Covalency between the uranyl ion and di­thio­phosphinate by sulfur K-edge X-ray absorption spectroscopy and density functional theory

The dithiophosphinic acids (HS₂PR₂) have been used for the selective separation of trivalent actinides (An^III) from lanthanides (Ln^III) over the past decades. The substituents on the di­thio­phosphinic acids dramatically impact the separation performance, but the mechanism is still open for debate. In this work, two di­thio­phosphinic acids with significantly different An^III/Ln^III separation performance, i.e. di­phenyl di­thio­phosphinic acid (HS₂PPh₂) and bis­(ortho-trifluoro­methyl­phenyl) di­thio­phosphinic acid [HS₂P(o-CF₃C₆H₄)₂], are employed to understand the substituent effect on the bonding covalency between the S₂PR₂⁻ anions (R = Ph and o-CF₃C₆H₄) and the uranyl ion by sulfur K-edge X-ray absorption spectroscopy (XAS) in combination with density functional theory calculations. The two UO₂(S₂PR₂)(EtOH) complexes display similar XAS spectra, in which the first pre-edge feature with an intensity of 0.16 is entirely attributed to the transitions from S 1s orbitals to the unoccupied molecular orbitals due to the mixing between U 5f and S 3p orbitals. The Mulliken population analysis indicates that the amount of S 3p character in these orbitals is essentially identical for the UO₂(S₂PPh₂)₂(EtOH) and UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH) complexes, which is lower than that in the U 6d-based orbitals. The essentially identical covalency in U—S bonds for the two UO₂(S₂PR₂)₂(EtOH) complexes are contradictory to the significantly different An^III/Ln^III separation performance of the two di­thio­phosphinic acids, thus the covalency seems to be unable to account for substituent effects in the An^III/Ln^III separation by the di­thio­phosphinic acids. The results in this work provide valuable insight into the understanding of the mechanism in the An^III/Ln^III separation by the di­thio­phosphinic acids.

1. Introduction

The selective separation of trivalent actinides (An^III) and lanthanides (Ln^III) is one of the most urgent issues for the implementation of the partitioning and transmutation strategy within advanced nuclear fuel cycles, and it is also recognized as a critical challenge in separation science due to the almost identical ionic radii as well as the similar chemical and physical properties between An^III and Ln^III. Soft-donor ligands have demonstrated good performance in An^III/Ln^III separation, in which the di­thio­phosphinic acids (HS₂PR₂) show great potential in the An^III/Ln^III separation process (Bessen et al., 2020). For example, bis­(2,4,4-tri­methyl­pentyl)­dithio­phosphinic acid (the purified Cyanex301) in kerosene can extract Am^III from Eu^III with a separation factor as high as 5000 (Chen et al., 1996, 2014). Other di­thio­phosphinic acids with different substituents were also reported for the An^III/Ln^III separation studies (Peterman et al., 2009, 2010; Xu et al., 2008; Wang, Jia, Pan et al., 2013; Pu et al., 2019, 2020; Wang et al., 2013, 2019). Strikingly, bis­(ortho-tri­fluoro­methyl­phenyl) di­thio­phosphinic acid [HS₂P(o-CF₃C₆H₄)₂] can afford an Am^III/Eu^III separation factor higher than 10⁴, which is three orders of magnitude higher than that for di­phenyl di­thio­phosphinic acid (HS₂PPh₂) (Xu et al., 2008; Peterman et al., 2010).

Several factors emerged in the previous studies that are responsible for the substituent effect in the An^III/Ln^III separation by the di­thio­phosphinic acids, including (1) the deprotonation properties of the di­thio­phosphinic acids (Wang et al., 2019; Pu et al., 2020), (2) the chemical stoichiometry and structure of the extracted complexes (Pu et al., 2020; Xu & Rao, 2014; Greer et al., 2020; Tian et al., 2002, 2003; Weigl et al., 2005), and (3) the difference in the binding affinity of the ligands to the metals (especially the covalent part) (Keith & Batista, 2012; Lan et al., 2012; Cao et al., 2010; Bhattacharyya et al., 2011). For instance, the unexpectedly high pK_a and strong nucleophile for HS₂P(o-CF₃C₆H₄)₂ may destabilize the anion to a greater extent and increase selectivity towards actinides (Benson et al., 2008; Leavitt et al., 2008). Pu et al. found that S₂PPh₂⁻ formed up to 2:1 complexes with Nd³⁺, whilst S₂P(o-CF₃C₆H₄)₂⁻ formed up to 3:1 complexes (Pu et al., 2020). The substituent effect on the bonding covalency between the di­thio­phosphinate ligands and metal ions has been raised as an important factor in driving An^III/Ln^III separation (Keith & Batista, 2012; Daly, Keith, Batista, Boland, Clark et al., 2012; Daly, Keith, Batista, Boland, Kozimor et al., 2012). Daly et al. examined the electronic structure of several S₂PR₂⁻ anions and found that the S₂P(o-CF₃C₆H₄)₂⁻ anion was a `softer' extractant as compared with the S₂PPh₂⁻ anion, which promoted the selectivity towards actinides (Daly, Keith, Batista, Boland, Clark et al., 2012). Despite the numerous theoretical calculations on modeling the extraction of Ln^III and An^III by the di­thio­phosphinic acids (Greer et al., 2020; Lan et al., 2012; Bhattacharyya et al., 2011; Diamond et al., 1954; Choppin, 2002; Ingram et al., 2008; Gaunt et al., 2008; Sadhu & Dolg, 2019; Kaneko & Watanabe, 2018; Kaneko et al., 2017; Cross et al., 2016; Kaneko et al., 2015; Jensen & Bond, 2002; Lehman-Andino et al., 2019), experimental evaluation on the covalency in M—S (where M is a metal) chemical bonding in the di­thio­phosphinate complexes, to the best of our knowledge, has not been reported up to now.

In this work, we are motivated to address whether the extent of covalency in the M—S bonds would account for the separation performance. The technique of ligand K-edge XAS in combination with density functional theory (DFT) calculations is employed. The intensity of the pre-edge features in XAS directly reflects the amount of ligand p character in metal-derived molecular orbitals (MOs) and thus the covalency in metal–ligand bonds (Solomon et al., 2005). This technique has proven to be one of the most versatile and direct spectroscopic techniques to directly probe the mixing of metal d and f orbitals with ligand p orbitals (Kozimor et al., 2008, 2009; Minasian et al., 2012, 2013, 2014, 2017; Spencer et al., 2013; Löble et al., 2015; Pemmaraju et al., 2014; Ha et al., 2017; Cross et al., 2017; Donahue et al., 2014; Su et al., 2018; Lee et al., 2019; Smiles et al., 2020; Sun et al., 2010; Sarangi et al., 2007; Queen et al., 2013). As the direct examination of complexes of the trivalent actinide such as Am^III by synchrotron XAS is not feasible due to high radioactivity, in this work we examined the UO₂(S₂PR₂)₂(EtOH) (R = Ph, o-CF₃C₆H₄) complexes by sulfur K-edge XAS to detect the substituent effect on the bonding covalency between the di­thio­phosphinate anions and the uranyl ion. Results in this work will be informative in terms of the substituent effect on the bonding covalency between the di­thio­phosphinate anions and trivalent actinides, and thus helpful for the understanding of the mechanism in the An^III/Ln^III separation by the di­thio­phosphinic acids.

2. Results and discussion

2.1. Sample preparation

Complexes of UO₂²⁺ with S₂PR₂⁻ (R = Ph, o-CF₃C₆H₄) ligands were prepared and isolated as highly pure crystalline solids before the XAS experiments. Note that the complexes of UO₂²⁺ with the S₂PPh₂⁻ ligand have been crystalized previously (Meng et al., 2018; Pinkerton et al., 1997; Storey et al., 1983). However, the crystal structures of the complexes of UO₂²⁺ with the S₂P(o-CF₃C₆H₄)₂⁻ ligand have not been reported. In this work, we successfully synthesized single crystals of UO₂²⁺ with the two S₂PR₂⁻ ligands. The crystal structures of the UO₂(S₂PR₂)₂(EtOH) complexes are shown in Fig. 1. Data collection and refinement details are available in Table S1 of the supporting information. Both the two S₂PR₂⁻ ligands form up to 2:1 complexes with UO₂²⁺, similar to previous reports (Meng et al., 2018; Pinkerton et al., 1997; Storey et al., 1983). Both the two UO₂(S₂PR₂)₂(EtOH) complexes contain four sulfur atoms from the two bidentate di­thio­phosphinate ligands and one oxygen atom from the coordinated ethanol in the first coordinated sphere of the equatorial plane of UO₂²⁺. The crystals of the two ligands S₂PR₂⁻ were also obtained by employing tetra­phenyl­phospho­nium (Ph₄P⁺) as the cation according to the procedure reported in the literature (Daly, Klaehn et al., 2012).

Figure 1 Crystal structure of UO2(S2PR2)2(EtOH) investigated in this work with thermal ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. (U: yellow; S: blue; P: pink; O: red; C: white; F: green.)

The selected bond lengths and bond angles for the crystal structures of the [PPh₄][S₂PR₂] ligands and the UO₂(S₂PR₂)₂(EtOH) complexes are provided in Table 1. The P—S bond lengths are 1.977 and 1.979 Å in S₂PPh₂⁻ and S₂P(o-CF₃C₆H₄)₂⁻, respectively, and these values prolong to 2.010 Å in the two UO₂(S₂PR₂)₂(EtOH) complexes, suggesting comparable bonding interactions of the two S₂PR₂⁻ ligands with the uranyl ion. The S—U—S bond angles are 70.74° and 70.23° for UO₂(S₂Ph₂)₂(EtOH) and UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH), respectively, and the S—P—S bond angles are 111.09° and 109.78° for UO₂(S₂PPh₂)₂(EtOH) and UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH), respectively. The comparable S—U—S and S—P—S bond angles suggest comparable bonding interactions of S₂PPh₂⁻ and S₂P(o-CF₃C₆H₄)₂⁻ with the uranyl ion.

Table 1
Selected bond lengths (Å) and bond angles (°) for [PPh₄][S₂PR₂] and UO₂(S₂PR₂)₂(EtOH) in the crystal structures

	Bond length			Bond angle
Compound	U−Oyl	U—S	P—S	O−U−O	S—U—S	S—P—S
[PPh4][S2PPh2]	–	–	1.977 (1)	–	–	117.80 (4)
[PPh4][S2P(o-CF3C6H4)2]	–	–	1.979 (2)	–	–	116.79 (3)
UO2(S2PPh2)2(EtOH)	1.765 (1)	2.863 (29)	2.010 (26)	175.77 (10)	70.74 (2)	111.09 (5)
UO2[S2P(o-CF3C6H4)2]2(EtOH)	1.740 (42)	2.858 (36)	2.010 (11)	177.1 (10)	70.23 (19)	109.78 (93)

2.2. P K-edge XAS

Before the collection of S K-edge XAS, we collected the P K-edge XAS spectra for the [PPh₄][S₂PR₂] ligands and the UO₂(S₂PR₂)₂(EtOH) complexes. The background-subtracted and normalized P K-edge XAS spectra are shown in Fig. 2, and the full spectra are presented in Fig. S1 of the supporting information. The spectrum of PPh₄Cl was also collected to compare with the spectra of the [PPh₄][S₂PR₂] ligands. According to the second derivatives (Fig. S2), the spectrum of PPh₄Cl contains three pre-edge features at 2147.6, 2149.4 and 2150.7 eV. The spectra of the [PPh₄][S₂PR₂] ligands both contain four pre-edge features at about 2147.6, 2149.2 and 2149.8, 2150.5 eV. The spectra of the UO₂(S₂PR₂)₂(EtOH) complexes both contain three pre-edge features at about 2147.6, 2148.9 and 2150 eV. The P K-edge XAS spectra are not very informative for the bonding interactions between the uranyl ion and the di­thio­phosphinate, thus collections of the S K-edge XAS proceeded for both the [PPh₄][S₂PR₂] ligands and the UO₂(S₂PR₂)₂(EtOH) complexes.

Figure 2 Background-subtracted and normalized P K-edge XAS spectra for PPh4Cl, [PPh4][S2PR2] and UO2(S2PR2)2(EtOH).

