Synthesis and crystallographic studies of 2-(diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)ferrocene

Uchchhal Bandyopadhyay, Basker Sundararaju, Rinaldo Poli, Eric Manoury, Jean-Claude Daran

► To cite this version:

Uchchhal Bandyopadhyay, Basker Sundararaju, Rinaldo Poli, Eric Manoury, Jean-Claude Daran. Synthesis and crystallographic studies of 2-(diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)ferrocene. Acta crystallographica Section E: Crystallographic communications [2015-..], 2021, 77 (8), pp.853-856. 10.1107/S205698902100760X. hal-03364269

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Acta Cryst.

E

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN 2056-9890

Received 12 July 2021

Accepted 26 July 2021

Edited by M. Zeller, Purdue University, USA

**Keywords:** crystal structure; organometallic chemistry; 2-(diphenylphosphinothioyl)ferrocene chemistry; aldol/elimination reaction.

CCDC reference: 2099273

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

# Synthesis and crystallographic studies of 2-(diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)-ferrocene

Uchchhal Bandyopadhyay,ª Basker Sundararaju,ᵇ Rinaldo Poli,ª Eric Manouryª and Jean-Claude Daranª*

As a follow-up to our research on the chemistry of disubstituted ferrocene derivatives, the synthesis and the structure of the title compound, 2-(diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)ferrocene, [Fe(C₅H₅)(C₂₁H₁₈OPS)], are described. The molecule is built up from a ferrocene unit disubstituted by an S-protected diphenylphosphine group and by a methylvinylketone chain. The crystal structure features weak C-H···O and C-H···S interactions, which build a two-dimensional network. This structure is compared to that of the related disubstituted diphenylphosphino ferrocene.

## 1. Chemical context

Over the last few years, our team has developed several bidentate phosphine-containing planar chiral ferrocene ligands and tested them in various asymmetric catalytic reactions (Manoury & Poli, 2011). In particular, some P,O ligands were synthesized from 2-(diphenylphosphinothioyl)ferrocenecarboxaldehyde (Mateus *et al.*, 2006). This compound can be easily obtained as a racemic mixture or as each pure enantiomer and bears a versatile aldehyde function, which can be used to obtain more complex molecules. In this context, we were delighted to report a new and efficient aldol/elimination reaction of the aldehyde group to yield the corresponding ene-one under mild conditions (see Scheme) using a weak base (*p*Ka of 2-picolyl amine is 8.60; Miletti *et al.*, 2010).

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

Similar compounds have been synthesized but using the Wittig reaction, which requires the synthesis of a specific phosphonium reagent and the use of a strong base, such as *n*-butyllithium (Ye *et al.*, 2017; Schaarschmidt *et al.*, 2014; Štěpnička *et al.* 2008) or sodium hydride (Stepnicka *et al.*, 2008). Indeed, the aldol/elimination sequence has been used to functionalize ferrocenecarboxaldehyde, which is a much less crowded analog of 2-(diphenylphosphinothioyl)ferrocenecarboxaldehyde but with a much stronger base such as NaOH, KOH or tBuOK (see, for instance, Achelle *et al.*, 2012; Romanov *et al.*, 2015; Li *et al.*, 2020; Wieczorek *et al.*, 2016).

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

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

OPEN

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ACCESS

<footnote>ªCNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 Route de Narbonne, F-31077 Toulouse Cedex 4, France, and ᵇDepartment of Chemistry, Indian Institute of Technology Kanpur, Uttar Pradesh, India. *Correspondence e-mail: jean-claude.daran@lcc-toulouse.fr</footnote>
<table><caption>**Table 1**
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>C22–H22···O1<sup>i</sup></td><td>0.95</td><td>2.63</td><td>3.548 (4)</td><td>164</td></tr><tr><td>C112–H112···S1<sup>ii</sup></td><td>0.95</td><td>2.83</td><td>3.576 (3)</td><td>136</td></tr><tr><td>C116–H116···S1</td><td>0.95</td><td>2.89</td><td>3.374 (3)</td><td>113</td></tr><tr><td>C21–H21···S1</td><td>0.95</td><td>2.87</td><td>3.604 (3)</td><td>135</td></tr></tbody></table>

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

## 2. Structural commentary

The molecule is built up from a ferrocene unit disubstituted by an S-protected diphenylphosphine group and by a methyl-vinylketone chain (Fig. 1). As is usually observed for thio-phenylphosphine ferrocenyl derivatives, the P atom is roughly in the plane of the Cp ring, deviating from the mean plane by –0.034 (5) Å, whereas the S atom is offset from this plane by 1.159 (6) Å. The two Cp rings have a staggered conformation with a twist angle of ca 37.1°. The O atom is *trans* to the ferrocene unit with respect to the C=C double bond. The torsion angle of the C2–C21–C22–C23 chain is 172.4 (4)° and the plane containing the double bond is twisted with respect to the Cp ring by 22.8 (2)°. This molecule has a planar chirality related to the occurrence of two different substituents on the Cp ring; however, as the space group is centrosymmetric, the two enantiomers *R/S* are present in equal numbers within the crystal. Two intramolecular C–H···S interactions occur (Table 1).

## 3. Supramolecular features

The packing of the structure is stabilized by weak C–H···O and C–H···S interactions (Table 1). The C–H···O interaction results in the formation of a pseudo-dimer through an $R_2^2(8)$ graph-set motif (Etter *et al.*, 1990; Bernstein *et al.*, 1995) (Fig. 2). The C–H···S intercations build up a chain parallel to the *b* axis and these chains are further associated by the C–

<figure><img src="image_7.png" /><figcaption>**Figure 1**
Molecular structure of the title compound with the atom-labeling scheme. Ellipsoids are drawn at the 50% probability level and the H atoms are represented as small circle of arbitrary radii.</figcaption></figure>

<figure><img src="image_8.png" /><figcaption>**Figure 2**
Partial packing view showing the formation of the $R_2^2(8)$ pseudo-ring arranged around the (1/2, 1, 1/2) inversion center.</figcaption></figure>

<figure><img src="image_9.png" /><figcaption>**Figure 3**
Partial packing view showing the formation of the ribbon parallel to the (011) plane.</figcaption></figure>

H···O interactions of the pseudo-dimer, building a ribbon parallel to the (011) plane (Fig. 3).

