30B</td><td>0.121215</td><td>0.423883</td><td>0.465898</td><td>0.103*</td><td>0.5</td></tr><tr><td>Cl1B</td><td>0.2146 (3)</td><td>0.4929 (2)</td><td>0.3278 (2)</td><td>0.0790 (6)</td><td>0.5</td></tr><tr><td>Cl2C</td><td>0.1919 (5)</td><td>0.6201 (4)</td><td>0.5491 (4)</td><td>0.0680 (11)</td><td>0.4</td></tr></table>

<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>Fe1</td><td>0.0183 (2)</td><td>0.0300 (2)</td><td>0.0302 (2)</td><td>-0.00341 (18)</td><td>0.00622 (17)</td><td>-0.0044 (2)</td></tr><tr><td>I1</td><td>0.03471 (13)</td><td>0.05047 (17)</td><td>0.04750 (16)</td><td>-0.00545 (12)</td><td>0.01253 (11)</td><td>0.00816 (14)</td></tr><tr><td>N1</td><td>0.0238 (13)</td><td>0.0291 (14)</td><td>0.0308 (15)</td><td>-0.0013 (11)</td><td>0.0099 (11)</td><td>-0.0001 (11)</td></tr><tr><td>C1</td><td>0.0183 (13)</td><td>0.0244 (15)</td><td>0.0269 (14)</td><td>-0.0016 (11)</td><td>0.0052 (11)</td><td>-0.0012 (12)</td></tr><tr><td>C2</td><td>0.0205 (13)</td><td>0.0268 (15)</td><td>0.0230 (13)</td><td>-0.0016 (12)</td><td>0.0041 (10)</td><td>-0.0013 (11)</td></tr><tr><td>C3</td><td>0.0294 (16)</td><td>0.0410 (19)</td><td>0.0267 (15)</td><td>-0.0056 (16)</td><td>0.0113 (13)</td><td>-0.0044 (15)</td></tr><tr><td>C4</td><td>0.0301 (17)</td><td>0.041 (2)</td><td>0.040 (2)</td><td>-0.0051 (15)</td><td>0.0170 (16)</td><td>-0.0133 (17)</td></tr><tr><td>C5</td><td>0.0237 (15)</td><td>0.0258 (16)</td><td>0.043 (2)</td><td>-0.0018 (12)</td><td>0.0102 (14)</td><td>-0.0055 (14)</td></tr><tr><td>C6</td><td>0.035 (2)</td><td>0.095 (5)</td><td>0.040 (2)</td><td>-0.026 (3)</td><td>0.0078 (18)</td><td>-0.027 (3)</td></tr><tr><td>C7</td><td>0.030 (2)</td><td>0.060 (3)</td><td>0.051 (3)</td><td>-0.014 (2)</td><td>-0.0078 (19)</td><td>0.011 (2)</td></tr><tr><td>C8</td><td>0.0196 (16)</td><td>0.059 (3)</td><td>0.062 (3)</td><td>-0.0088 (19)</td><td>0.0115 (17)</td><td>-0.013 (3)</td></tr><tr><td>C9</td><td>0.036 (2)</td><td>0.053 (3)</td><td>0.058 (3)</td><td>-0.020 (2)</td><td>0.010 (2)</td><td>0.003 (2)</td></tr><tr><td>C10</td><td>0.030 (2)</td><td>0.048 (3)</td><td>0.072 (4)</td><td>-0.0106 (19)</td><td>0.007 (2)</td><td>-0.024 (3)</td></tr><tr><td>C11</td><td>0.0221 (14)</td><td>0.0273 (15)</td><td>0.0253 (14)</td><td>-0.0034 (12)</td><td>0.0050 (12)</td><td>-0.0001 (12)</td></tr><tr><td>C12</td><td>0.0215 (16)</td><td>0.045 (2)</td><td>0.065 (3)</td><td>0.0037 (16)</td><td>0.0092 (18)</td><td>0.016 (2)</td></tr><tr><td>C13</td><td>0.036 (2)</td><td>0.0298 (19)</td><td>0.050 (2)</td><td>-0.0059 (15)</td><td>0.0161 (18)</td><td>-0.0073 (17)</td></tr><tr><td>C14</td><td>0.054 (3)</td><td>0.062 (3)</td><td>0.042 (2)</td><td>-0.023 (2)</td><td>0.027 (2)</td><td>-0.010 (2)</td></tr><tr><td>C21</td><td>0.0245 (14)</td><td>0.0288 (18)</td><td>0.0265 (14)</td><td>0.0016 (12)</td><td>0.0058 (12)</td><td>0.0030 (12)</td></tr><tr><td>C22</td><td>0.041 (2)</td><td>0.045 (2)</td><td>0.0309 (19)</td><td>0.0142 (19)</td><td>0.0026 (17)</td><td>0.0023 (17)</td></tr><tr><td>C23</td><td>0.050 (3)</td><td>0.064 (3)</td><td>0.046 (3)</td><td>0.030 (3)</td><td>-0.001 (2)</td><td>0.007 (2)</td></tr><tr><td>C24</td><td>0.044 (2)</td><td>0.041 (2)</td><td>0.057 (3)</td><td>0.018 (2)</td><td>0.021 (2)</td><td>0.010 (2)</td></tr></tbody></table>
<table><tr><td>C25</td><td>0.041 (2)</td><td>0.0325 (17)</td><td>0.044 (2)</td><td>0.0020 (16)</td><td>0.0226 (18)</td><td>-0.0021 (15)</td></tr><tr><td>C26</td><td>0.0319 (17)</td><td>0.0299 (17)</td><td>0.0298 (16)</td><td>0.0016 (14)</td><td>0.0112 (14)</td><td>0.0025 (13)</td></tr><tr><td>C30A</td><td>0.071 (5)</td><td>0.121 (8)</td><td>0.060 (4)</td><td>0.051 (5)</td><td>0.021 (3)</td><td>0.005 (4)</td></tr><tr><td>Cl1A</td><td>0.1058 (16)</td><td>0.0728 (11)</td><td>0.0816 (12)</td><td>0.0165 (10)</td><td>0.0615 (12)</td><td>0.0079 (9)</td></tr><tr><td>Cl2B</td><td>0.0526 (12)</td><td>0.107 (2)</td><td>0.0579 (13)</td><td>0.0290 (14)</td><td>0.0379 (11)</td><td>0.0377 (14)</td></tr><tr><td>C30B</td><td>0.071 (5)</td><td>0.121 (8)</td><td>0.060 (4)</td><td>0.051 (5)</td><td>0.021 (3)</td><td>0.005 (4)</td></tr><tr><td>Cl1B</td><td>0.1058 (16)</td><td>0.0728 (11)</td><td>0.0816 (12)</td><td>0.0165 (10)</td><td>0.0615 (12)</td><td>0.0079 (9)</td></tr><tr><td>Cl2C</td><td>0.105 (3)</td><td>0.0471 (19)</td><td>0.0525 (17)</td><td>0.005 (2)</td><td>0.0320 (19)</td><td>-0.0071 (15)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>Fe1—C1</td><td>2.025 (3)</td><td>C9—H9</td><td>0.9500</td></tr><tr><td>Fe1—C6</td><td>2.030 (5)</td><td>C10—H10</td><td>0.9500</td></tr><tr><td>Fe1—C7</td><td>2.034 (5)</td><td>C11—H11A</td><td>0.9900</td></tr><tr><td>Fe1—C8</td><td>2.037 (4)</td><td>C11—H11B</td><td>0.9900</td></tr><tr><td>Fe1—C5</td><td>2.037 (4)</td><td>C12—H12A</td><td>0.9800</td></tr><tr><td>Fe1—C10</td><td>2.038 (5)</td><td>C12—H12B</td><td>0.9800</td></tr><tr><td>Fe1—C9</td><td>2.041 (5)</td><td>C12—H12C</td><td>0.9800</td></tr><tr><td>Fe1—C2</td><td>2.043 (3)</td><td>C13—H13A</td><td>0.9800</td></tr><tr><td>Fe1—C4</td><td>2.048 (4)</td><td>C13—H13B</td><td>0.9800</td></tr><tr><td>Fe1—C3</td><td>2.055 (4)</td><td>C13—H13C</td><td>0.9800</td></tr><tr><td>N1—C12</td><td>1.488 (6)</td><td>C14—H14A</td><td>0.9800</td></tr><tr><td>N1—C13</td><td>1.489 (5)</td><td>C14—H14B</td><td>0.9800</td></tr><tr><td>N1—C14</td><td>1.500 (6)</td><td>C14—H14C</td><td>0.9800</td></tr><tr><td>N1—C11</td><td>1.529 (5)</td><td>C21—C26</td><td>1.390 (5)</td></tr><tr><td>C1—C5</td><td>1.435 (5)</td><td>C21—C22</td><td>1.402 (5)</td></tr><tr><td>C1—C2</td><td>1.449 (5)</td><td>C22—C23</td><td>1.404 (7)</td></tr><tr><td>C1—C11</td><td>1.495 (5)</td><td>C22—H22</td><td>0.9500</td></tr><tr><td>C2—C3</td><td>1.435 (5)</td><td>C23—C24</td><td>1.359 (9)</td></tr><tr><td>C2—C21</td><td>1.465 (5)</td><td>C23—H23</td><td>0.9500</td></tr><tr><td>C3—C4</td><td>1.433 (7)</td><td>C24—C25</td><td>1.398 (8)</td></tr><tr><td>C3—H3</td><td>0.9500</td><td>C24—H24</td><td>0.9500</td></tr><tr><td>C4—C5</td><td>1.412 (6)</td><td>C25—C26</td><td>1.391 (6)</td></tr><tr><td>C4—H4</td><td>0.9500</td><td>C25—H25</td><td>0.9500</td></tr><tr><td>C5—H5</td><td>0.9500</td><td>C26—H26</td><td>0.9500</td></tr><tr><td>C6—C10</td><td>1.400 (10)</td><td>C30A—Cl2B</td><td>1.748 (11)</td></tr><tr><td>C6—C7</td><td>1.422 (10)</td><td>C30A—Cl1A</td><td>1.758 (8)</td></tr><tr><td>C6—H6</td><td>0.9500</td><td>C30A—H30C</td><td>0.9900</td></tr><tr><td>C7—C8</td><td>1.406 (9)</td><td>C30A—H30A</td><td>0.9900</td></tr><tr><td>C7—H7</td><td>0.9500</td><td>C30B—Cl2C</td><td>1.695 (11)</td></tr><tr><td>C8—C9</td><td>1.418 (9)</td><td>C30B—Cl1B</td><td>1.758 (8)</td></tr><tr><td>C8—H8</td><td>0.9500</td><td>C30B—H30D</td><td>0.9900</td></tr><tr><td>C9—C10</td><td>1.411 (9)</td><td>C30B—H30B</td><td>0.9900</td></tr><tr><td>C1—Fe1—C6</td><td>108.39 (19)</td><td>C7—C6—Fe1</td><td>69.7 (3)</td></tr><tr><td>C1—Fe1—C7</td><td>119.30 (19)</td><td>C10—C6—H6</td><td>125.7</td></tr><tr><td>C6—Fe1—C7</td><td>41.0 (3)</td><td>C7—C6—H6</td><td>125.7</td></tr><tr><td>C1—Fe1—C8</td><td>153.2 (2)</td><td>Fe1—C6—H6</td><td>126.0</td></tr></table>
<table>
  <tr>
    <td>C6-Fe1-C8</td>
    <td>68.1 (2)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C8</td>
    <td>40.4 (2)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C5</td>
    <td>41.37 (15)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C5</td>
    <td>126.6 (2)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C5</td>
    <td>106.4 (2)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C5</td>
    <td>117.9 (2)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C10</td>
    <td>127.2 (2)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C10</td>
    <td>40.3 (3)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C10</td>
    <td>68.5 (3)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C10</td>
    <td>68.3 (2)</td>
  </tr>
  <tr>
    <td>C5-Fe1-C10</td>
    <td>164.6 (2)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C9</td>
    <td>164.8 (2)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C9</td>
    <td>67.8 (3)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C9</td>
    <td>68.3 (2)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C9</td>
    <td>40.7 (2)</td>
  </tr>
  <tr>
    <td>C5-Fe1-C9</td>
    <td>152.8 (2)</td>
  </tr>
  <tr>
    <td>C10-Fe1-C9</td>
    <td>40.5 (3)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C2</td>
    <td>41.75 (14)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C2</td>