2.3. S K-edge XAS

The normalized and background-subtracted S K-edge XAS spectra of the [PPh₄][S₂PR₂] (R = Ph, o-CF₃C₆H₄) ligands and the UO₂(S₂PR₂)₂(EtOH) complexes are shown in Fig. 3. According to the second derivatives (Fig. S4), the spectrum of [PPh₄][S₂PPh₂] contains three pre-edge features at 2471.3, 2472.4 and 2473.6 eV, and the spectrum of [PPh₄][(S₂P(o-CF₃C₆H₄)₂] contains four pre-edge features at 2471.3, 2472.4, 2473.4 and 2474.3 eV. This result is in agreement with the previous observations by Daly and co-workers, except that there is no small contribution to the spectra (>2480 eV) from sulfate contaminant (Fig. S3) (Daly, Keith, Batista, Boland, Clark et al., 2012). The pre-edge features in the spectra of the [PPh₄][S₂PR₂] ligands can be assigned to electron transitions from S 1s orbitals to the aryl orbitals containing small amounts of sulfur 3p character, P—S σ* and P—S σ* + π* orbitals (Daly, Keith, Batista, Boland, Clark et al., 2012). Compared with the spectra of [PPh₄][S₂PR₂], the two UO₂(S₂PR₂) (EtOH) complexes display pre-edge features around 2472.0, 2473.5 and 2474.8 eV and also contain a shoulder feature at about 2470.5 eV (Fig. S5). This shoulder feature in the S K-edge XAS of the UO₂(S₂PR₂)₂(EtOH) complexes is ascribed to the covalent interaction between the uranyl ion and the S₂PR₂⁻ ligands.

Figure 3 Comparison of the S K-edge XAS spectra of [PPh4][S2PR2] and UO2(S2PR2)2(EtOH).

To quantify the intensities of the pre-edge features, the S K-edge XAS spectra of the UO₂(S₂PR₂)₂(EtOH) complexes were modeled using pseudo-Voigt functions with a 1:1 ratio of Lorentzian and Gaussian function contributions and a step function with a 1:1 ratio of arctangent and error function contributions. The energy positions of the features determined by the second derivatives are fixed during the curve-fits (Figs. S5 and S6). The curve-fits parameters are summarized in Table S2.

The pre-edge region in the spectrum of UO₂(S₂PPh₂)₂(EtOH) is best modeled by four pseudo-Voigt functions at 2470.5, 2472.0, 2473.5 and 2474.8 eV, and that of UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH) by five pseudo-Voigt functions at 2470.6, 2471.9, 2473.1, 2474.0 and 2474.7 eV, as shown in Fig. 4 and Table 2. Note that the shoulder at the energy of 2470.5 eV and 2470.6 eV are both 0.16 of the intensity for UO₂(S₂Ph₂)₂(EtOH) and UO₂[S₂P(o-CF₃C₆H₄)₂)]₂(EtOH). Resembling the spectra of [PPh₄][S₂PR₂], the fourth feature observed in the spectrum of UO₂(S₂PPh₂)₂(EtOH) at 2474.8 eV splits into two features at 2474.0 and 2474.7 eV in the spectrum of UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH), which may be attributed to the orbital splitting resulting from symmetry change and nonuniform C—P—S angles, according to the results reported by Daly and co-workers (Daly, Keith, Batista, Boland, Clark et al., 2012).

Table 2
The energy and intensity obtained by curve-fitting of the S K-edge XAS for UO₂(S₂PR₂)₂

Compound	Energy (eV)	Intensity
UO2(S2PPh2)2(EtOH)	2470.5	0.16
	2472.0	2.65
	2473.5	1.85
	2474.8	2.26
UO2[S2P(o-CF3C6H4)2]2(EtOH)	2470.6	0.16
	2471.9	2.99
	2473.1	1.05
	2474.0	1.46
	2474.7	0.89

Figure 4 Curve-fitting results of S K-edge XAS for UO2(S2PR2)2(EtOH). The experimental data are shown by black circles, and the total curve fits are shown by red traces. Post-edge residuals (dashed gray traces) are generated by subtracting the pre-edge pseudo-Voigt functions (blue, green, purple, yellow, light blue) from the total curve fits.

2.4. DFT and time-dependent DFT (TDDFT) calculations

The electronic structure of the S₂PR₂⁻ anions has been deeply investigated by Daly and co-workers, revealing that the S 3p orbitals mix with P 3p orbitals to form two σ-type and one π-type P—S bonds in the S₂P⁻ moiety of S₂PR₂⁻, and the orbitals of the S₂P⁻ moiety mix with the σ- and π-type orbitals of the aryl groups (Daly, Keith, Batista, Boland, Clark et al., 2012; Daly, Keith, Batista, Boland, Kozimor et al., 2012). Therefore, the S₂PR₂⁻ ligands can provide both σ and π orbitals to interact with the uranyl ion in the UO₂(S₂PR₂)₂(EtOH) complexes.

The involvement of both U 5f and 6d orbitals in the covalent bonds between uranium and axial oxygen (O_yl) atoms induces a geometrically linear and redox-stable uranyl ion (Denning, 1992, 2007; Denning et al., 2002; Cowie et al., 2019), around which other ligands are confined to the equatorial plane to interact with the U 5f and 6d orbitals. DFT calculations were employed to account for the XAS spectra of the UO₂(S₂PR₂)₂(EtOH) complexes in this work. The energy level diagram of the truncated unoccupied MOs for the two UO₂(S₂PR₂)₂(EtOH) complexes is presented in Fig. 5, and has been shifted by a constant to ensure the energies of the S 1s orbitals are equivalent to each other, in order to directly compare with the S K-edge XAS. The U 5f- and 6d-dominant MOs are shown by red and blue lines, respectively. There are four orbitals (1–4a) belonging to the σ- and π-type mixing of the S₂P orbitals with U 5f orbitals near −3 eV, and the contours of these four orbitals are illustrated in Fig. 6. Other U 5f-dominant MOs locate around −1.25 eV showing the orbital mixing between U 5f and S 3p orbitals, blending in with some orbitals (black lines, ranging from −1.5 eV to −0.5 eV) that contain significant phenyl character () and only small contributions from S₂P fragment orbitals. The U 6d-dominant MOs (5–9a, blue lines) are distributed ranging from −0.5 eV to 2.0 eV, interspersing with some σ* S₂P orbitals (gray lines) containing little S 3p character. The contours of the U 6d-dominant MOs (5–9a) for UO₂(S₂PR₂)₂(EtOH) are illustrated in Fig. 7, and those of the orbitals containing significant phenyl character () for UO₂(S₂PR₂)₂(EtOH) are illustrated in Fig. S7.

Figure 5 The truncated orbitals energy levels for UO2(S2PR2)2(EtOH) calculated at the B3LYP/TZ2P level. The red and blue lines denote the orbitals containing primarily U 5f and 6d character, respectively.

Figure 6 The contours of unoccupied Kohn–Sham orbitals (1–4a) containing primarily U 5f character for UO2(S2PR2)2(EtOH) in 0.02 a.u.

Figure 7 The contours of unoccupied Kohn–Sham orbitals (5–9a) containing primarily U 6d character for UO2(S2PR2)2(EtOH) in 0.02 a.u.

According to the orbital energies obtained by the ground-state DFT calculations in Fig. 5, the first pre-edge features around 2470.5 eV in the S K-edge XAS of the UO₂(S₂PR₂)₂(EtOH) complexes in Fig. 4 are reasonably assigned to the transitions from S 1s orbitals to the U 5f-dominant MOs (1–4a). The second pre-edge features around 2472.0 eV are dominated by the transitions associated with primarily phenyl character (). The other pre-edge features at energy from 2473 to 2475 eV are contributed by U 6d-dominant MOs and orbitals containing little S 3p components without U 5f or 6d character.

The S K-edge XAS spectra for the UO₂(S₂PR₂)₂(EtOH) complexes were simulated by TDDFT calculations to directly compare with the experiment XAS (Fig. 8). The simulated spectra for both UO₂(S₂PR₂)₂(EtOH) complexes have been shifted by +49.7 eV to account for the omission of the atomic and extra-atomic relaxation associated with the core excitation, relativistic stabilization, and errors associated with the functional (Martin & Shirley, 1977; Segala & Chong, 2010).

Figure 8 Comparison of the simulated spectra obtained by calculations (red) with the experimental S K-edge XAS data for UO2(S2PR2)2(EtOH) (black). The purple, blue, orange and light gray bars represent the energies and oscillator strengths for the calculated transitions involving U 5f, 6d, and S2P orbitals containing little S 3p character without U 5f or 6d character, respectively.

The simulated spectra are in good agreement with the experimental spectra. The transitions around 2470.5 eV in the simulated spectra are observed for both the UO₂(S₂PR₂)₂(EtOH) complexes, which is entirely attributed to the transitions from S 1s orbitals to the U 5f-dominant unoccupied MOs (1–4a), indicating the covalent mixing between S 3p orbitals and U 5f orbitals. The transitions from S 1s orbitals to the primarily phenyl character () unoccupied MOs and little U 5f character unoccupied MOs both contribute to the pre-edge features around 2472.0 eV obtained by curve-fits in Fig. 4. The other pre-edge features above 2473 eV are associated with the transitions to the U 6d-dominant MOs and to the orbitals containing little S 3p components without U 5f or 6d character.

2.5. Evaluation of the bonding covalency between the uranyl ion and the S₂PR₂⁻ ligands

It has been well known that the amount of ligand np character in metal-derived MOs can be determined from the intensities observed in the pre-edge features in the ligand K-edge XAS (Solomon et al., 2005; Barton et al., 2015). Generally, an intensity standard is used to convert the experimental intensity of a pre-edge feature to the amount of ligand np character in metal–ligand bonds. For example, an intensity of 0.53 = 7.5% Cl 3p-character per bond obtained from Cs₂CuCl₄ is used as the Cl K-edge XAS intensity standard (Solomon et al., 2005). The standards for thiol­ate (SR⁻) (Shadle et al., 1993), sulfide (S²⁻) (Rose et al., 1999) and enedi­thiol­ate (S₂R₂²⁻) (Szilagyi et al., 2003) have been established to evaluate the amount of S 3p character in M—S bonds. Since the intrinsic transition dipole for the S 1s → 3p excitation is dependent on the effective nuclear charge Z_eff (S) for each S-ligand (Solomon et al., 2005), it is not appropriate to directly use the standard for thiol­ate, sulfide or enedi­thiol­ate to convert the intensities in this work (S in the form of S₂PR₂⁻) to % S 3p character. Therefore, we herein use the data from Mulliken population analysis that are associated with the experimental XAS data to evaluate the bonding covalency between the uranyl ion and the S₂PR₂⁻ ligands (Table 3).