## 4. Database survey

A search of the Cambridge Structural Database (CSD version 5.42, update 2020.3; Groom *et al.*, 2016) does not reveal any structures with ferrocenyl disubstituted by a thiodiphenylphosphine and a vinyl; however, a search using a fragment containing a ferrocenyl disubstituted by an unprotected phosphine and a vinyl substituent (Fig. 4) reveals 15 hits of which seven can be compared with the title compound, having only different substituents $R^1$ and $R^2$ (Fig. 4). A comparison of C–C and C–P distances and dihedral angles between the Cp ring

<figure><img src="image_10.png" /><figcaption>**Figure 4**
The model used for the CCDC search.</figcaption></figure>
<table><caption>Figure 5</caption><thead><tr><th>Ref</th><th>X</th><th>C2-C21</th><th>C21-C22</th><th>C22-C23</th><th>C1-P1</th><th>Cp1/C2>C23</th><th>R<sup>1</sup></th><th>R<sup>2</sup></th></tr><tr><th>Title compound</th><th>S</th><th>1.459 (4)</th><th>1.340 (4)</th><th>1.470 (4)</th><th>1.795 (3)</th><th>22.8 (2)</th><th>Ph</th><th>Me</th></tr></thead><tbody><tr><td>BETBOU</td><td>Lone pair</td><td>1.454</td><td>1.334</td><td>1.465</td><td>1.819</td><td>6.7</td><td>Ph</td><td>Ph</td></tr><tr><td>CIVHAR</td><td>Lone pair</td><td>1.448</td><td>1.330</td><td>1.467</td><td>1.818</td><td>9.7</td><td>Ph</td><td>C(O)Me</td></tr><tr><td>KOBXUW</td><td>Lone pair</td><td>1.460</td><td>1.326</td><td>1.472</td><td>1.819</td><td>8.5</td><td>Ph</td><td>Ph</td></tr><tr><td>KOBYAD</td><td>Lone pair</td><td>1.456</td><td>1.321</td><td>1.469</td><td>1.827</td><td>17.7</td><td>Ph</td><td>Ph</td></tr><tr><td>KOBYEH</td><td>Lone pair</td><td>1.466</td><td>1.336</td><td>1.469</td><td>1.805</td><td>6.4</td><td>Ph</td><td>Ph</td></tr><tr><td>KOCLEV</td><td>Lone pair</td><td>1.455</td><td>1.334</td><td>1.460</td><td>1.811</td><td>12.3</td><td>Ph</td><td>Ph</td></tr><tr><td>KOCLIZ</td><td>Lone pair</td><td>1.458</td><td>1.331</td><td>1.468</td><td>1.812</td><td>13.9</td><td>Ph</td><td>Ph</td></tr><tr><td>WIXYAD</td><td>Lone pair</td><td>1.469</td><td>1.323</td><td>1.462</td><td>1.804</td><td>13.1</td><td>Ph</td><td>Ph</td></tr></tbody></table>

Comparison of bond distances (Å) and dihedral angles between the substituted Cp ring (Cp1) and the vinyl mean plane (°) for closely related compounds (CIVHAR: Stepnicka *et al.*, 2008; BETBOU: Kehr *et al.*, 2017; KOB***: Schaarschmidt *et al.*, 2014; WIXYAD: Iftime *et al.*, 2000).

and vinyl mean plane are shown in Fig. 5. Clearly the substituent on the phosphine has some influence on the C—P bond lengths, which range from 1.795 (3) Å for the title compound to 1.827 Å for the [η⁵-1-dicyclohexylphosphino-2-(2-phenylethenyl)cyclopentadienyl]([η⁵-cyclopentadienyl]-iron compound (Schaarschmidt *et al.*, 2014) in which the phosphine bears two cyclohexyl substituents that are rather bulky. The occurrence of the S atom attached to the phosphine in the title compound may explain why the shortest value observed for the title compound. There is no significant difference in the C—C bonds within the vinyl moiety, showing that these values are not affected by the substituent, whereas the discrepancy observed for the dihedral angles between the vinyl unit and the Cp rings (6.4 to 22.8°) is related to the nature of the R¹ and R² substituents on the vinyl unit. The largest value of 22.8°, observed for the title compound, is related to the weak C21—H21···S1 interaction.

## 5. Synthesis and crystallization

To a solution of 2-(diphenylphosphinothioyl)ferrocene-carboxaldehyde (220 mg, 0.51 mmol) in acetone (40 mL) was added 2-picolylamine (0.2 mL, 1.53 mmol). The reaction mixture was refluxed for 24–36h with TLC monitoring of the consumption of aldehyde. After complete consumption, the reaction mixture was evaporated *in vacuo* and extracted with dichloromethane and washed with three portions of water. The combined organic layers were dried over Na₂SO₄, filtered and evaporated to dryness. The crude material was purified by silica gel column chromatography with a hexane–ether mixture (1/1, v/v) to obtain the product as a red solid (0.13 g, 55%). Monocrystals suitable for X-ray diffraction analysis were obtained by slow diffusion of pentane into a dichloromethane solution of 4-(2-thiodiphenylphosphinoferrocenyl)-but-3-ene-one.

¹H NMR (ppm, CD₂Cl₂): δ 8.46 (1H, *d*, *J* = 16.3Hz, vinyl); 7.90–7.80 (*m*, 1H, Ph); 7.65–7.15 (9H, *m*, Ph); 6.28 (1H, *d*, *J* =

<caption>Table 2</caption>

Experimental details.

<table><tbody><tr><td colspan="2">Crystal data</td></tr><tr><td>Chemical formula</td><td>[Fe(C₅H₅)(C₂₁H₁₈OPS)]</td></tr><tr><td>M<sub>r</sub></td><td>470.32</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>7.3643 (9), 17.909 (2), 16.710 (2)</td></tr><tr><td>β (°)</td><td>95.230 (4)</td></tr><tr><td>V (Å<sup>3</sup>)</td><td>2194.8 (5)</td></tr><tr><td>Z</td><td>4</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm<sup>-1</sup>)</td><td>0.87</td></tr><tr><td>Crystal size (mm)</td><td>0.1 × 0.07 × 0.01</td></tr><tr><td colspan="2">Data collection</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>0.673, 0.730</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>43009, 5657, 3907</td></tr><tr><td>R<sub>int</sub></td><td>0.113</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å<sup>-1</sup>)</td><td>0.688</td></tr><tr><td colspan="2">Refinement</td></tr><tr><td>R[F<sup>2</sup> > 2σ(F<sup>2</sup>)], wR(F<sup>2</sup>), S</td><td>0.053, 0.144, 1.03</td></tr><tr><td>No. of reflections</td><td>5657</td></tr><tr><td>No. of parameters</td><td>272</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å<sup>-3</sup>)</td><td>1.43, -0.50</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).