    <td>120.6 (2)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C2</td>
    <td>155.2 (2)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C2</td>
    <td>163.3 (2)</td>
  </tr>
  <tr>
    <td>C5-Fe1-C2</td>
    <td>69.89 (15)</td>
  </tr>
  <tr>
    <td>C10-Fe1-C2</td>
    <td>108.24 (19)</td>
  </tr>
  <tr>
    <td>C9-Fe1-C2</td>
    <td>126.2 (2)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C4</td>
    <td>68.89 (16)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C4</td>
    <td>163.1 (3)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C4</td>
    <td>124.6 (2)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C4</td>
    <td>106.3 (2)</td>
  </tr>
  <tr>
    <td>C5-Fe1-C4</td>
    <td>40.44 (18)</td>
  </tr>
  <tr>
    <td>C10-Fe1-C4</td>
    <td>154.4 (3)</td>
  </tr>
  <tr>
    <td>C9-Fe1-C4</td>
    <td>119.1 (2)</td>
  </tr>
  <tr>
    <td>C2-Fe1-C4</td>
    <td>69.31 (16)</td>
  </tr>
  <tr>
    <td>C1-Fe1-C3</td>
    <td>69.09 (15)</td>
  </tr>
  <tr>
    <td>C6-Fe1-C3</td>
    <td>155.3 (2)</td>
  </tr>
  <tr>
    <td>C7-Fe1-C3</td>
    <td>162.3 (2)</td>
  </tr>
  <tr>
    <td>C8-Fe1-C3</td>
    <td>125.5 (2)</td>
  </tr>
  <tr>
    <td>C5-Fe1-C3</td>
    <td>68.75 (18)</td>
  </tr>
  <tr>
    <td>C10-Fe1-C3</td>
    <td>120.5 (2)</td>
  </tr>
  <tr>
    <td>C9-Fe1-C3</td>
    <td>107.8 (2)</td>
  </tr>
  <tr>
    <td>C2-Fe1-C3</td>
    <td>40.99 (14)</td>
  </tr>
  <tr>
    <td>C4-Fe1-C3</td>
    <td>40.88 (19)</td>
  </tr>
  <tr>
    <td>C12-N1-C13</td>
    <td>108.7 (4)</td>
  </tr>
  <tr>
    <td>C12-N1-C14</td>
    <td>110.2 (4)</td>
  </tr>
  <tr>
    <td>C13-N1-C14</td>
    <td>108.1 (4)</td>
  </tr>
  <tr>
    <td>C12-N1-C11</td>
    <td>110.9 (3)</td>
  </tr>
  <tr>
    <td>C13-N1-C11</td>
    <td>111.6 (3)</td>
  </tr>
  <tr>
    <td>C14-N1-C11</td>
    <td>107.2 (3)</td>
  </tr>
  <tr>
    <td>C5-C1-C2</td>
    <td>108.2 (3)</td>
  </tr>
</table>

<table>
  <tr>
    <td>C8-C7-C6</td>
    <td>107.3 (5)</td>
  </tr>
  <tr>
    <td>C8-C7-Fe1</td>
    <td>69.9 (3)</td>
  </tr>
  <tr>
    <td>C6-C7-Fe1</td>
    <td>69.3 (3)</td>
  </tr>
  <tr>
    <td>C8-C7-H7</td>
    <td>126.4</td>
  </tr>
  <tr>
    <td>C6-C7-H7</td>
    <td>126.4</td>
  </tr>
  <tr>
    <td>Fe1-C7-H7</td>
    <td>126.0</td>
  </tr>
  <tr>
    <td>C7-C8-C9</td>
    <td>108.2 (5)</td>
  </tr>
  <tr>
    <td>C7-C8-Fe1</td>
    <td>69.7 (3)</td>
  </tr>
  <tr>
    <td>C9-C8-Fe1</td>
    <td>69.8 (3)</td>
  </tr>
  <tr>
    <td>C7-C8-H8</td>
    <td>125.9</td>
  </tr>
  <tr>
    <td>C9-C8-H8</td>
    <td>125.9</td>
  </tr>
  <tr>
    <td>Fe1-C8-H8</td>
    <td>126.2</td>
  </tr>
  <tr>
    <td>C10-C9-C8</td>
    <td>108.0 (5)</td>
  </tr>
  <tr>
    <td>C10-C9-Fe1</td>
    <td>69.7 (3)</td>
  </tr>
  <tr>
    <td>C8-C9-Fe1</td>