Table 3
Mulliken population analysis for unoccupied MOs of the UO₂(S₂PR₂)₂(EtOH)

Compound	MO		Energy (eV)	% S 3p	% S 3p average
UO2(S2PPh2)2(EtOH)	5f	1a	−2.96	2.68	2.86
		2a	−2.93	3.75
		3a	−2.91	1.95
		4a	−2.90	3.04
	6d	5a	0.32	12.11	13.15
		6a	0.67	9.00
		7a	0.73	13.43
		8a	1.73	14.43
		9a	1.86	16.78
		10a	−1.34	9.25	2.25
		11a	−0.80	0.39
		12a	−0.77	0.62
		13a	−0.59	0.51
		14a	−0.56	0.50
UO2[S2P(o-CF3C6H4)2]2(EtOH)	5f	1a	−3.30	1.95	2.81
		2a	−3.27	4.09
		3a	−3.25	2.48
		4a	−3.24	2.73
	6d	5a	−0.80	13.00	12.71
		6a	−0.35	21.93
		7a	0.50	8.94
		8a	1.45	6.29
		9a	1.51	13.39
		10a	−1.88	6.95	3.65
		11a	−1.85	4.78
		12a	−1.80	6.15
		13a	−1.74	5.48
		14a	−1.27	0.73
		15a	−1.26	0.80
		16a	−1.18	2.77
		17a	−1.16	1.54

The DFT calculations show that the amount of S 3p character in the U 5f-dominant unoccupied MOs of 1a, 2a, 3a and 4a for UO₂(S₂PPh)₂(EtOH) is 2.68%, 3.75%, 1.95% and 3.04%, respectively. For UO₂{[S₂P(o-CF₃C₆H₄)]₂}₂(EtOH), these values are 1.95%, 4.09%, 2.48% and 2.73%, respectively. The total amount of S 3p character of the orbitals of 1a, 2a, 3a and 4a are 11.42% and 11.25%, corresponding to 2.86% and 2.81% per U—S bond in UO₂(S₂PPh)₂(EtOH) and UO₂{[S₂P(o-CF₃C₆H₄)]₂}₂(EtOH), respectively. The DFT calculations also show that the amount of S 3p character in the U 6d-dominant unoccupied MOs of 5a, 6a, 7a, 8a and 9a for UO₂(S₂PPh)₂(EtOH) is 12.11%, 9.0%, 13.43%, 14.43% and 16.78%, respectively. For UO₂[(S₂P(o-CF₃C₆H₄))₂]₂(EtOH), these values are 13.00%, 21.93%, 8.94%, 6.29% and 13.39%, respectively. The average amount of S 3p character in U 6d-based orbitals (5–9a) obtained from the DFT calculations are 13.15% and 12.71% for UO₂(S₂PPh)₂(EtOH) and UO₂{[S₂P(o-CF₃C₆H₄)]₂}₂(EtOH), respectively, thus the S 3p orbitals are engaged more in the U 6d orbitals than that in the U 5f orbitals, consistent with the previous reports that the 6d orbitals play a significant role in actinide bonding relative to the 5f orbitals (Minasian et al., 2012; Pepper & Bursten, 1991; Su et al., 2018; Cross et al., 2017). The average amount of S 3p character in the orbitals with primarily phenyl character () obtained from the DFT calculations is 2.25% and 3.65% for UO₂(S₂PPh)₂(EtOH) and UO₂{[S₂P(o-CF₃C₆H₄)]₂}₂(EtOH), respectively, indicating an important contribution to the pre-edge features. Although only the first pre-edge feature around 2470.5 eV in each spectrum is exclusively attributed to the transitions from S 1s orbitals to the U 5f-dominant unoccupied MOs (1–4a), the XAS data and DFT calculations both suggest that the mixing of U 5f and 6d orbitals with S 3p orbitals are similar in the two UO₂(S₂PR₂)₂(EtOH) complexes, indicating that introduction of o-CF₃ into phenyl has little effect on the covalent bonding between S₂PR₂⁻ and UO₂²⁺.

3. Conclusion

A combination of the S K-edge XAS technique and DFT calculations has been conducted on UO₂(S₂PR₂)₂(EtOH) (R = Ph and o-CF₃C₆H₄) complexes to obtain direct insight into the contributions of U 6d and especially 5f orbitals to the covalency in the U—S bonds, in order to illuminate the role of the bonding covalency in the An^III/Ln^III separation by the di­thio­phosphinic acids. The two UO₂(S₂PR₂)₂(EtOH) complexes display similar pre-edge features in the S K-edge XAS, the first of which is entirely attributed to the transitions from S 1s orbitals to the U 5f orbitals mixing with the S 3p orbitals. Curve-fitting analysis indicates identical intensities of 0.16 for the first pre-edge feature of the two UO₂(S₂PR₂)₂(EtOH) complexes. Consistently, the amounts of S 3p character per U—S bond for UO₂(S₂Ph₂)₂(EtOH) and UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH) by Mulliken population analysis are essentially identical to each other. In addition, the DFT calculations show that the amounts of S 3p character in U 6d-based orbitals are also nearly equivalent for the two UO₂(S₂PR₂)₂(EtOH) complexes. The XAS data and DFT calculations demonstrate essentially identical bonding covalency in the two UO₂(S₂PR₂)₂(EtOH) complexes, indicating that the introduction of o-CF₃ into phenyl has little effect on the covalent bonding between the S₂PR₂⁻ ligands and UO₂²⁺. The essentially identical covalency in the U—S bonds for the two UO₂(S₂PR₂)₂(EtOH) complexes are contradictory to the significantly different An^III/Ln^III separation performance of the two di­thio­phosphinic acids. The M—S bonding covalency seems to be unable to account for the substituent effect in the An^III/Ln^III separation by the di­thio­phosphinic acids. According to the results in the previous work as mentioned in the Introduction, we speculate that the different chemical stoichiometry and structure of the extracted complexes should be the main reason for the significantly different separation performance of HS₂PPh₂ and HS₂P(o-CF₃C₆H₄)₂ in the An^III/Ln^III separation. Nevertheless, it is worthwhile conducting an experimental investigation on the bonding covalency between the trivalent actinides and di­thio­phosphinate ligands with different substituents in the future.

4. Experimental section

4.1. Synthesis of UO₂(S₂PR₂)₂(EtOH)

All manipulations were carried out in a glove box under an atmosphere of nitro­gen to rigorously exclude air and moisture. Ethanol was dried and degassed by the solvent purification system, and transferred to the glove box without exposure to air. Super dry di­chloro­methane was stored over activated molecular sieves prior to use. Single crystals of [PPh₄][S₂PR₂] suitable for X-ray diffraction characterization were obtained by recrystallization from a 1:1 aceto­nitrile/toluene solution under air and at ambient conditions, according to the procedure reported in the literature (Daly, Klaehn et al., 2012). In synthesizing the single crystals of the two UO₂(S₂PR₂)₂(EtOH) complexes, two di­thio­phosphinate ligands in the ammonium form [NH₄][S₂PR₂] were used according to the previous procedures (Daly, Klaehn et al., 2012).

UO₂(S₂PPh₂)₂(EtOH). Single crystals of the UO₂(S₂PR₂)₂(EtOH) complexes were prepared using the reported procedures with slight modifications (Meng et al., 2018; Pinkerton et al., 1997; Storey et al., 1983). A solution of [NH₄][S₂PPh₂] (54.2 mg, 0.203 mmol) in ethanol (2 ml) was mixed with a solution of UO₂Cl₂ (35.8 mg) in ethanol (2 ml). The mixture was stirred for 20 min at 70°C to give an orange solution. A slight white precipitate was generated over the course of the reaction. The orange solution was taken to dryness and the resulting complexes were extracted from the white–orange solid residue with di­chloro­methane (10 ml). The products were recrystallized after solvent removal from 1.5 ml ethanol. After one week, single crystals suitable for X-ray diffraction were obtained at room temperature. IR (cm⁻¹, solid sample on ATR cell): 923 (asymmetric O=U=O stretching), 559 (symmetric PS₂ stretching), 631 (asymmetric PS₂ stretching). Raman (cm⁻¹): 840 (symmetric O=U=O stretching). Anal. Calcd for C₂₆H₂₆O₃P₂S₄U: C, 38.33; H, 3.22. Found: C, 38.24; H, 3.27.

[UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH)]·EtOH. Single crystals of UO₂[S₂P(o-CF₃C₆H₄)₂]₂(EtOH) were prepared as described above for UO₂(S₂PPh₂)₂(EtOH) from [NH₄][S₂P(o-CF₃C₆H₄)₂] (71.4 mg, 0.177 mmol) and UO₂Cl₂ (35.4 mg). IR (cm⁻¹, solid sample on ATR cell): 930 (asymmetric O=U=O stretching), 560 (symmetric PS₂ stretching), 646 (asymmetric PS₂ stretching). Raman (cm⁻¹): 845 (symmetric O=U=O stretching). Anal. Calcd for C₃₂H₂₈F₁₂O₄P₂S₄U: C, 33.93; H, 2.49. Found: C, 33.79; H, 2.66.

4.2. X-ray crystallography

The single-crystal X-ray diffraction data for [PPh₄][S₂PR₂] and UO₂(S₂PR₂)₂(EtOH) complexes were collected on a Rigaku Super Nova, Dual, Cu at zero, AtlasS2 diffractometer. The measurements were performed with Cu/Kα (λ = 1.54184 Å) or Mo/Kα (λ = 0.71073 Å) radiation. All crystals were kept at 173 K during data collection. Data collection and reduction were carried out in CrysAlisPro, Version 1.171.39.46 (Rigaku Oxford Diffraction, 2018). A multi-scan method for absorption corrections was applied to the data sets. All the structures were solved by intrinsic phasing method and refined by full matrix least-squares techniques with anisotropic temperature factors of all non-hydrogen atoms on F², using the SHELX-97 and Olex2-1.2 program (Sheldrick, 2008; Dolomanov et al., 2009). All H atoms were refined with anisotropic displacement parameters. The H atoms were placed in ideal sites and were not refined for good refinement convergence. Further data collection and refinement details are summarized in Table S1. The CIF files containing the supplementary crystallographic data for [PPh₄][S₂PR₂] and UO₂(S₂PR₂)₂(EtOH) are available through the Cambridge Crystallographic Data Centre (CCDC 2103608–2103611).

4.3. XAS measurements and data analysis

The S and P K-edge XAS measurements were conducted on beamline 4B7A of Beijing Synchrotron Radiation Facility (BSRF) over an energy range from 1750 eV to 6000 eV. The energy of the electron beam is 2.5 GeV in the storage ring with a maximum beam current of 250 mA. A beam spot tightly focused at a sample is about 1.5 mm × 0.4 mm, and the measured flux is over 3 × 10¹⁰ photons s⁻¹ (250 mA)⁻¹ (Zheng et al., 2014). The samples were measured by partial fluorescence yield mode using a 13-element Si (Li) array detector.

For S and P K-edge XAS measurements, single-crystal samples were finely ground into a homogeneous powder which was dispersed as thinly as possible on the carbon tape. The energy scale in the S and P K-edge XAS was calibrated by using Na₂S₂O₃ and Na₄P₂O₇ standards, respectively, which was repeatedly analyzed at intervals between sample scans. All spectra were collected in duplicate at least twice to obtain adequate statistics. Spectra showed no signs of radiation damage and were reproduced over multiple regions of the sample.

Background subtraction and normalization of S and P K-edge XAS data were manipulated using the Athena interface in the Demeter software program (Ravel & Newville, 2005). In a typical example, a line was fit to the pre-edge region and then subtracted from the experimental data to eliminate the background of the spectrum. The data were normalized to a unit step height by fitting a second-order polynomial to the post-edge region of the spectrum. Curve-fitting of the S K-edge XAS was performed using the program IGOR Pro 8.04 and a modified version of EDG_FIT (George, 2001). Second-derivative spectra were used as guides to determine the number and position of peaks. Pre-edge and rising edge features were modeled by symmetrically constrained pseudo-Voigt line shapes with a fixed 1:1 Lorentzian to Gaussian ratio and a step function with a 1:1 ratio of arctangent and error function, respectively. Fits were performed over several energy ranges. The quality of each curve-fit was determined by evaluating changes in χ² and by inspecting the residual intensity, which is obtained by subtracting the fit from the experiment data and should resemble a horizontal line at zero. The area under the pre-edge features (defined as the intensity) was used as the transition intensity.

4.4. DFT calculations

All DFT calculations were carried out with the Amsterdam Density Functional (ADF 2019) program (Baerends et al., 2019; te Velde et al., 2001), employing the B3LYP hybrid functional (Becke, 1988; Lee et al., 1988). The all-electron Slater-type orbital (STO) basis sets of triple-ζ augmented by two sets of polarization functions (TZ2P) were adapted for the description of all atoms. The zero-order regular approximation (ZORA) approach was used to account for the scalar relativistic (SR) effects (Faas et al., 1995). Mulliken population analyses were conducted on particular MOs to obtain the reported orbital populations in the two UO₂(S₂PR₂)₂(EtOH) complexes (Mulliken, 1955).

The S K-edge XAS spectra for all complexes were simulated by TDDFT using the Davidson method. The simulated spectra were obtained by calculating core electron excitations originating from S 1s dominated MOs to virtual MOs at the optimized crystal structure. Only excitations from S 1s core levels to virtual orbitals were analyzed by restricting the energy range of core level and virtual orbitals involved in excitation. The calculated oscillator strengths were evenly broadened with a pseudo-Voigt functions with a 1:1 ratio of Lorentzian and Gaussian function contributions of 1 eV full width at half-maximum to generate the simulated absorption spectra. An energy shift of +49.7 eV was applied for the simulated spectra to account for the omission of atomic and extra-atomic relaxation associated with the core excitation, relativistic stabilization, and errors associated with the functional, according to the literature (Martin & Shirley, 1977; Segala & Chong, 2010).