16.3Hz, vinyl); 5.01 (1H, *m*, subst. Cp); 4.65 (1H, *m*, subst. Cp); 4.39 (5H, *s*, subst. Cp); 4.07 (1H, *m*, subst. Cp); 3.87 (3H, *s*, CH₃).

¹³C NMR (ppm, CD₂Cl₂): δ 198.16 (s, C=O); 143.46 (s, vinyl); 134.93 (δ, *J*<sub>CP</sub> = 87.4Hz, quat Ph); 133.01 (δ, *J*<sub>CP</sub> = 86.6Hz, quat Ph); 132.03 (δ, *J*<sub>CP</sub> = 11.0Hz, CH Ph); 131.69 (δ, *J*<sub>CP</sub> = 10.7Hz, CH Ph); 131.54 (δ, *J*<sub>CP</sub> = 3.0Hz, CH Ph para); 131.39 (δ, *J*<sub>CP</sub> = 3.0Hz, CH Ph para); 128.40 (δ, *J*<sub>CP</sub> = 12.5Hz, CH Ph); 128.19 (δ, *J*<sub>CP</sub> = 12.4Hz, CH Ph); 126.89 (s, vinyl); 83.06 (δ, *J*<sub>CP</sub> = 10.7Hz, quat Cp); 77.44 (δ, *J*<sub>CP</sub> = 11.9Hz, subst Cp); 77.00 (δ, *J*<sub>CP</sub> = 93.2Hz, quat Cp); 71.87 (s, Cp); 71.85 (δ, *J*<sub>CP</sub> = 10.3Hz, subst Cp); 69.90 (δ, *J*<sub>CP</sub> = 8.4Hz, subst Cp); 25.87 (s, CH₃).

³¹P NMR (δ, ppm, CD₂Cl₂): δ 41.01.

HRMS (DCI, CH₄): 471.0638 (100%, calculated for C₂₆H₂₄FeOPS [*M*] 471.0635).

M.p.: 441 K (dec).

IR (ATR mode, diamond crystal): ν<sub>max</sub>(solid)/cm<sup>-1</sup>: 1630 (s), 1607 (s), 1677 (w), 1364 (m), 1335 (m), 1264 (s), 1226 (m), 1165 (s), 1099 (s), 1055 (m), 987 (s), 863 (w), 832 (m), 822 (s), 760 (s), 7478 (m), 712 (s), 698 (s), 690 (s), 660 (s), 640 (s), 614 (sm), 583 (m), 534 (s).

## 6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H =
0.95 Å (aromatic) or 0.98 Å (methyl) with $U_{iso}(H) = 1.2U_{eq}(CH)$ aromatic) or $U_{iso}(H) = 1.5U_{eq}(CH_3)$. In the final difference-Fourier map, there is a large residual density, 1.43 e Å⁻³ in the vicinity (1.20 Å) of the H24A atom of the terminal methyl group; it is roughly located in the (100) plane; no chemically logical explanation could be found to explain this residual density.

## Funding information

The authors thank the Indo-French Centre for the Promotion of Advanced Research (IFCPRA/CEFIPRA) for funding (contract No. 5805).

## References

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supporting information

Acta Cryst. (2021). E77, 853-856 [https://doi.org/10.1107/S205698902100760X]

Synthesis and crystallographic studies of 2-(diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)ferrocene

Uchchhal Bandyopadhyay, Basker Sundararaju, Rinaldo Poli, Eric Manoury 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).

2-(Diphenylphosphinothioyl)-2-(3-oxobut-1-en-yl)ferrocene

Crystal data

[Fe(C₅H₅)(C₂₁H₁₈OPS)]

$M_r = 470.32$

Monoclinic, P2₁/c

$a = 7.3643 (9) Å$

$b = 17.909 (2) Å$

$c = 16.710 (2) Å$

$\beta = 95.230 (4)°$

$V = 2194.8 (5) Å³$

$Z = 4$

$F(000) = 976$

$D_x = 1.425 Mg m⁻³$

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 4518 reflections

$\theta = 2.7–24.2°$

$\mu = 0.87 mm⁻¹$

$T = 110 K$

Platelet, orange yellow

0.1 × 0.07 × 0.01 mm

Data collection

Bruker APEXII CCD

diffractometer

Radiation source: micro-focus sealed tube

Graphite monochromator

$\varphi$ and $\omega$ scans

Absorption correction: multi-scan

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

$T_{min} = 0.673, T_{max} = 0.730$

43009 measured reflections

5657 independent reflections

3907 reflections with *I* > 2σ(*I*)

$R_{int} = 0.113$

$\theta_{max} = 29.3°, \theta_{min} = 3.7°$

$h = -10 \rightarrow 10$

$k = -24 \rightarrow 24$

$l = -22 \rightarrow 20$

Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.053$

$wR(F^2) = 0.144$

$S = 1.03$

5657 reflections

272 parameters

0 restraints

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
$$ w = 1/[\sigma^2(F_o^2) + (0.0664P)^2 + 1.8414P] $$
where $P = (F_o^2 + 2F_c^2)/3$
($\Delta/\sigma_{max} = 0.001$)

$$ \Delta\rho_{max} = 1.43 \text{ e Å}^{-3} $$
$$ \Delta\rho_{min} = -0.50 \text{ e Å}^{-3} $$

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.