    <td>69.5 (3)</td>
  </tr>
  <tr>
    <td>C10-C9-H9</td>
    <td>126.0</td>
  </tr>
  <tr>
    <td>C8-C9-H9</td>
    <td>126.0</td>
  </tr>
  <tr>
    <td>Fe1-C9-H9</td>
    <td>126.4</td>
  </tr>
  <tr>
    <td>C6-C10-C9</td>
    <td>107.8 (5)</td>
  </tr>
  <tr>
    <td>C6-C10-Fe1</td>
    <td>69.6 (3)</td>
  </tr>
  <tr>
    <td>C9-C10-Fe1</td>
    <td>69.9 (3)</td>
  </tr>
  <tr>
    <td>C6-C10-H10</td>
    <td>126.1</td>
  </tr>
  <tr>
    <td>C9-C10-H10</td>
    <td>126.1</td>
  </tr>
  <tr>
    <td>Fe1-C10-H10</td>
    <td>126.1</td>
  </tr>
  <tr>
    <td>C1-C11-N1</td>
    <td>114.3 (3)</td>
  </tr>
  <tr>
    <td>C1-C11-H11A</td>
    <td>108.7</td>
  </tr>
  <tr>
    <td>N1-C11-H11A</td>
    <td>108.7</td>
  </tr>
  <tr>
    <td>C1-C11-H11B</td>
    <td>108.7</td>
  </tr>
  <tr>
    <td>N1-C11-H11B</td>
    <td>108.7</td>
  </tr>
  <tr>
    <td>H11A-C11-H11B</td>
    <td>107.6</td>
  </tr>
  <tr>
    <td>N1-C12-H12A</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C12-H12B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H12A-C12-H12B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C12-H12C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H12A-C12-H12C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H12B-C12-H12C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C13-H13A</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C13-H13B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H13A-C13-H13B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C13-H13C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H13A-C13-H13C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H13B-C13-H13C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C14-H14A</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C14-H14B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H14A-C14-H14B</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>N1-C14-H14C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H14A-C14-H14C</td>
    <td>109.5</td>
  </tr>
  <tr>
    <td>H14B-C14-H14C</td>
    <td>109.5</td>
  </tr>
</table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><tr><td>C5—C1—C11</td><td>124.2 (3)</td><td>C26—C21—C22</td><td>118.3 (4)</td></tr><tr><td>C2—C1—C11</td><td>127.5 (3)</td><td>C26—C21—C2</td><td>123.4 (3)</td></tr><tr><td>C5—C1—Fe1</td><td>69.8 (2)</td><td>C22—C21—C2</td><td>118.3 (4)</td></tr><tr><td>C2—C1—Fe1</td><td>69.78 (19)</td><td>C21—C22—C23</td><td>119.8 (4)</td></tr><tr><td>C11—C1—Fe1</td><td>123.7 (2)</td><td>C21—C22—H22</td><td>120.1</td></tr><tr><td>C3—C2—C1</td><td>106.7 (3)</td><td>C23—C22—H22</td><td>120.1</td></tr><tr><td>C3—C2—C21</td><td>125.2 (3)</td><td>C24—C23—C22</td><td>121.6 (5)</td></tr><tr><td>C1—C2—C21</td><td>127.9 (3)</td><td>C24—C23—H23</td><td>119.2</td></tr><tr><td>C3—C2—Fe1</td><td>70.0 (2)</td><td>C22—C23—H23</td><td>119.2</td></tr><tr><td>C1—C2—Fe1</td><td>68.47 (19)</td><td>C23—C24—C25</td><td>119.0 (4)</td></tr><tr><td>C21—C2—Fe1</td><td>129.6 (3)</td><td>C23—C24—H24</td><td>120.5</td></tr><tr><td>C4—C3—C2</td><td>108.4 (4)</td><td>C25—C24—H24</td><td>120.5</td></tr><tr><td>C4—C3—Fe1</td><td>69.3 (2)</td><td>C26—C25—C24</td><td>120.3 (4)</td></tr><tr><td>C2—C3—Fe1</td><td>69.0 (2)</td><td>C26—C25—H25</td><td>119.9</td></tr><tr><td>C4—C3—H3</td><td>125.8</td><td>C24—C25—H25</td><td>119.9</td></tr><tr><td>C2—C3—H3</td><td>125.8</td><td>C21—C26—C25</td><td>121.1 (4)</td></tr><tr><td>Fe1—C3—H3</td><td>127.5</td><td>C21—C26—H26</td><td>119.5</td></tr><tr><td>C5—C4—C3</td><td>108.6 (3)</td><td>C25—C26—H26</td><td>119.5</td></tr><tr><td>C5—C4—Fe1</td><td>69.4 (2)</td><td>Cl2B—C30A—Cl1A</td><td>110.2 (5)</td></tr><tr><td>C3—C4—Fe1</td><td>69.8 (2)</td><td>Cl2B—C30A—H30C</td><td>109.6</td></tr><tr><td>C5—C4—H4</td><td>125.7</td><td>Cl1A—C30A—H30C</td><td>109.6</td></tr><tr><td>C3—C4—H4</td><td>125.7</td><td>Cl2B—C30A—H30A</td><td>109.6</td></tr><tr><td>Fe1—C4—H4</td><td>126.7</td><td>Cl1A—C30A—H30A</td><td>109.6</td></tr><tr><td>C4—C5—C1</td><td>108.1 (4)</td><td>H30C—C30A—H30A</td><td>108.1</td></tr><tr><td>C4—C5—Fe1</td><td>70.2 (2)</td><td>Cl2C—C30B—Cl1B</td><td>114.9 (7)</td></tr><tr><td>C1—C5—Fe1</td><td>68.9 (2)</td><td>Cl2C—C30B—H30D</td><td>113.2</td></tr><tr><td>C4—C5—H5</td><td>126.0</td><td>Cl1B—C30B—H30D</td><td>109.6</td></tr><tr><td>C1—C5—H5</td><td>126.0</td><td>Cl2C—C30B—H30B</td><td>108.5</td></tr><tr><td>Fe1—C5—H5</td><td>126.5</td><td>Cl1B—C30B—H30B</td><td>108.5</td></tr><tr><td>C10—C6—C7</td><td>108.7 (5)</td><td>H30D—C30B—H30B</td><td>101.0</td></tr><tr><td>C10—C6—Fe1</td><td>70.2 (3)</td><td></td><td></td></tr><tr><td>N1—C11—C1—C2</td><td>92.4 (4)</td><td>N1—C11—C1—C5</td><td>-91.2 (4)</td></tr></table>

<table><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>C11—H11A···I1<sup>i</sup></td><td>0.99</td><td>3.17</td><td>3.988 (4)</td><td>140</td></tr><tr><td>C12—H12C···I1</td><td>0.98</td><td>3.21</td><td>4.117 (5)</td><td>154</td></tr><tr><td>C12—H12B···Cl2C</td><td>0.98</td><td>3.51</td><td>3.787 (7)</td><td>99</td></tr><tr><td>C13—H13A···I1</td><td>0.98</td><td>3.27</td><td>4.158 (5)</td><td>151</td></tr><tr><td>C14—H14A···I1</td><td>0.98</td><td>3.14</td><td>4.057 (5)</td><td>157</td></tr><tr><td>C14—H14B···I1<sup>i</sup></td><td>0.98</td><td>3.25</td><td>4.077 (5)</td><td>143</td></tr><tr><td>C30A—H30A···I1<sup>ii</sup></td><td>1.00</td><td>2.89</td><td>3.867 (7)</td><td>166</td></tr><tr><td>C13—H13B···CT2<sup>iii</sup></td><td>0.98</td><td>2.98</td><td>3.901 (6)</td><td>158</td></tr><tr><td>C23—H23···CT1<sup>iv</sup></td><td>0.95</td><td>2.69</td><td>3.600 (7)</td><td>160</td></tr></tbody></table>

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