Supporting information

Computing details

Data collection: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018) for (I), (II); CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for (III), (IV). Cell refinement: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018) for (I), (II); CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for (III), (IV). Data reduction: CrysAlis PRO 1.171.39.46e (Rigaku OD, 2018) for (I), (II); CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for (III), (IV). For all structures, program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

C12H10PS2·C24H20P	F(000) = 1232
Mr = 588.66	Dx = 1.252 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.5406 (12) Å	Cell parameters from 4174 reflections
b = 13.2405 (7) Å	θ = 3.8–26.5°
c = 17.1497 (12) Å	µ = 0.30 mm^−1
β = 108.962 (8)°	T = 173 K
V = 3122.6 (4) Å^3	Plate, clear colourless
Z = 4	0.2 × 0.15 × 0.02 mm

Data collection

SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	8252 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	5300 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.064
Detector resolution: 5.2137 pixels mm^-1	θmax = 30.3°, θmin = 3.2°
ω scans	h = −20→18
Absorption correction: multi-scan CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −13→18
Tmin = 0.770, Tmax = 1.000	l = −24→20
23257 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0395P)^2 + 0.683P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8252 reflections	Δρmax = 0.40 e Å^−3
361 parameters	Δρmin = −0.43 e Å^−3
12 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq
P001	0.55441 (5)	0.77436 (4)	0.82839 (4)	0.02232 (15)
P002	0.39630 (5)	0.25980 (4)	0.61352 (4)	0.02175 (15)
S003	0.59486 (6)	0.74518 (5)	0.94779 (4)	0.0413 (2)
S004	0.55272 (6)	0.91705 (5)	0.79403 (5)	0.0422 (2)
C005	0.29649 (17)	0.34618 (16)	0.58323 (14)	0.0204 (5)
C006	0.48765 (18)	0.29347 (16)	0.56900 (14)	0.0229 (5)
C007	0.44632 (17)	0.26074 (16)	0.72395 (14)	0.0230 (5)
C008	0.35646 (19)	0.13472 (17)	0.57684 (14)	0.0267 (6)
C009	0.28465 (18)	0.41488 (17)	0.51927 (15)	0.0268 (6)
H009	0.3299	0.4177	0.4915	0.032*
C00A	0.13847 (18)	0.47523 (17)	0.53797 (15)	0.0282 (6)
H00A	0.0857	0.5191	0.5229	0.034*
C00B	0.20549 (19)	0.47870 (17)	0.49728 (15)	0.0293 (6)
H00B	0.1974	0.5245	0.4545	0.035*
C00C	0.22776 (19)	0.34274 (17)	0.62429 (15)	0.0277 (6)
H00C	0.2353	0.2971	0.6672	0.033*
C00D	0.43369 (19)	0.72041 (19)	0.77832 (17)	0.0325 (6)
C00E	0.14877 (19)	0.40701 (17)	0.60120 (16)	0.0303 (6)
H00E	0.1026	0.4044	0.6281	0.036*
C00F	0.63279 (18)	0.70301 (19)	0.78335 (15)	0.0296 (6)
C00G	0.6270 (2)	0.33488 (18)	0.49581 (17)	0.0358 (7)
H00G	0.6742	0.3484	0.4714	0.043*
C00H	0.47521 (19)	0.17185 (18)	0.76727 (15)	0.0286 (6)
H00H	0.4688	0.1107	0.7393	0.034*
C00I	0.57958 (19)	0.32417 (18)	0.61695 (16)	0.0329 (6)
H00I	0.5945	0.3315	0.6736	0.039*
C00J	0.5350 (2)	0.30587 (19)	0.44758 (16)	0.0348 (6)
H00J	0.5198	0.3011	0.3907	0.042*
C00K	0.4656 (2)	0.28389 (18)	0.48406 (16)	0.0315 (6)
H00K	0.4040	0.2627	0.4518	0.038*
C00L	0.6493 (2)	0.3439 (2)	0.57985 (17)	0.0400 (7)
H00L	0.7116	0.3634	0.6119	0.048*
C00M	0.4567 (2)	0.35190 (19)	0.76602 (16)	0.0394 (7)
H00M	0.4380	0.4120	0.7372	0.047*
C00N	0.5231 (2)	0.2635 (2)	0.89397 (16)	0.0395 (7)
H00N	0.5485	0.2644	0.9512	0.047*
C00O	0.5137 (2)	0.1743 (2)	0.85243 (16)	0.0356 (7)
H00O	0.5333	0.1145	0.8816	0.043*
C00P	0.4264 (2)	0.06288 (18)	0.57609 (17)	0.0380 (7)
H00P	0.4920	0.0799	0.5946	0.046*
C00Q	0.2594 (2)	0.1086 (2)	0.54958 (18)	0.0441 (8)
H00Q	0.2124	0.1559	0.5503	0.053*
C00R	0.6776 (2)	0.7495 (2)	0.73288 (18)	0.0440 (7)
H00R	0.6649	0.8171	0.7189	0.053*
C00S	0.3979 (2)	−0.03348 (19)	0.54779 (18)	0.0451 (8)
H00S	0.4444	−0.0815	0.5475	0.054*
C00T	0.3685 (2)	0.7672 (3)	0.71056 (17)	0.0497 (8)
H00T	0.3863	0.8265	0.6902	0.060*
C00U	0.4949 (2)	0.3525 (2)	0.85104 (17)	0.0475 (8)
H00U	0.5017	0.4133	0.8795	0.057*
C00V	0.3015 (3)	−0.0586 (2)	0.52019 (19)	0.0511 (9)
H00V	0.2828	−0.1235	0.5007	0.061*
C00W	0.6513 (2)	0.6018 (2)	0.8027 (2)	0.0549 (9)
H00W	0.6220	0.5692	0.8365	0.066*
C00X	0.4058 (2)	0.6325 (2)	0.8081 (2)	0.0596 (10)
H00X	0.4482	0.6011	0.8544	0.072*
C00Y	0.2322 (3)	0.0115 (2)	0.5210 (2)	0.0593 (10)
H00Y	0.1667	−0.0063	0.5024	0.071*
C00Z	0.7414 (2)	0.6961 (3)	0.7029 (2)	0.0667 (11)
H00Z	0.7718	0.7285	0.6698	0.080*
C010	0.2766 (3)	0.7263 (4)	0.6727 (2)	0.0821 (14)
H010	0.2327	0.7586	0.6278	0.098*
C011	0.7595 (3)	0.5973 (4)	0.7216 (3)	0.0829 (14)
H011	0.8023	0.5620	0.7015	0.099*
C012	0.2517 (3)	0.6390 (4)	0.7019 (3)	0.0938 (17)
H012	0.1907	0.6110	0.6758	0.113*
C013	0.3141 (3)	0.5910 (3)	0.7689 (3)	0.0856 (15)
H013	0.2957	0.5312	0.7882	0.103*
C014	0.7145 (3)	0.5490 (3)	0.7708 (3)	0.0804 (13)
H014	0.7262	0.4807	0.7828	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P001	0.0209 (4)	0.0253 (3)	0.0204 (3)	0.0020 (3)	0.0063 (3)	−0.0036 (2)
P002	0.0238 (4)	0.0225 (3)	0.0191 (3)	0.0010 (3)	0.0071 (3)	0.0020 (2)
S003	0.0456 (5)	0.0553 (4)	0.0224 (3)	0.0144 (4)	0.0102 (3)	0.0045 (3)
S004	0.0504 (5)	0.0281 (3)	0.0499 (5)	0.0008 (3)	0.0186 (4)	0.0051 (3)
C005	0.0200 (13)	0.0209 (11)	0.0202 (12)	−0.0016 (10)	0.0063 (10)	−0.0008 (9)
C006	0.0223 (14)	0.0245 (12)	0.0222 (12)	0.0050 (10)	0.0077 (10)	0.0001 (10)
C007	0.0216 (14)	0.0275 (12)	0.0201 (12)	0.0014 (10)	0.0070 (10)	0.0019 (10)
C008	0.0343 (16)	0.0243 (12)	0.0206 (13)	0.0001 (11)	0.0076 (11)	0.0021 (10)
C009	0.0259 (15)	0.0321 (13)	0.0225 (13)	−0.0004 (11)	0.0080 (11)	0.0065 (10)
C00A	0.0202 (14)	0.0241 (12)	0.0349 (15)	0.0006 (10)	0.0014 (12)	−0.0027 (11)
C00B	0.0276 (15)	0.0286 (13)	0.0272 (14)	−0.0015 (11)	0.0027 (12)	0.0080 (11)
C00C	0.0318 (16)	0.0239 (12)	0.0294 (14)	−0.0025 (11)	0.0128 (12)	0.0053 (10)
C00D	0.0229 (15)	0.0376 (14)	0.0392 (16)	−0.0027 (12)	0.0133 (12)	−0.0202 (12)
C00E	0.0272 (15)	0.0298 (13)	0.0389 (16)	−0.0047 (11)	0.0174 (13)	−0.0025 (11)
C00F	0.0215 (14)	0.0415 (15)	0.0227 (13)	0.0041 (12)	0.0029 (11)	−0.0114 (11)
C00G	0.0360 (18)	0.0384 (15)	0.0406 (17)	−0.0021 (13)	0.0228 (14)	−0.0003 (12)
C00H	0.0282 (15)	0.0288 (13)	0.0287 (14)	0.0045 (11)	0.0089 (12)	0.0038 (11)
C00I	0.0315 (17)	0.0429 (15)	0.0231 (14)	−0.0020 (12)	0.0073 (12)	0.0034 (11)
C00J	0.0389 (18)	0.0465 (15)	0.0232 (14)	−0.0023 (13)	0.0159 (13)	−0.0049 (12)
C00K	0.0291 (16)	0.0393 (14)	0.0259 (14)	−0.0027 (12)	0.0088 (12)	−0.0060 (11)
C00L	0.0252 (16)	0.0577 (18)	0.0349 (16)	−0.0093 (13)	0.0067 (13)	0.0008 (13)
C00M	0.058 (2)	0.0294 (14)	0.0267 (15)	0.0028 (13)	0.0074 (14)	0.0034 (11)
C00N	0.0334 (17)	0.0619 (19)	0.0208 (13)	−0.0029 (14)	0.0055 (12)	0.0030 (13)
C00O	0.0321 (17)	0.0421 (15)	0.0297 (15)	0.0025 (12)	0.0063 (13)	0.0118 (12)
C00P	0.0431 (19)	0.0302 (14)	0.0451 (18)	0.0023 (12)	0.0204 (15)	−0.0019 (12)
C00Q	0.0340 (19)	0.0332 (15)	0.055 (2)	0.0028 (13)	−0.0001 (15)	−0.0065 (13)
C00R	0.0287 (17)	0.072 (2)	0.0331 (16)	−0.0030 (14)	0.0130 (13)	−0.0159 (14)
C00S	0.059 (2)	0.0281 (14)	0.053 (2)	0.0029 (14)	0.0244 (17)	−0.0048 (13)
C00T	0.0250 (17)	0.097 (2)	0.0264 (15)	0.0028 (16)	0.0073 (13)	−0.0215 (16)
C00U	0.063 (2)	0.0466 (17)	0.0277 (16)	0.0026 (16)	0.0077 (15)	−0.0084 (13)
C00V	0.069 (3)	0.0300 (15)	0.0463 (19)	−0.0045 (16)	0.0071 (18)	−0.0098 (13)
C00W	0.054 (2)	0.0514 (18)	0.064 (2)	0.0192 (16)	0.0245 (19)	−0.0075 (16)
C00X	0.040 (2)	0.0342 (16)	0.113 (3)	−0.0066 (14)	0.036 (2)	−0.0236 (17)
C00Y	0.044 (2)	0.0437 (18)	0.069 (2)	−0.0095 (16)	−0.0104 (18)	−0.0131 (16)
C00Z	0.035 (2)	0.127 (3)	0.043 (2)	−0.001 (2)	0.0194 (17)	−0.032 (2)
C010	0.030 (2)	0.168 (4)	0.044 (2)	0.005 (3)	0.0061 (17)	−0.053 (3)
C011	0.043 (2)	0.132 (4)	0.072 (3)	0.025 (2)	0.017 (2)	−0.052 (3)
C012	0.039 (2)	0.127 (4)	0.123 (4)	−0.025 (3)	0.037 (3)	−0.101 (3)
C013	0.061 (3)	0.053 (2)	0.162 (4)	−0.024 (2)	0.062 (3)	−0.058 (3)
C014	0.075 (3)	0.071 (2)	0.092 (3)	0.037 (2)	0.022 (3)	−0.021 (2)