<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>Fe1</td><td>0.39674 (5)</td><td>0.81999 (2)</td><td>0.74273 (2)</td><td>0.01578 (14)</td></tr><tr><td>S1</td><td>0.61309 (10)</td><td>0.63480 (5)</td><td>0.64301 (5)</td><td>0.0248 (2)</td></tr><tr><td>P1</td><td>0.35129 (10)</td><td>0.65181 (4)</td><td>0.64545 (5)</td><td>0.01527 (18)</td></tr><tr><td>O1</td><td>0.7131 (3)</td><td>0.95064 (13)</td><td>0.44772 (14)</td><td>0.0292 (5)</td></tr><tr><td>C1</td><td>0.2847 (4)</td><td>0.74695 (16)</td><td>0.65962 (17)</td><td>0.0147 (6)</td></tr><tr><td>C2</td><td>0.3485 (4)</td><td>0.81389 (16)</td><td>0.62101 (17)</td><td>0.0151 (6)</td></tr><tr><td>C3</td><td>0.2527 (4)</td><td>0.87556 (17)</td><td>0.65055 (18)</td><td>0.0183 (6)</td></tr><tr><td>H3</td><td>0.267892</td><td>0.926260</td><td>0.635831</td><td>0.022*</td></tr><tr><td>C4</td><td>0.1317 (4)</td><td>0.84957 (18)</td><td>0.70518 (19)</td><td>0.0196 (6)</td></tr><tr><td>H4</td><td>0.051683</td><td>0.879705</td><td>0.732889</td><td>0.024*</td></tr><tr><td>C5</td><td>0.1495 (4)</td><td>0.77100 (17)</td><td>0.71171 (18)</td><td>0.0181 (6)</td></tr><tr><td>H5</td><td>0.084008</td><td>0.739506</td><td>0.744651</td><td>0.022*</td></tr><tr><td>C6</td><td>0.6382 (4)</td><td>0.8733 (2)</td><td>0.7754 (2)</td><td>0.0296 (8)</td></tr><tr><td>H6</td><td>0.699427</td><td>0.906469</td><td>0.742541</td><td>0.036*</td></tr><tr><td>C7</td><td>0.6625 (5)</td><td>0.7957 (2)</td><td>0.7792 (2)</td><td>0.0344 (9)</td></tr><tr><td>H7</td><td>0.742647</td><td>0.767350</td><td>0.749659</td><td>0.041*</td></tr><tr><td>C8</td><td>0.5462 (5)</td><td>0.7670 (2)</td><td>0.8349 (2)</td><td>0.0336 (9)</td></tr><tr><td>H8</td><td>0.534168</td><td>0.716032</td><td>0.849153</td><td>0.040*</td></tr><tr><td>C9</td><td>0.4507 (5)</td><td>0.8281 (2)</td><td>0.86554 (19)</td><td>0.0287 (8)</td></tr><tr><td>H9</td><td>0.363864</td><td>0.825418</td><td>0.904144</td><td>0.034*</td></tr><tr><td>C10</td><td>0.5090 (4)</td><td>0.89381 (19)</td><td>0.8279 (2)</td><td>0.0259 (7)</td></tr><tr><td>H10</td><td>0.467609</td><td>0.943108</td><td>0.836689</td><td>0.031*</td></tr><tr><td>C21</td><td>0.4977 (4)</td><td>0.81952 (17)</td><td>0.56951 (17)</td><td>0.0182 (6)</td></tr><tr><td>H21</td><td>0.573671</td><td>0.777207</td><td>0.564631</td><td>0.022*</td></tr><tr><td>C22</td><td>0.5325 (4)</td><td>0.88155 (17)</td><td>0.52879 (17)</td><td>0.0192 (6)</td></tr><tr><td>H22</td><td>0.446573</td><td>0.921101</td><td>0.528844</td><td>0.023*</td></tr><tr><td>C23</td><td>0.6929 (4)</td><td>0.89337 (17)</td><td>0.48403 (18)</td><td>0.0202 (6)</td></tr><tr><td>C24</td><td>0.8396 (5)</td><td>0.8344 (2)</td><td>0.4856 (2)</td><td>0.0289 (8)</td></tr><tr><td>H24A</td><td>0.918833</td><td>0.844327</td><td>0.442775</td><td>0.043*</td></tr><tr><td>H24B</td><td>0.783093</td><td>0.785139</td><td>0.477308</td><td>0.043*</td></tr><tr><td>H24C</td><td>0.912153</td><td>0.835465</td><td>0.537758</td><td>0.043*</td></tr><tr><td>C111</td><td>0.2541 (4)</td><td>0.60087 (16)</td><td>0.72528 (17)</td><td>0.0157 (6)</td></tr><tr><td>C112</td><td>0.0667 (4)</td><td>0.58941 (18)</td><td>0.72292 (18)</td><td>0.0207 (7)</td></tr><tr><td>H112</td><td>-0.010291</td><td>0.605709</td><td>0.677569</td><td>0.025*</td></tr><tr><td>C113</td><td>-0.0085 (4)</td><td>0.55449 (18)</td><td>0.78603 (19)</td><td>0.0246 (7)</td></tr><tr><td>H113</td><td>-0.136781</td><td>0.547765</td><td>0.784222</td><td>0.029*</td></tr></tbody></table>
<table><tr><td>C114</td><td>0.1032 (5)</td><td>0.52926 (19)</td><td>0.8520 (2)</td><td>0.0265 (7)</td></tr><tr><td>H114</td><td>0.051826</td><td>0.505580</td><td>0.895551</td><td>0.032*</td></tr><tr><td>C115</td><td>0.2907 (5)</td><td>0.53900 (19)</td><td>0.8537 (2)</td><td>0.0267 (7)</td></tr><tr><td>H115</td><td>0.367996</td><td>0.520842</td><td>0.898038</td><td>0.032*</td></tr><tr><td>C116</td><td>0.3662 (4)</td><td>0.57508 (17)</td><td>0.79095 (18)</td><td>0.0202 (6)</td></tr><tr><td>H116</td><td>0.494365</td><td>0.582127</td><td>0.792935</td><td>0.024*</td></tr><tr><td>C121</td><td>0.2198 (4)</td><td>0.62196 (17)</td><td>0.55413 (17)</td><td>0.0172 (6)</td></tr><tr><td>C122</td><td>0.0639 (5)</td><td>0.65958 (19)</td><td>0.5239 (2)</td><td>0.0258 (7)</td></tr><tr><td>H122</td><td>0.025180</td><td>0.702742</td><td>0.550738</td><td>0.031*</td></tr><tr><td>C123</td><td>-0.0366 (5)</td><td>0.63428 (19)</td><td>0.4543 (2)</td><td>0.0294 (8)</td></tr><tr><td>H123</td><td>-0.143308</td><td>0.660150</td><td>0.433628</td><td>0.035*</td></tr><tr><td>C124</td><td>0.0204 (5)</td><td>0.57107 (19)</td><td>0.41551 (19)</td><td>0.0257 (7)</td></tr><tr><td>H124</td><td>-0.046804</td><td>0.553753</td><td>0.367907</td><td>0.031*</td></tr><tr><td>C125</td><td>0.1738 (5)</td><td>0.53371 (18)</td><td>0.4459 (2)</td><td>0.0253 (7)</td></tr><tr><td>H125</td><td>0.211159</td><td>0.490163</td><td>0.419431</td><td>0.030*</td></tr><tr><td>C126</td><td>0.2746 (4)</td><td>0.55824 (17)</td><td>0.51434 (19)</td><td>0.0211 (7)</td></tr><tr><td>H126</td><td>0.381137</td><td>0.531932</td><td>0.534462</td><td>0.025*</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>Fe1</td><td>0.0149 (2)</td><td>0.0185 (2)</td><td>0.0138 (2)</td><td>0.00177 (17)</td><td>0.00064 (16)</td><td>-0.00037 (17)</td></tr><tr><td>S1</td><td>0.0137 (4)</td><td>0.0228 (4)</td><td>0.0384 (5)</td><td>0.0056 (3)</td><td>0.0057 (3)</td><td>0.0026 (3)</td></tr><tr><td>P1</td><td>0.0126 (4)</td><td>0.0148 (4)</td><td>0.0185 (4)</td><td>0.0030 (3)</td><td>0.0017 (3)</td><td>0.0020 (3)</td></tr><tr><td>O1</td><td>0.0346 (13)</td><td>0.0265 (13)</td><td>0.0273 (13)</td><td>-0.0097 (11)</td><td>0.0069 (10)</td><td>0.0070 (10)</td></tr><tr><td>C1</td><td>0.0107 (13)</td><td>0.0166 (15)</td><td>0.0165 (14)</td><td>0.0022 (11)</td><td>0.0000 (11)</td><td>0.0008 (11)</td></tr><tr><td>C2</td><td>0.0122 (13)</td><td>0.0180 (15)</td><td>0.0145 (14)</td><td>0.0019 (11)</td><td>-0.0022 (11)</td><td>0.0008 (11)</td></tr><tr><td>C3</td><td>0.0205 (15)</td><td>0.0158 (15)</td><td>0.0179 (15)</td><td>0.0014 (12)</td><td>-0.0017 (12)</td><td>0.0000 (12)</td></tr><tr><td>C4</td><td>0.0136 (14)</td><td>0.0210 (16)</td><td>0.0243 (16)</td><td>0.0060 (12)</td><td>0.0023 (12)</td><td>-0.0021 (13)</td></tr><tr><td>C5</td><td>0.0092 (13)</td><td>0.0238 (17)</td><td>0.0217 (15)</td><td>0.0022 (12)</td><td>0.0033 (11)</td><td>0.0012 (12)</td></tr><tr><td>C6</td><td>0.0207 (17)</td><td>0.043 (2)</td><td>0.0235 (17)</td><td>-0.0084 (15)</td><td>-0.0076 (13)</td><td>0.0031 (15)</td></tr><tr><td>C7</td><td>0.0179 (16)</td><td>0.055 (3)</td><td>0.0286 (19)</td><td>0.0117 (16)</td><td>-0.0066 (14)</td><td>-0.0145 (17)</td></tr><tr><td>C8</td><td>0.043 (2)</td><td>0.0265 (19)</td><td>0.0271 (18)</td><td>-0.0002 (16)</td><td>-0.0214 (16)</td><td>0.0042 (15)</td></tr><tr><td>C9</td><td>0.0310 (18)</td><td>0.040 (2)</td><td>0.0150 (16)</td><td>-0.0072 (16)</td><td>0.0017 (13)</td><td>-0.0031 (14)</td></tr><tr><td>C10</td><td>0.0279 (17)</td><td>0.0236 (18)</td><td>0.0247 (17)</td><td>-0.0024 (14)</td><td>-0.0059 (13)</td><td>-0.0083 (14)</td></tr><tr><td>C21</td><td>0.0204 (15)</td><td>0.0175 (15)</td><td>0.0164 (15)</td><td>0.0020 (12)</td><td>0.0003 (12)</td><td>-0.0009 (12)</td></tr><tr><td>C22</td><td>0.0209 (15)</td><td>0.0192 (16)</td><td>0.0174 (15)</td><td>0.0015 (12)</td><td>0.0014 (12)</td><td>-0.0006 (12)</td></tr><tr><td>C23</td><td>0.0218 (16)</td><td>0.0196 (16)</td><td>0.0188 (15)</td><td>0.0001 (13)</td><td>-0.0008 (12)</td><td>-0.0028 (12)</td></tr><tr><td>C24</td><td>0.0243 (17)</td><td>0.030 (2)</td><td>0.0331 (19)</td><td>0.0044 (14)</td><td>0.0069 (14)</td><td>0.0034 (15)</td></tr><tr><td>C111</td><td>0.0158 (14)</td><td>0.0145 (14)</td><td>0.0168 (14)</td><td>0.0003 (11)</td><td>0.0008 (11)</td><td>0.0007 (11)</td></tr><tr><td>C112</td><td>0.0160 (14)</td><td>0.0256 (17)</td><td>0.0196 (15)</td><td>-0.0015 (13)</td><td>-0.0038 (12)</td><td>0.0041 (13)</td></tr><tr><td>C113</td><td>0.0203 (16)</td><td>0.0262 (18)</td><td>0.0273 (18)</td><td>-0.0057 (13)</td><td>0.0024 (13)</td><td>0.0008 (14)</td></tr><tr><td>C114</td><td>0.0316 (18)</td><td>0.0254 (18)</td><td>0.0229 (17)</td><td>-0.0034 (14)</td><td>0.0046 (14)</td><td>0.0056 (14)</td></tr><tr><td>C115</td><td>0.0310 (18)</td><td>0.0242 (18)</td><td>0.0237 (17)</td><td>0.0003 (14)</td><td>-0.0049 (14)</td><td>0.0095 (14)</td></tr><tr><td>C116</td><td>0.0187 (15)</td><td>0.0168 (16)</td><td>0.0241 (16)</td><td>0.0009 (12)</td><td>-0.0030 (12)</td><td>0.0018 (12)</td></tr><tr><td>C121</td><td>0.0188 (14)</td><td>0.0190 (15)</td><td>0.0143 (14)</td><td>0.0019 (12)</td><td>0.0037 (11)</td><td>0.0008 (12)</td></tr><tr><td>C122</td><td>0.0301 (18)</td><td>0.0209 (17)</td><td>0.0254 (17)</td><td>0.0101 (14)</td><td>-0.0032 (14)</td><td>-0.0046 (13)</td></tr><tr><td>C123</td><td>0.036 (2)</td><td>0.0261 (18)</td><td>0.0241 (17)</td><td>0.0089 (15)</td><td>-0.0073 (14)</td><td>-0.0014 (14)</td></tr></tbody></table>
<table><tr><td>C124</td><td>0.0356 (19)</td><td>0.0241 (17)</td><td>0.0172 (16)</td><td>-0.0054 (15)</td><td>0.0020 (13)</td><td>-0.0005 (13)</td></tr><tr><td>C125</td><td>0.0314 (18)</td><td>0.0191 (16)</td><td>0.0271 (18)</td><td>-0.0006 (14)</td><td>0.0112 (14)</td><td>-0.0053 (13)</td></tr><tr><td>C126</td><td>0.0215 (15)</td><td>0.0183 (16)</td><td>0.0245 (16)</td><td>0.0023 (13)</td><td>0.0072 (12)</td><td>-0.0015 (13)</td></tr></table>

Geometric parameters (Å, °)

<table><tr><td>Fe1—C1</td><td>2.028 (3)</td><td>C9—H9</td><td>0.9500</td></tr><tr><td>Fe1—C2</td><td>2.035 (3)</td><td>C10—H10</td><td>0.9500</td></tr><tr><td>Fe1—C7</td><td>2.043 (3)</td><td>C21—C22</td><td>1.340 (4)</td></tr><tr><td>Fe1—C8</td><td>2.043 (3)</td><td>C21—H21</td><td>0.9500</td></tr><tr><td>Fe1—C5</td><td>2.045 (3)</td><td>C22—C23</td><td>1.470 (4)</td></tr><tr><td>Fe1—C3</td><td>2.047 (3)</td><td>C22—H22</td><td>0.9500</td></tr><tr><td>Fe1—C6</td><td>2.048 (3)</td><td>C23—C24</td><td>1.509 (4)</td></tr><tr><td>Fe1—C10</td><td>2.059 (3)</td><td>C24—H24A</td><td>0.9800</td></tr><tr><td>Fe1—C9</td><td>2.060 (3)</td><td>C24—H24B</td><td>0.9800</td></tr><tr><td>Fe1—C4</td><td>2.064 (3)</td><td>C24—H24C</td><td>0.9800</td></tr><tr><td>S1—P1</td><td>1.9560 (11)</td><td>C111—C116</td><td>1.391 (4)</td></tr><tr><td>P1—C1</td><td>1.795 (3)</td><td>C111—C112</td><td>1.392 (4)</td></tr><tr><td>P1—C121</td><td>1.812 (3)</td><td>C112—C113</td><td>1.384 (4)</td></tr><tr><td>P1—C111</td><td>1.816 (3)</td><td>C112—H112</td><td>0.9500</td></tr><tr><td>O1—C23</td><td>1.208 (4)</td><td>C113—C114</td><td>1.390 (5)</td></tr><tr><td>C1—C5</td><td>1.446 (4)</td><td>C113—H113</td><td>0.9500</td></tr><tr><td>C1—C2</td><td>1.459 (4)</td><td>C114—C115</td><td>1.390 (5)</td></tr><tr><td>C2—C3</td><td>1.423 (4)</td><td>C114—H114</td><td>0.9500</td></tr><tr><td>C2—C21</td><td>1.459 (4)</td><td>C115—C116</td><td>1.389 (4)</td></tr><tr><td>C3—C4</td><td>1.412 (4)</td><td>C115—H115</td><td>0.9500</td></tr><tr><td>C3—H3</td><td>0.9500</td><td>C116—H116</td><td>0.9500</td></tr><tr><td>C4—C5</td><td>1.417 (4)</td><td>C121—C122</td><td>1.386 (4)</td></tr><tr><td>C4—H4</td><td>0.9500</td><td>C121—C126</td><td>1.399 (4)</td></tr><tr><td>C5—H5</td><td>0.9500</td><td>C122—C123</td><td>1.396 (4)</td></tr><tr><td>C6—C10</td><td>1.401 (5)</td><td>C122—H122</td><td>0.9500</td></tr><tr><td>C6—C7</td><td>1.401 (5)</td><td>C123—C124</td><td>1.389 (5)</td></tr><tr><td>C6—H6</td><td>0.9500</td><td>C123—H123</td><td>0.9500</td></tr><tr><td>C7—C8</td><td>1.417 (6)</td><td>C124—C125</td><td>1.370 (5)</td></tr><tr><td>C7—H7</td><td>0.9500</td><td>C124—H124</td><td>0.9500</td></tr><tr><td>C8—C9</td><td>1.421 (5)</td><td>C125—C126</td><td>1.377 (5)</td></tr><tr><td>C8—H8</td><td>0.9500</td><td>C125—H125</td><td>0.9500</td></tr><tr><td>C9—C10</td><td>1.420 (5)</td><td>C126—H126</td><td>0.9500</td></tr><tr><td>C1—Fe1—C2</td><td>42.10 (11)</td><td>C10—C6—C7</td><td>108.8 (3)</td></tr><tr><td>C1—Fe1—C7</td><td>112.69 (13)</td><td>C10—C6—Fe1</td><td>70.49 (19)</td></tr><tr><td>C2—Fe1—C7</td><td>111.19 (13)</td><td>C7—C6—Fe1</td><td>69.8 (2)</td></tr><tr><td>C1—Fe1—C8</td><td>111.98 (13)</td><td>C10—C6—H6</td><td>125.6</td></tr><tr><td>C2—Fe1—C8</td><td>139.56 (14)</td><td>C7—C6—H6</td><td>125.6</td></tr><tr><td>C7—Fe1—C8</td><td>40.60 (16)</td><td>Fe1—C6—H6</td><td>125.7</td></tr><tr><td>C1—Fe1—C5</td><td>41.60 (11)</td><td>C6—C7—C8</td><td>107.9 (3)</td></tr><tr><td>C2—Fe1—C5</td><td>69.73 (12)</td><td>C6—C7—Fe1</td><td>70.16 (19)</td></tr><tr><td>C7—Fe1—C5</td><td>142.26 (15)</td><td>C8—C7—Fe1</td><td>69.70 (19)</td></tr></table>