Geometric parameters (Å, º)

P001—S003	1.9763 (9)	C00J—C00K	1.381 (3)
P001—S004	1.9769 (9)	C00K—H00K	0.9300
P001—C00D	1.830 (3)	C00L—H00L	0.9300
P001—C00F	1.833 (2)	C00M—H00M	0.9300
P002—C005	1.787 (2)	C00M—C00U	1.382 (4)
P002—C006	1.790 (2)	C00N—H00N	0.9300
P002—C007	1.795 (2)	C00N—C00O	1.364 (4)
P002—C008	1.799 (2)	C00N—C00U	1.380 (4)
C005—C009	1.392 (3)	C00O—H00O	0.9300
C005—C00C	1.398 (3)	C00P—H00P	0.9300
C006—C00I	1.383 (3)	C00P—C00S	1.380 (4)
C006—C00K	1.392 (3)	C00Q—H00Q	0.9300
C007—C00H	1.382 (3)	C00Q—C00Y	1.387 (4)
C007—C00M	1.389 (3)	C00R—H00R	0.9300
C008—C00P	1.396 (3)	C00R—C00Z	1.391 (4)
C008—C00Q	1.379 (4)	C00S—H00S	0.9300
C009—H009	0.9300	C00S—C00V	1.366 (4)
C009—C00B	1.378 (3)	C00T—H00T	0.9300
C00A—H00A	0.9300	C00T—C010	1.391 (5)
C00A—C00B	1.371 (3)	C00U—H00U	0.9300
C00A—C00E	1.382 (3)	C00V—H00V	0.9300
C00B—H00B	0.9300	C00V—C00Y	1.375 (4)
C00C—H00C	0.9300	C00W—H00W	0.9300
C00C—C00E	1.380 (3)	C00W—C014	1.399 (4)
C00D—C00T	1.385 (4)	C00X—H00X	0.9300
C00D—C00X	1.384 (4)	C00X—C013	1.396 (5)
C00E—H00E	0.9300	C00Y—H00Y	0.9300
C00F—C00R	1.385 (4)	C00Z—H00Z	0.9300
C00F—C00W	1.386 (4)	C00Z—C011	1.352 (5)
C00G—H00G	0.9300	C010—H010	0.9300
C00G—C00J	1.379 (4)	C010—C012	1.356 (6)
C00G—C00L	1.376 (4)	C011—H011	0.9300
C00H—H00H	0.9300	C011—C014	1.382 (6)
C00H—C00O	1.384 (3)	C012—H012	0.9300
C00I—H00I	0.9300	C012—C013	1.367 (6)
C00I—C00L	1.386 (4)	C013—H013	0.9300
C00J—H00J	0.9300	C014—H014	0.9300
S003—P001—S004	117.80 (4)	C00G—C00L—C00I	120.4 (3)
C00D—P001—S003	109.09 (10)	C00G—C00L—H00L	119.8
C00D—P001—S004	108.42 (10)	C00I—C00L—H00L	119.8
C00D—P001—C00F	103.53 (11)	C007—C00M—H00M	120.3
C00F—P001—S003	108.63 (9)	C00U—C00M—C007	119.5 (2)
C00F—P001—S004	108.43 (9)	C00U—C00M—H00M	120.3
C005—P002—C006	111.19 (10)	C00O—C00N—H00N	120.0
C005—P002—C007	108.34 (11)	C00O—C00N—C00U	120.0 (2)
C005—P002—C008	110.41 (11)	C00U—C00N—H00N	120.0
C006—P002—C007	110.23 (11)	C00H—C00O—H00O	119.7
C006—P002—C008	106.22 (11)	C00N—C00O—C00H	120.6 (2)
C007—P002—C008	110.46 (11)	C00N—C00O—H00O	119.7
C009—C005—P002	121.87 (18)	C008—C00P—H00P	120.1
C009—C005—C00C	119.5 (2)	C00S—C00P—C008	119.8 (3)
C00C—C005—P002	118.60 (17)	C00S—C00P—H00P	120.1
C00I—C006—P002	121.81 (19)	C008—C00Q—H00Q	120.2
C00I—C006—C00K	119.9 (2)	C008—C00Q—C00Y	119.7 (3)
C00K—C006—P002	118.22 (19)	C00Y—C00Q—H00Q	120.2
C00H—C007—P002	120.63 (18)	C00F—C00R—H00R	119.7
C00H—C007—C00M	119.9 (2)	C00F—C00R—C00Z	120.7 (3)
C00M—C007—P002	119.51 (18)	C00Z—C00R—H00R	119.7
C00P—C008—P002	118.5 (2)	C00P—C00S—H00S	119.8
C00Q—C008—P002	121.8 (2)	C00V—C00S—C00P	120.3 (3)
C00Q—C008—C00P	119.7 (2)	C00V—C00S—H00S	119.8
C005—C009—H009	120.2	C00D—C00T—H00T	119.7
C00B—C009—C005	119.6 (2)	C00D—C00T—C010	120.6 (4)
C00B—C009—H009	120.2	C010—C00T—H00T	119.7
C00B—C00A—H00A	119.7	C00M—C00U—H00U	119.8
C00B—C00A—C00E	120.5 (2)	C00N—C00U—C00M	120.4 (3)
C00E—C00A—H00A	119.7	C00N—C00U—H00U	119.8
C009—C00B—H00B	119.7	C00S—C00V—H00V	119.8
C00A—C00B—C009	120.6 (2)	C00S—C00V—C00Y	120.3 (3)
C00A—C00B—H00B	119.7	C00Y—C00V—H00V	119.8
C005—C00C—H00C	120.0	C00F—C00W—H00W	120.3
C00E—C00C—C005	120.0 (2)	C00F—C00W—C014	119.4 (3)
C00E—C00C—H00C	120.0	C014—C00W—H00W	120.3
C00T—C00D—P001	120.7 (2)	C00D—C00X—H00X	119.9
C00X—C00D—P001	120.4 (2)	C00D—C00X—C013	120.1 (4)
C00X—C00D—C00T	118.9 (3)	C013—C00X—H00X	119.9
C00A—C00E—H00E	120.1	C00Q—C00Y—H00Y	119.9
C00C—C00E—C00A	119.8 (2)	C00V—C00Y—C00Q	120.3 (3)
C00C—C00E—H00E	120.1	C00V—C00Y—H00Y	119.9
C00R—C00F—P001	121.2 (2)	C00R—C00Z—H00Z	119.8
C00R—C00F—C00W	119.0 (3)	C011—C00Z—C00R	120.4 (4)
C00W—C00F—P001	119.8 (2)	C011—C00Z—H00Z	119.8
C00J—C00G—H00G	119.8	C00T—C010—H010	120.3
C00L—C00G—H00G	119.8	C012—C010—C00T	119.4 (4)
C00L—C00G—C00J	120.4 (3)	C012—C010—H010	120.3
C007—C00H—H00H	120.1	C00Z—C011—H011	120.0
C007—C00H—C00O	119.7 (2)	C00Z—C011—C014	119.9 (3)
C00O—C00H—H00H	120.1	C014—C011—H011	120.0
C006—C00I—H00I	120.3	C010—C012—H012	119.2
C006—C00I—C00L	119.5 (2)	C010—C012—C013	121.5 (4)
C00L—C00I—H00I	120.3	C013—C012—H012	119.2
C00G—C00J—H00J	120.1	C00X—C013—H013	120.3
C00G—C00J—C00K	119.8 (2)	C012—C013—C00X	119.4 (4)
C00K—C00J—H00J	120.1	C012—C013—H013	120.3
C006—C00K—H00K	120.0	C00W—C014—H014	119.7
C00J—C00K—C006	120.1 (2)	C011—C014—C00W	120.6 (4)
C00J—C00K—H00K	120.0	C011—C014—H014	119.7

(II)

Crystal data

C24H20P·C14H8F6PS2	Z = 2
Mr = 724.66	F(000) = 744
Triclinic, P1	Dx = 1.397 Mg m^−3
a = 8.7782 (3) Å	Cu Kα radiation, λ = 1.54184 Å
b = 13.2640 (5) Å	Cell parameters from 6063 reflections
c = 15.3166 (4) Å	θ = 4.4–74.6°
α = 87.778 (3)°	µ = 2.80 mm^−1
β = 88.384 (3)°	T = 173 K
γ = 75.173 (3)°	Needle, clear colourless
V = 1722.39 (10) Å^3	0.3 × 0.15 × 0.1 mm