<table>
  <tbody>
    <tr><td>C8—Fe1—C5</td><td>113.44 (14)</td></tr>
    <tr><td>C1—Fe1—C3</td><td>69.37 (12)</td></tr>
    <tr><td>C2—Fe1—C3</td><td>40.80 (11)</td></tr>
    <tr><td>C7—Fe1—C3</td><td>138.11 (14)</td></tr>
    <tr><td>C8—Fe1—C3</td><td>178.29 (14)</td></tr>
    <tr><td>C5—Fe1—C3</td><td>68.27 (12)</td></tr>
    <tr><td>C1—Fe1—C6</td><td>140.55 (13)</td></tr>
    <tr><td>C2—Fe1—C6</td><td>111.05 (13)</td></tr>
    <tr><td>C7—Fe1—C6</td><td>40.06 (15)</td></tr>
    <tr><td>C8—Fe1—C6</td><td>67.70 (15)</td></tr>
    <tr><td>C5—Fe1—C6</td><td>177.42 (14)</td></tr>
    <tr><td>C3—Fe1—C6</td><td>110.59 (14)</td></tr>
    <tr><td>C1—Fe1—C10</td><td>179.48 (13)</td></tr>
    <tr><td>C2—Fe1—C10</td><td>138.35 (13)</td></tr>
    <tr><td>C7—Fe1—C10</td><td>67.51 (14)</td></tr>
    <tr><td>C8—Fe1—C10</td><td>67.83 (14)</td></tr>
    <tr><td>C5—Fe1—C10</td><td>137.97 (13)</td></tr>
    <tr><td>C3—Fe1—C10</td><td>110.83 (13)</td></tr>
    <tr><td>C6—Fe1—C10</td><td>39.90 (14)</td></tr>
    <tr><td>C1—Fe1—C9</td><td>139.22 (13)</td></tr>
    <tr><td>C2—Fe1—C9</td><td>178.56 (13)</td></tr>
    <tr><td>C7—Fe1—C9</td><td>68.00 (14)</td></tr>
    <tr><td>C8—Fe1—C9</td><td>40.52 (15)</td></tr>
    <tr><td>C5—Fe1—C9</td><td>111.67 (13)</td></tr>
    <tr><td>C3—Fe1—C9</td><td>139.05 (13)</td></tr>
    <tr><td>C6—Fe1—C9</td><td>67.54 (14)</td></tr>
    <tr><td>C10—Fe1—C9</td><td>40.33 (14)</td></tr>
    <tr><td>C1—Fe1—C4</td><td>69.08 (12)</td></tr>
    <tr><td>C2—Fe1—C4</td><td>68.66 (12)</td></tr>
    <tr><td>C7—Fe1—C4</td><td>177.37 (15)</td></tr>
    <tr><td>C8—Fe1—C4</td><td>141.06 (15)</td></tr>
    <tr><td>C5—Fe1—C4</td><td>40.33 (12)</td></tr>
    <tr><td>C3—Fe1—C4</td><td>40.17 (12)</td></tr>
    <tr><td>C6—Fe1—C4</td><td>137.36 (14)</td></tr>
    <tr><td>C10—Fe1—C4</td><td>110.75 (13)</td></tr>
    <tr><td>C9—Fe1—C4</td><td>112.09 (13)</td></tr>
    <tr><td>C1—P1—C121</td><td>105.06 (14)</td></tr>
    <tr><td>C1—P1—C111</td><td>104.43 (13)</td></tr>
    <tr><td>C121—P1—C111</td><td>104.73 (14)</td></tr>
    <tr><td>C1—P1—S1</td><td>115.62 (10)</td></tr>
    <tr><td>C121—P1—S1</td><td>112.86 (10)</td></tr>
    <tr><td>C111—P1—S1</td><td>113.10 (10)</td></tr>
    <tr><td>C5—C1—C2</td><td>106.8 (2)</td></tr>
    <tr><td>C5—C1—P1</td><td>125.0 (2)</td></tr>
    <tr><td>C2—C1—P1</td><td>128.2 (2)</td></tr>
    <tr><td>C5—C1—Fe1</td><td>69.82 (17)</td></tr>
    <tr><td>C2—C1—Fe1</td><td>69.23 (16)</td></tr>
    <tr><td>P1—C1—Fe1</td><td>127.14 (15)</td></tr>
  </tbody>
</table>