Data collection

SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	6868 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	5863 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
Detector resolution: 5.2137 pixels mm^-1	θmax = 74.9°, θmin = 3.5°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −16→16
Tmin = 0.647, Tmax = 1.000	l = −12→19
12466 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 0.5269P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6868 reflections	Δρmax = 0.58 e Å^−3
433 parameters	Δρmin = −0.44 e Å^−3
0 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq
P001	0.50818 (6)	0.25857 (4)	0.67923 (3)	0.02278 (12)
P002	0.90759 (6)	0.77901 (4)	0.73817 (3)	0.02398 (12)
S003	0.89325 (6)	0.71151 (4)	0.62619 (3)	0.03123 (13)
S004	0.98152 (6)	0.90828 (4)	0.73102 (3)	0.03141 (13)
F005	0.92195 (16)	0.83346 (12)	0.93356 (8)	0.0454 (3)
F006	0.75341 (19)	0.60931 (12)	0.80333 (10)	0.0509 (4)
F007	0.72886 (19)	0.87295 (14)	1.02322 (9)	0.0600 (4)
F008	0.8079 (2)	0.71688 (13)	0.97890 (10)	0.0653 (5)
F009	0.9124 (3)	0.46888 (14)	0.76099 (14)	0.0861 (7)
C00A	0.6063 (2)	0.22884 (16)	0.78218 (12)	0.0253 (4)
C00B	0.4893 (2)	0.39393 (16)	0.65288 (12)	0.0276 (4)
C00C	0.6178 (2)	0.17720 (15)	0.59628 (11)	0.0230 (4)
C00D	0.7087 (2)	0.82076 (16)	0.79079 (12)	0.0260 (4)
C00E	0.7110 (2)	0.21462 (16)	0.53446 (12)	0.0278 (4)
H00E	0.7150	0.2840	0.5345	0.033*
C00F	0.3180 (2)	0.23240 (16)	0.68711 (12)	0.0265 (4)
F00G	0.8503 (3)	0.48825 (19)	0.89620 (14)	0.1076 (9)
C00H	0.5861 (2)	0.84386 (17)	0.73117 (14)	0.0319 (4)
H00H	0.6094	0.8283	0.6728	0.038*
C00I	0.6670 (2)	0.84369 (17)	0.87858 (13)	0.0298 (4)
C00J	0.6254 (3)	0.43064 (17)	0.64858 (14)	0.0334 (5)
H00J	0.7237	0.3846	0.6569	0.040*
C00K	0.6851 (2)	0.12753 (17)	0.80566 (13)	0.0311 (4)
H00K	0.6870	0.0735	0.7684	0.037*
C00L	0.2352 (2)	0.23565 (18)	0.61054 (13)	0.0324 (4)
H00L	0.2773	0.2532	0.5574	0.039*
C00M	0.6119 (3)	0.07311 (17)	0.59537 (14)	0.0337 (5)
H00M	0.5485	0.0479	0.6358	0.040*
C00N	0.7974 (2)	0.14870 (18)	0.47311 (13)	0.0326 (4)
H00N	0.8591	0.1739	0.4317	0.039*
C00O	0.3422 (3)	0.46297 (17)	0.64139 (13)	0.0338 (5)
H00O	0.2517	0.4387	0.6443	0.041*
C00P	1.0438 (3)	0.67773 (17)	0.80632 (13)	0.0313 (4)
C00Q	0.7927 (3)	0.04569 (18)	0.47310 (13)	0.0332 (5)
H00Q	0.8517	0.0016	0.4318	0.040*
C00R	0.7007 (3)	0.00745 (18)	0.53420 (14)	0.0372 (5)
H00R	0.6985	−0.0623	0.5342	0.045*
C00S	0.7813 (3)	0.81714 (19)	0.95208 (13)	0.0374 (5)
C00T	0.4312 (3)	0.88899 (19)	0.75557 (16)	0.0393 (5)
H00T	0.3529	0.9037	0.7139	0.047*
C00U	0.0899 (3)	0.21269 (19)	0.61374 (15)	0.0381 (5)
H00U	0.0336	0.2154	0.5628	0.046*
C00V	0.2559 (3)	0.2073 (2)	0.76684 (14)	0.0395 (5)
H00V	0.3107	0.2062	0.8181	0.047*
C00W	0.5112 (3)	0.88851 (19)	0.90279 (15)	0.0393 (5)
H00W	0.4857	0.9029	0.9611	0.047*
C00X	1.0262 (3)	0.57976 (18)	0.83672 (14)	0.0421 (6)
C00Y	0.7612 (3)	0.10691 (19)	0.88513 (14)	0.0378 (5)
H00Y	0.8150	0.0389	0.9008	0.045*
C00Z	0.0289 (3)	0.1859 (2)	0.69245 (17)	0.0431 (6)
H00Z	−0.0678	0.1691	0.6942	0.052*
C010	1.1885 (3)	0.6994 (2)	0.82077 (14)	0.0396 (5)
H010	1.2036	0.7634	0.8012	0.048*
C011	0.3935 (3)	0.9120 (2)	0.84156 (17)	0.0437 (6)
H011	0.2899	0.9430	0.8583	0.052*
C012	0.7576 (3)	0.1867 (2)	0.94098 (14)	0.0386 (5)
H012	0.8069	0.1723	0.9946	0.046*
C013	0.6050 (3)	0.30946 (19)	0.83804 (15)	0.0452 (6)
H013	0.5534	0.3778	0.8223	0.054*
C014	0.6131 (3)	0.53528 (19)	0.63190 (15)	0.0429 (6)
H014	0.7034	0.5597	0.6279	0.052*
C015	0.3312 (3)	0.56847 (19)	0.62550 (16)	0.0446 (6)
H015	0.2332	0.6152	0.6178	0.053*
C016	0.4671 (3)	0.60362 (19)	0.62117 (16)	0.0474 (6)
H016	0.4595	0.6743	0.6109	0.057*
C017	0.1097 (3)	0.1837 (2)	0.76876 (16)	0.0478 (6)
H017	0.0666	0.1665	0.8217	0.057*
C018	1.3101 (3)	0.6291 (3)	0.86315 (16)	0.0543 (7)
H018	1.4057	0.6455	0.8704	0.065*
C019	0.8851 (4)	0.5388 (2)	0.82406 (18)	0.0562 (8)
C01A	0.6811 (4)	0.2871 (2)	0.91716 (15)	0.0517 (7)
H01A	0.6802	0.3409	0.9545	0.062*
C01B	1.1493 (4)	0.5105 (2)	0.88095 (17)	0.0587 (8)
H01B	1.1359	0.4464	0.9016	0.070*
C01C	1.2893 (4)	0.5348 (2)	0.89462 (18)	0.0623 (9)
H01C	1.3694	0.4880	0.9248	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P001	0.0239 (2)	0.0246 (2)	0.0205 (2)	−0.00767 (18)	0.00042 (17)	0.00034 (18)
P002	0.0246 (2)	0.0272 (3)	0.0217 (2)	−0.00964 (19)	−0.00032 (17)	0.00091 (18)
S003	0.0379 (3)	0.0360 (3)	0.0230 (2)	−0.0152 (2)	−0.00126 (19)	−0.00168 (19)
S004	0.0321 (3)	0.0307 (3)	0.0352 (3)	−0.0153 (2)	0.0059 (2)	−0.0032 (2)
F005	0.0357 (7)	0.0695 (10)	0.0309 (6)	−0.0121 (7)	−0.0060 (5)	−0.0050 (6)
F006	0.0582 (9)	0.0423 (8)	0.0602 (9)	−0.0285 (7)	0.0020 (7)	0.0035 (7)
F007	0.0590 (10)	0.0856 (13)	0.0264 (7)	−0.0007 (9)	0.0020 (6)	−0.0136 (7)
F008	0.0923 (13)	0.0524 (10)	0.0515 (9)	−0.0205 (9)	−0.0222 (9)	0.0235 (8)
F009	0.1061 (16)	0.0404 (9)	0.1108 (16)	−0.0083 (10)	−0.0534 (13)	−0.0224 (10)
C00A	0.0260 (9)	0.0289 (10)	0.0220 (9)	−0.0089 (8)	0.0007 (7)	0.0003 (7)
C00B	0.0337 (10)	0.0253 (10)	0.0238 (9)	−0.0077 (8)	−0.0026 (8)	0.0005 (7)
C00C	0.0231 (9)	0.0271 (10)	0.0196 (8)	−0.0083 (7)	0.0002 (7)	0.0002 (7)
C00D	0.0260 (9)	0.0287 (10)	0.0255 (9)	−0.0117 (8)	0.0006 (7)	0.0047 (8)
C00E	0.0303 (10)	0.0302 (10)	0.0256 (9)	−0.0130 (8)	0.0015 (8)	0.0014 (8)
C00F	0.0246 (9)	0.0285 (10)	0.0270 (9)	−0.0081 (8)	0.0035 (7)	0.0001 (8)
F00G	0.164 (2)	0.1113 (18)	0.0804 (14)	−0.0995 (18)	−0.0475 (15)	0.0605 (13)
C00H	0.0308 (10)	0.0391 (12)	0.0296 (10)	−0.0162 (9)	−0.0033 (8)	0.0050 (9)
C00I	0.0315 (10)	0.0330 (11)	0.0268 (10)	−0.0124 (9)	0.0030 (8)	0.0035 (8)
C00J	0.0366 (11)	0.0292 (11)	0.0355 (11)	−0.0102 (9)	−0.0087 (9)	0.0031 (8)
C00K	0.0350 (11)	0.0289 (11)	0.0304 (10)	−0.0099 (9)	−0.0013 (8)	−0.0001 (8)
C00L	0.0312 (11)	0.0404 (12)	0.0285 (10)	−0.0147 (9)	0.0023 (8)	−0.0016 (9)
C00M	0.0436 (12)	0.0308 (11)	0.0292 (10)	−0.0152 (9)	0.0073 (9)	−0.0002 (8)
C00N	0.0316 (10)	0.0399 (12)	0.0278 (10)	−0.0126 (9)	0.0076 (8)	−0.0011 (8)
C00O	0.0372 (11)	0.0306 (11)	0.0310 (10)	−0.0039 (9)	−0.0016 (8)	−0.0003 (8)
C00P	0.0365 (11)	0.0329 (11)	0.0231 (9)	−0.0053 (9)	−0.0035 (8)	−0.0044 (8)
C00Q	0.0334 (11)	0.0382 (12)	0.0256 (9)	−0.0047 (9)	0.0034 (8)	−0.0057 (8)
C00R	0.0516 (13)	0.0269 (11)	0.0338 (11)	−0.0116 (10)	0.0059 (10)	−0.0050 (9)
C00S	0.0432 (13)	0.0441 (13)	0.0233 (10)	−0.0092 (10)	0.0021 (9)	0.0022 (9)
C00T	0.0281 (11)	0.0469 (14)	0.0446 (12)	−0.0135 (10)	−0.0068 (9)	0.0092 (10)
C00U	0.0290 (11)	0.0455 (13)	0.0419 (12)	−0.0128 (10)	−0.0023 (9)	−0.0030 (10)
C00V	0.0331 (11)	0.0554 (15)	0.0293 (10)	−0.0119 (10)	0.0027 (9)	0.0077 (10)
C00W	0.0367 (12)	0.0477 (14)	0.0353 (11)	−0.0152 (10)	0.0098 (9)	−0.0010 (10)
C00X	0.0632 (16)	0.0321 (12)	0.0288 (10)	−0.0074 (11)	−0.0119 (10)	0.0001 (9)
C00Y	0.0368 (12)	0.0386 (13)	0.0361 (11)	−0.0067 (10)	−0.0054 (9)	0.0081 (9)
C00Z	0.0250 (11)	0.0484 (14)	0.0572 (15)	−0.0136 (10)	0.0034 (10)	0.0060 (11)
C010	0.0320 (11)	0.0518 (15)	0.0319 (11)	−0.0040 (10)	−0.0038 (9)	−0.0064 (10)
C011	0.0269 (11)	0.0494 (15)	0.0545 (14)	−0.0102 (10)	0.0068 (10)	0.0012 (11)
C012	0.0394 (12)	0.0543 (15)	0.0268 (10)	−0.0211 (11)	−0.0069 (9)	0.0072 (10)
C013	0.0716 (17)	0.0305 (12)	0.0297 (11)	−0.0053 (11)	−0.0080 (11)	−0.0023 (9)
C014	0.0575 (15)	0.0360 (13)	0.0425 (12)	−0.0246 (11)	−0.0153 (11)	0.0074 (10)
C015	0.0526 (15)	0.0318 (12)	0.0419 (13)	0.0032 (11)	−0.0094 (11)	0.0015 (10)
C016	0.0721 (18)	0.0258 (12)	0.0462 (13)	−0.0151 (12)	−0.0189 (12)	0.0047 (10)
C017	0.0337 (12)	0.0688 (18)	0.0411 (13)	−0.0167 (12)	0.0099 (10)	0.0138 (12)
C018	0.0384 (13)	0.077 (2)	0.0373 (13)	0.0060 (13)	−0.0109 (10)	−0.0151 (13)
C019	0.093 (2)	0.0338 (14)	0.0468 (14)	−0.0256 (14)	−0.0223 (15)	0.0127 (11)
C01A	0.084 (2)	0.0446 (15)	0.0294 (11)	−0.0210 (14)	−0.0112 (12)	−0.0040 (10)
C01B	0.091 (2)	0.0361 (14)	0.0386 (13)	0.0040 (14)	−0.0204 (14)	0.0000 (11)
C01C	0.0663 (19)	0.0607 (19)	0.0409 (14)	0.0222 (15)	−0.0233 (13)	−0.0102 (13)

Geometric parameters (Å, º)

P001—C00A	1.7996 (19)	C00O—H00O	0.9300
P001—C00B	1.791 (2)	C00O—C015	1.390 (3)
P001—C00C	1.7919 (19)	C00P—C00X	1.408 (3)
P001—C00F	1.790 (2)	C00P—C010	1.397 (3)
P002—S003	1.9870 (7)	C00Q—H00Q	0.9300
P002—S004	1.9810 (7)	C00Q—C00R	1.384 (3)
P002—C00D	1.861 (2)	C00R—H00R	0.9300
P002—C00P	1.861 (2)	C00T—H00T	0.9300
F005—C00S	1.328 (3)	C00T—C011	1.376 (4)
F006—C019	1.325 (3)	C00U—H00U	0.9300
F007—C00S	1.344 (3)	C00U—C00Z	1.376 (3)
F008—C00S	1.340 (3)	C00V—H00V	0.9300
F009—C019	1.339 (3)	C00V—C017	1.396 (3)
C00A—C00K	1.383 (3)	C00W—H00W	0.9300
C00A—C013	1.393 (3)	C00W—C011	1.382 (3)
C00B—C00J	1.400 (3)	C00X—C019	1.494 (4)
C00B—C00O	1.390 (3)	C00X—C01B	1.399 (3)
C00C—C00E	1.393 (3)	C00Y—H00Y	0.9300
C00C—C00M	1.395 (3)	C00Y—C012	1.380 (3)
C00D—C00H	1.397 (3)	C00Z—H00Z	0.9300
C00D—C00I	1.408 (3)	C00Z—C017	1.380 (4)
C00E—H00E	0.9300	C010—H010	0.9300
C00E—C00N	1.381 (3)	C010—C018	1.383 (3)
C00F—C00L	1.391 (3)	C011—H011	0.9300
C00F—C00V	1.387 (3)	C012—H012	0.9300
F00G—C019	1.339 (3)	C012—C01A	1.370 (4)
C00H—H00H	0.9300	C013—H013	0.9300
C00H—C00T	1.385 (3)	C013—C01A	1.385 (3)
C00I—C00S	1.500 (3)	C014—H014	0.9300
C00I—C00W	1.391 (3)	C014—C016	1.377 (4)
C00J—H00J	0.9300	C015—H015	0.9300
C00J—C014	1.379 (3)	C015—C016	1.386 (4)
C00K—H00K	0.9300	C016—H016	0.9300
C00K—C00Y	1.389 (3)	C017—H017	0.9300
C00L—H00L	0.9300	C018—H018	0.9300
C00L—C00U	1.384 (3)	C018—C01C	1.377 (5)
C00M—H00M	0.9300	C01A—H01A	0.9300
C00M—C00R	1.385 (3)	C01B—H01B	0.9300
C00N—H00N	0.9300	C01B—C01C	1.371 (5)
C00N—C00Q	1.377 (3)	C01C—H01C	0.9300
C00B—P001—C00A	107.62 (9)	F007—C00S—C00I	112.4 (2)
C00B—P001—C00C	111.43 (9)	F008—C00S—F007	105.64 (18)
C00C—P001—C00A	110.29 (9)	F008—C00S—C00I	112.1 (2)
C00F—P001—C00A	110.23 (9)	C00H—C00T—H00T	120.1
C00F—P001—C00B	110.35 (10)	C011—C00T—C00H	119.9 (2)
C00F—P001—C00C	106.94 (9)	C011—C00T—H00T	120.1
S004—P002—S003	116.79 (3)	C00L—C00U—H00U	120.1
C00D—P002—S003	109.91 (7)	C00Z—C00U—C00L	119.9 (2)
C00D—P002—S004	103.72 (7)	C00Z—C00U—H00U	120.1
C00D—P002—C00P	111.40 (9)	C00F—C00V—H00V	120.6
C00P—P002—S003	105.32 (7)	C00F—C00V—C017	118.8 (2)
C00P—P002—S004	109.82 (7)	C017—C00V—H00V	120.6
C00K—C00A—P001	120.89 (15)	C00I—C00W—H00W	119.5
C00K—C00A—C013	119.79 (19)	C011—C00W—C00I	121.1 (2)
C013—C00A—P001	119.31 (16)	C011—C00W—H00W	119.5
C00J—C00B—P001	118.73 (16)	C00P—C00X—C019	125.6 (2)
C00O—C00B—P001	121.10 (16)	C01B—C00X—C00P	119.8 (3)
C00O—C00B—C00J	120.1 (2)	C01B—C00X—C019	114.5 (2)
C00E—C00C—P001	121.69 (15)	C00K—C00Y—H00Y	119.8
C00E—C00C—C00M	119.54 (18)	C012—C00Y—C00K	120.4 (2)
C00M—C00C—P001	118.75 (14)	C012—C00Y—H00Y	119.8
C00H—C00D—P002	113.43 (15)	C00U—C00Z—H00Z	119.7
C00H—C00D—C00I	116.55 (19)	C00U—C00Z—C017	120.6 (2)
C00I—C00D—P002	129.53 (15)	C017—C00Z—H00Z	119.7
C00C—C00E—H00E	120.0	C00P—C010—H010	118.8
C00N—C00E—C00C	120.02 (19)	C018—C010—C00P	122.4 (3)
C00N—C00E—H00E	120.0	C018—C010—H010	118.8
C00L—C00F—P001	118.09 (15)	C00T—C011—C00W	119.3 (2)
C00V—C00F—P001	121.22 (16)	C00T—C011—H011	120.4
C00V—C00F—C00L	120.68 (19)	C00W—C011—H011	120.4
C00D—C00H—H00H	118.7	C00Y—C012—H012	120.1
C00T—C00H—C00D	122.5 (2)	C01A—C012—C00Y	119.8 (2)
C00T—C00H—H00H	118.7	C01A—C012—H012	120.1
C00D—C00I—C00S	123.68 (19)	C00A—C013—H013	120.2
C00W—C00I—C00D	120.7 (2)	C01A—C013—C00A	119.6 (2)
C00W—C00I—C00S	115.58 (19)	C01A—C013—H013	120.2
C00B—C00J—H00J	120.1	C00J—C014—H014	120.0
C014—C00J—C00B	119.8 (2)	C016—C014—C00J	120.0 (2)
C014—C00J—H00J	120.1	C016—C014—H014	120.0
C00A—C00K—H00K	120.1	C00O—C015—H015	120.2
C00A—C00K—C00Y	119.7 (2)	C016—C015—C00O	119.6 (2)
C00Y—C00K—H00K	120.1	C016—C015—H015	120.2
C00F—C00L—H00L	120.1	C014—C016—C015	120.9 (2)
C00U—C00L—C00F	119.72 (19)	C014—C016—H016	119.6
C00U—C00L—H00L	120.1	C015—C016—H016	119.6
C00C—C00M—H00M	120.1	C00V—C017—H017	119.9
C00R—C00M—C00C	119.90 (19)	C00Z—C017—C00V	120.3 (2)
C00R—C00M—H00M	120.1	C00Z—C017—H017	119.9
C00E—C00N—H00N	119.9	C010—C018—H018	120.1
C00Q—C00N—C00E	120.24 (19)	C01C—C018—C010	119.9 (3)
C00Q—C00N—H00N	119.9	C01C—C018—H018	120.1
C00B—C00O—H00O	120.2	F006—C019—F009	106.4 (2)
C00B—C00O—C015	119.6 (2)	F006—C019—F00G	105.8 (3)
C015—C00O—H00O	120.2	F006—C019—C00X	116.0 (2)
C00X—C00P—P002	128.67 (17)	F009—C019—C00X	110.9 (3)
C010—C00P—P002	114.06 (17)	F00G—C019—F009	105.7 (2)
C010—C00P—C00X	116.9 (2)	F00G—C019—C00X	111.4 (2)
C00N—C00Q—H00Q	119.8	C012—C01A—C013	120.7 (2)
C00N—C00Q—C00R	120.3 (2)	C012—C01A—H01A	119.6
C00R—C00Q—H00Q	119.8	C013—C01A—H01A	119.6
C00M—C00R—H00R	120.0	C00X—C01B—H01B	119.2
C00Q—C00R—C00M	119.9 (2)	C01C—C01B—C00X	121.6 (3)
C00Q—C00R—H00R	120.0	C01C—C01B—H01B	119.2
F005—C00S—F007	105.15 (19)	C018—C01C—H01C	120.4
F005—C00S—F008	106.1 (2)	C01B—C01C—C018	119.3 (2)
F005—C00S—C00I	114.70 (17)	C01B—C01C—H01C	120.4

(III)

Crystal data

C26H26O3P2S4U	Z = 2
Mr = 814.68	F(000) = 784
Triclinic, P1	Dx = 1.834 Mg m^−3
a = 11.5443 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6402 (3) Å	Cell parameters from 14083 reflections
c = 13.0973 (3) Å	θ = 3.9–30.4°
α = 113.227 (2)°	µ = 5.92 mm^−1
β = 110.729 (2)°	T = 173 K
γ = 92.865 (2)°	Plate, clear orange
V = 1475.39 (7) Å^3	0.35 × 0.3 × 0.05 mm

Data collection

SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	8094 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	7324 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.047
Detector resolution: 5.2137 pixels mm^-1	θmax = 30.4°, θmin = 3.3°
ω scans	h = −15→16
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −16→16
Tmin = 0.364, Tmax = 1.000	l = −18→18
27638 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0213P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
8094 reflections	Δρmax = 1.30 e Å^−3
340 parameters	Δρmin = −1.39 e Å^−3
3 restraints