<table>
  <tbody>
    <tr><td>C6—C7—H7</td><td>126.1</td></tr>
    <tr><td>C8—C7—H7</td><td>126.1</td></tr>
    <tr><td>Fe1—C7—H7</td><td>125.7</td></tr>
    <tr><td>C7—C8—C9</td><td>107.9 (3)</td></tr>
    <tr><td>C7—C8—Fe1</td><td>69.70 (19)</td></tr>
    <tr><td>C9—C8—Fe1</td><td>70.38 (19)</td></tr>
    <tr><td>C7—C8—H8</td><td>126.1</td></tr>
    <tr><td>C9—C8—H8</td><td>126.1</td></tr>
    <tr><td>Fe1—C8—H8</td><td>125.4</td></tr>
    <tr><td>C10—C9—C8</td><td>107.4 (3)</td></tr>
    <tr><td>C10—C9—Fe1</td><td>69.82 (18)</td></tr>
    <tr><td>C8—C9—Fe1</td><td>69.10 (18)</td></tr>
    <tr><td>C10—C9—H9</td><td>126.3</td></tr>
    <tr><td>C8—C9—H9</td><td>126.3</td></tr>
    <tr><td>Fe1—C9—H9</td><td>126.3</td></tr>
    <tr><td>C6—C10—C9</td><td>108.1 (3)</td></tr>
    <tr><td>C6—C10—Fe1</td><td>69.62 (19)</td></tr>
    <tr><td>C9—C10—Fe1</td><td>69.85 (18)</td></tr>
    <tr><td>C6—C10—H10</td><td>126.0</td></tr>
    <tr><td>C9—C10—H10</td><td>126.0</td></tr>
    <tr><td>Fe1—C10—H10</td><td>126.1</td></tr>
    <tr><td>C22—C21—C2</td><td>123.1 (3)</td></tr>
    <tr><td>C22—C21—H21</td><td>118.4</td></tr>
    <tr><td>C2—C21—H21</td><td>118.4</td></tr>
    <tr><td>C21—C22—C23</td><td>125.3 (3)</td></tr>
    <tr><td>C21—C22—H22</td><td>117.3</td></tr>
    <tr><td>C23—C22—H22</td><td>117.3</td></tr>
    <tr><td>O1—C23—C22</td><td>121.3 (3)</td></tr>
    <tr><td>O1—C23—C24</td><td>118.8 (3)</td></tr>
    <tr><td>C22—C23—C24</td><td>119.8 (3)</td></tr>
    <tr><td>C23—C24—H24A</td><td>109.5</td></tr>
    <tr><td>C23—C24—H24B</td><td>109.5</td></tr>
    <tr><td>H24A—C24—H24B</td><td>109.5</td></tr>
    <tr><td>C23—C24—H24C</td><td>109.5</td></tr>
    <tr><td>H24A—C24—H24C</td><td>109.5</td></tr>
    <tr><td>H24B—C24—H24C</td><td>109.5</td></tr>
    <tr><td>C116—C111—C112</td><td>119.3 (3)</td></tr>
    <tr><td>C116—C111—P1</td><td>120.1 (2)</td></tr>
    <tr><td>C112—C111—P1</td><td>120.6 (2)</td></tr>
    <tr><td>C113—C112—C111</td><td>120.6 (3)</td></tr>
    <tr><td>C113—C112—H112</td><td>119.7</td></tr>
    <tr><td>C111—C112—H112</td><td>119.7</td></tr>
    <tr><td>C112—C113—C114</td><td>120.2 (3)</td></tr>
    <tr><td>C112—C113—H113</td><td>119.9</td></tr>
    <tr><td>C114—C113—H113</td><td>119.9</td></tr>
    <tr><td>C113—C114—C115</td><td>119.4 (3)</td></tr>
    <tr><td>C113—C114—H114</td><td>120.3</td></tr>
    <tr><td>C115—C114—H114</td><td>120.3</td></tr>
  </tbody>
</table>
<table><caption>Hydrogen-bond geometry (Å, °)</caption><tr><td>C3—C2—C21</td><td>125.1 (3)</td><td>C116—C115—C114</td><td>120.6 (3)</td></tr><tr><td>C3—C2—C1</td><td>107.1 (2)</td><td>C116—C115—H115</td><td>119.7</td></tr><tr><td>C21—C2—C1</td><td>127.4 (3)</td><td>C114—C115—H115</td><td>119.7</td></tr><tr><td>C3—C2—Fe1</td><td>70.03 (16)</td><td>C115—C116—C111</td><td>120.0 (3)</td></tr><tr><td>C21—C2—Fe1</td><td>120.9 (2)</td><td>C115—C116—H116</td><td>120.0</td></tr><tr><td>C1—C2—Fe1</td><td>68.67 (16)</td><td>C111—C116—H116</td><td>120.0</td></tr><tr><td>C4—C3—C2</td><td>109.3 (3)</td><td>C122—C121—C126</td><td>119.3 (3)</td></tr><tr><td>C4—C3—Fe1</td><td>70.58 (17)</td><td>C122—C121—P1</td><td>121.6 (2)</td></tr><tr><td>C2—C3—Fe1</td><td>69.17 (16)</td><td>C126—C121—P1</td><td>119.1 (2)</td></tr><tr><td>C4—C3—H3</td><td>125.3</td><td>C121—C122—C123</td><td>120.3 (3)</td></tr><tr><td>C2—C3—H3</td><td>125.3</td><td>C121—C122—H122</td><td>119.9</td></tr><tr><td>Fe1—C3—H3</td><td>126.5</td><td>C123—C122—H122</td><td>119.9</td></tr><tr><td>C3—C4—C5</td><td>108.5 (3)</td><td>C124—C123—C122</td><td>119.6 (3)</td></tr><tr><td>C3—C4—Fe1</td><td>69.25 (17)</td><td>C124—C123—H123</td><td>120.2</td></tr><tr><td>C5—C4—Fe1</td><td>69.09 (16)</td><td>C122—C123—H123</td><td>120.2</td></tr><tr><td>C3—C4—H4</td><td>125.7</td><td>C125—C124—C123</td><td>119.9 (3)</td></tr><tr><td>C5—C4—H4</td><td>125.7</td><td>C125—C124—H124</td><td>120.0</td></tr><tr><td>Fe1—C4—H4</td><td>127.5</td><td>C123—C124—H124</td><td>120.0</td></tr><tr><td>C4—C5—C1</td><td>108.3 (3)</td><td>C124—C125—C126</td><td>121.1 (3)</td></tr><tr><td>C4—C5—Fe1</td><td>70.58 (17)</td><td>C124—C125—H125</td><td>119.5</td></tr><tr><td>C1—C5—Fe1</td><td>68.58 (16)</td><td>C126—C125—H125</td><td>119.5</td></tr><tr><td>C4—C5—H5</td><td>125.9</td><td>C125—C126—C121</td><td>119.9 (3)</td></tr><tr><td>C1—C5—H5</td><td>125.9</td><td>C125—C126—H126</td><td>120.1</td></tr><tr><td>Fe1—C5—H5</td><td>126.5</td><td>C121—C126—H126</td><td>120.1</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>C22—H22···O1<sup>i</sup></td><td>0.95</td><td>2.63</td><td>3.548 (4)</td><td>164</td></tr><tr><td>C112—H112···S1<sup>ii</sup></td><td>0.95</td><td>2.83</td><td>3.576 (3)</td><td>136</td></tr><tr><td>C116—H116···S1</td><td>0.95</td><td>2.89</td><td>3.374 (3)</td><td>113</td></tr><tr><td>C21—H21···S1</td><td>0.95</td><td>2.87</td><td>3.604 (3)</td><td>135</td></tr></tbody></table>

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