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
U001	0.60323 (2)	0.56478 (2)	0.24900 (2)	0.01772 (4)
S002	0.79312 (8)	0.78792 (9)	0.33879 (7)	0.02241 (17)
S003	0.44606 (8)	0.32557 (9)	0.04784 (7)	0.02342 (18)
S004	0.64466 (8)	0.72848 (9)	0.49339 (8)	0.02519 (18)
P005	0.79040 (8)	0.83951 (9)	0.50399 (7)	0.01821 (17)
S006	0.42426 (9)	0.46166 (9)	0.31375 (8)	0.0287 (2)
P007	0.37367 (8)	0.30095 (9)	0.15976 (8)	0.02130 (18)
O008	0.6852 (2)	0.5215 (2)	0.0956 (2)	0.0257 (5)
H008	0.656 (3)	0.549 (3)	0.042 (2)	0.039*
O009	0.7136 (2)	0.4809 (3)	0.3034 (2)	0.0286 (6)
O00A	0.4930 (2)	0.6425 (2)	0.1839 (2)	0.0255 (5)
C00B	0.9409 (3)	0.8236 (3)	0.6011 (3)	0.0222 (7)
C00C	0.7827 (3)	1.0060 (3)	0.5690 (3)	0.0198 (7)
C00D	0.7651 (4)	0.4320 (4)	0.0632 (4)	0.0411 (10)
H00A	0.7450	0.3986	−0.0231	0.049*	0.48 (2)
H00B	0.7491	0.3605	0.0806	0.049*	0.48 (2)
H00C	0.8044	0.4100	0.1299	0.049*	0.52 (2)
H00D	0.7110	0.3539	−0.0072	0.049*	0.52 (2)
C00E	0.9551 (4)	0.7009 (4)	0.5872 (3)	0.0343 (9)
H00E	0.8857	0.6319	0.5379	0.041*
C00F	1.0436 (3)	0.9243 (4)	0.6747 (3)	0.0260 (8)
H00F	1.0346	1.0066	0.6850	0.031*
C00G	0.4293 (3)	0.1697 (3)	0.1885 (3)	0.0219 (7)
C00H	0.8555 (3)	1.0960 (4)	0.5580 (3)	0.0256 (7)
H00H	0.9088	1.0701	0.5181	0.031*
C00I	0.2033 (3)	0.2459 (3)	0.0831 (3)	0.0244 (7)
C00J	0.1357 (3)	0.2260 (4)	−0.0355 (3)	0.0325 (9)
H00J	0.1780	0.2421	−0.0787	0.039*
C00K	0.7025 (3)	1.0461 (4)	0.6279 (3)	0.0306 (8)
H00K	0.6533	0.9872	0.6360	0.037*
C00L	1.0728 (4)	0.6818 (5)	0.6468 (4)	0.0424 (10)
H00L	1.0821	0.5998	0.6375	0.051*
C00M	0.5117 (3)	0.1876 (4)	0.3022 (3)	0.0303 (8)
H00M	0.5390	0.2681	0.3682	0.036*
C00N	1.1758 (4)	0.7833 (5)	0.7194 (4)	0.0390 (10)
H00N	1.2548	0.7697	0.7583	0.047*
C00O	1.1624 (3)	0.9045 (4)	0.7346 (3)	0.0323 (9)
H00O	1.2319	0.9733	0.7846	0.039*
C00P	0.6960 (4)	1.1739 (4)	0.6745 (4)	0.0404 (10)
H00P	0.6422	1.2004	0.7138	0.049*
C00Q	0.8492 (4)	1.2238 (4)	0.6061 (3)	0.0363 (9)
H00Q	0.8993	1.2837	0.5999	0.044*
C00R	0.0046 (4)	0.1820 (4)	−0.0900 (4)	0.0395 (10)
H00R	−0.0408	0.1706	−0.1691	0.047*
C00S	0.3889 (4)	0.0486 (4)	0.0908 (4)	0.0358 (9)
H00S	0.3330	0.0368	0.0143	0.043*
C00T	0.1386 (3)	0.2190 (4)	0.1454 (4)	0.0384 (10)
H00T	0.1826	0.2323	0.2253	0.046*
C00U	0.7682 (4)	1.2619 (4)	0.6634 (4)	0.0432 (10)
H00U	0.7626	1.3473	0.6944	0.052*
C00V	−0.0580 (4)	0.1552 (4)	−0.0283 (4)	0.0380 (9)
H00V	−0.1457	0.1254	−0.0654	0.046*
C00W	0.5145 (4)	−0.0368 (4)	0.2198 (4)	0.0415 (11)
H00W	0.5442	−0.1058	0.2305	0.050*
C00X	0.0083 (4)	0.1723 (5)	0.0883 (4)	0.0464 (12)
H00X	−0.0344	0.1524	0.1295	0.056*
C00Y	0.4314 (4)	−0.0541 (4)	0.1071 (4)	0.0432 (10)
H00Y	0.4038	−0.1352	0.0417	0.052*
C00Z	0.5536 (4)	0.0817 (5)	0.3160 (4)	0.0399 (10)
H00Z	0.6091	0.0923	0.3923	0.048*
C010	0.9020 (9)	0.5005 (11)	0.1353 (14)	0.050 (4)	0.48 (2)
H01A	0.9155	0.5757	0.1236	0.075*	0.48 (2)
H01B	0.9544	0.4447	0.1084	0.075*	0.48 (2)
H01C	0.9238	0.5251	0.2201	0.075*	0.48 (2)
C0	0.8611 (16)	0.4772 (13)	0.037 (2)	0.087 (7)	0.52 (2)
H0A	0.8239	0.5019	−0.0272	0.130*	0.52 (2)
H0B	0.9050	0.4107	0.0120	0.130*	0.52 (2)
H0C	0.9200	0.5500	0.1084	0.130*	0.52 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U001	0.01807 (7)	0.01618 (7)	0.01906 (7)	0.00627 (5)	0.00713 (5)	0.00801 (5)
S002	0.0226 (4)	0.0243 (5)	0.0186 (4)	0.0016 (4)	0.0089 (3)	0.0079 (4)
S003	0.0294 (4)	0.0198 (5)	0.0235 (4)	0.0055 (4)	0.0140 (4)	0.0090 (4)
S004	0.0262 (4)	0.0233 (5)	0.0236 (4)	0.0003 (4)	0.0133 (4)	0.0059 (4)
P005	0.0170 (4)	0.0185 (5)	0.0178 (4)	0.0047 (3)	0.0068 (3)	0.0070 (4)
S006	0.0364 (5)	0.0202 (5)	0.0260 (4)	0.0015 (4)	0.0169 (4)	0.0038 (4)
P007	0.0246 (4)	0.0181 (5)	0.0225 (4)	0.0051 (4)	0.0102 (4)	0.0096 (4)
O008	0.0257 (13)	0.0317 (16)	0.0237 (12)	0.0099 (11)	0.0121 (11)	0.0138 (12)
O009	0.0312 (13)	0.0340 (17)	0.0320 (13)	0.0194 (12)	0.0159 (12)	0.0212 (13)
O00A	0.0228 (12)	0.0260 (15)	0.0304 (13)	0.0096 (11)	0.0091 (11)	0.0161 (12)
C00B	0.0224 (17)	0.027 (2)	0.0172 (15)	0.0099 (15)	0.0080 (14)	0.0094 (15)
C00C	0.0175 (15)	0.0197 (19)	0.0173 (15)	0.0041 (14)	0.0029 (13)	0.0071 (15)
C00D	0.039 (2)	0.046 (3)	0.041 (2)	0.017 (2)	0.020 (2)	0.017 (2)
C00E	0.033 (2)	0.029 (2)	0.033 (2)	0.0125 (18)	0.0049 (17)	0.0126 (19)
C00F	0.0209 (17)	0.035 (2)	0.0254 (17)	0.0077 (16)	0.0083 (15)	0.0172 (18)
C00G	0.0208 (16)	0.0198 (19)	0.0281 (17)	0.0045 (14)	0.0102 (15)	0.0133 (16)
C00H	0.0254 (18)	0.025 (2)	0.0249 (17)	0.0074 (16)	0.0093 (15)	0.0101 (16)
C00I	0.0243 (17)	0.021 (2)	0.0281 (18)	0.0063 (15)	0.0094 (15)	0.0120 (16)
C00J	0.031 (2)	0.038 (3)	0.0275 (19)	0.0047 (18)	0.0114 (17)	0.0144 (19)
C00K	0.0259 (19)	0.025 (2)	0.036 (2)	0.0044 (16)	0.0146 (17)	0.0070 (18)
C00L	0.042 (2)	0.039 (3)	0.045 (2)	0.023 (2)	0.012 (2)	0.020 (2)
C00M	0.0228 (18)	0.038 (3)	0.0295 (19)	0.0042 (17)	0.0075 (16)	0.0173 (19)
C00N	0.030 (2)	0.060 (3)	0.038 (2)	0.023 (2)	0.0141 (19)	0.029 (2)
C00O	0.0223 (18)	0.046 (3)	0.0272 (19)	0.0060 (18)	0.0078 (16)	0.0174 (19)
C00P	0.037 (2)	0.031 (3)	0.048 (2)	0.013 (2)	0.022 (2)	0.008 (2)
C00Q	0.041 (2)	0.026 (2)	0.040 (2)	0.0057 (19)	0.0130 (19)	0.016 (2)
C00R	0.031 (2)	0.047 (3)	0.030 (2)	0.006 (2)	0.0063 (18)	0.013 (2)
C00S	0.046 (2)	0.025 (2)	0.034 (2)	0.0111 (19)	0.0138 (19)	0.0132 (19)
C00T	0.028 (2)	0.062 (3)	0.033 (2)	0.009 (2)	0.0130 (18)	0.029 (2)
C00U	0.048 (3)	0.023 (2)	0.050 (3)	0.015 (2)	0.019 (2)	0.008 (2)
C00V	0.0214 (19)	0.039 (3)	0.043 (2)	0.0051 (18)	0.0084 (18)	0.013 (2)
C00W	0.036 (2)	0.038 (3)	0.078 (3)	0.023 (2)	0.033 (2)	0.043 (3)
C00X	0.033 (2)	0.065 (4)	0.053 (3)	0.010 (2)	0.024 (2)	0.031 (3)
C00Y	0.048 (3)	0.020 (2)	0.062 (3)	0.012 (2)	0.024 (2)	0.017 (2)
C00Z	0.030 (2)	0.054 (3)	0.051 (3)	0.016 (2)	0.014 (2)	0.039 (3)
C010	0.031 (5)	0.050 (7)	0.069 (8)	0.015 (5)	0.021 (5)	0.026 (6)
C0	0.105 (12)	0.058 (9)	0.17 (2)	0.052 (9)	0.111 (15)	0.071 (12)

Geometric parameters (Å, º)

U001—S002	2.8516 (9)	C00J—H00J	0.9300
U001—S003	2.8829 (9)	C00J—C00R	1.390 (5)
U001—S004	2.8496 (8)	C00K—H00K	0.9300
U001—S006	2.8678 (8)	C00K—C00P	1.385 (5)
U001—O008	2.404 (2)	C00L—H00L	0.9300
U001—O009	1.764 (2)	C00L—C00N	1.374 (6)
U001—O00A	1.766 (2)	C00M—H00M	0.9300
S002—P005	2.0169 (10)	C00M—C00Z	1.400 (5)
S003—P007	2.0259 (11)	C00N—H00N	0.9300
S004—P005	1.9991 (12)	C00N—C00O	1.369 (6)
P005—C00B	1.823 (3)	C00O—H00O	0.9300
P005—C00C	1.805 (3)	C00P—H00P	0.9300
S006—P007	1.9974 (13)	C00P—C00U	1.372 (6)
P007—C00G	1.808 (3)	C00Q—H00Q	0.9300
P007—C00I	1.804 (3)	C00Q—C00U	1.381 (5)
O008—H008	0.851 (9)	C00R—H00R	0.9300
O008—C00D	1.463 (4)	C00R—C00V	1.365 (5)
C00B—C00E	1.392 (5)	C00S—H00S	0.9300
C00B—C00F	1.368 (5)	C00S—C00Y	1.379 (5)
C00C—C00H	1.393 (5)	C00T—H00T	0.9300
C00C—C00K	1.391 (4)	C00T—C00X	1.384 (5)
C00D—H00A	0.9700	C00U—H00U	0.9300
C00D—H00B	0.9700	C00V—H00V	0.9300
C00D—H00C	0.9700	C00V—C00X	1.370 (5)
C00D—H00D	0.9700	C00W—H00W	0.9300
C00D—C010	1.500 (10)	C00W—C00Y	1.372 (6)
C00D—C0	1.406 (10)	C00W—C00Z	1.363 (6)
C00E—H00E	0.9300	C00X—H00X	0.9300
C00E—C00L	1.387 (5)	C00Y—H00Y	0.9300
C00F—H00F	0.9300	C00Z—H00Z	0.9300
C00F—C00O	1.401 (4)	C010—H01A	0.9600
C00G—C00M	1.378 (4)	C010—H01B	0.9600
C00G—C00S	1.389 (5)	C010—H01C	0.9600
C00H—H00H	0.9300	C0—H0A	0.9600
C00H—C00Q	1.385 (5)	C0—H0B	0.9600
C00I—C00J	1.384 (5)	C0—H0C	0.9600
C00I—C00T	1.390 (4)
S002—U001—S003	148.08 (2)	C00Q—C00H—C00C	120.6 (3)
S002—U001—S006	141.05 (2)	C00Q—C00H—H00H	119.7
S004—U001—S002	71.00 (2)	C00J—C00I—P007	122.8 (2)
S004—U001—S003	140.85 (2)	C00J—C00I—C00T	119.1 (3)
S004—U001—S006	70.41 (3)	C00T—C00I—P007	118.1 (3)
S006—U001—S003	70.48 (2)	C00I—C00J—H00J	120.0
O008—U001—S002	74.84 (6)	C00I—C00J—C00R	120.1 (3)
O008—U001—S003	73.86 (6)	C00R—C00J—H00J	120.0
O008—U001—S004	144.85 (6)	C00C—C00K—H00K	120.0
O008—U001—S006	144.11 (7)	C00P—C00K—C00C	119.9 (3)
O009—U001—S002	93.70 (9)	C00P—C00K—H00K	120.0
O009—U001—S003	89.63 (9)	C00E—C00L—H00L	119.8
O009—U001—S004	89.27 (8)	C00N—C00L—C00E	120.3 (4)
O009—U001—S006	90.88 (8)	C00N—C00L—H00L	119.8
O009—U001—O008	84.85 (9)	C00G—C00M—H00M	120.8
O009—U001—O00A	175.77 (10)	C00G—C00M—C00Z	118.5 (4)
O00A—U001—S002	86.95 (8)	C00Z—C00M—H00M	120.8
O00A—U001—S003	87.63 (9)	C00L—C00N—H00N	119.9
O00A—U001—S004	94.89 (8)	C00O—C00N—C00L	120.1 (3)
O00A—U001—S006	91.24 (7)	C00O—C00N—H00N	119.9
O00A—U001—O008	91.29 (9)	C00F—C00O—H00O	120.1
P005—S002—U001	88.14 (4)	C00N—C00O—C00F	119.7 (4)
P007—S003—U001	87.88 (4)	C00N—C00O—H00O	120.1
P005—S004—U001	88.54 (4)	C00K—C00P—H00P	119.7
S004—P005—S002	111.04 (5)	C00U—C00P—C00K	120.6 (4)
C00B—P005—S002	106.98 (10)	C00U—C00P—H00P	119.7
C00B—P005—S004	110.60 (11)	C00H—C00Q—H00Q	120.2
C00C—P005—S002	109.85 (10)	C00U—C00Q—C00H	119.7 (4)
C00C—P005—S004	110.66 (11)	C00U—C00Q—H00Q	120.2
C00C—P005—C00B	107.58 (16)	C00J—C00R—H00R	119.8
P007—S006—U001	88.85 (4)	C00V—C00R—C00J	120.4 (3)
S006—P007—S003	111.13 (6)	C00V—C00R—H00R	119.8
C00G—P007—S003	107.54 (11)	C00G—C00S—H00S	119.9
C00G—P007—S006	111.74 (12)	C00Y—C00S—C00G	120.2 (4)
C00I—P007—S003	110.52 (11)	C00Y—C00S—H00S	119.9
C00I—P007—S006	111.27 (12)	C00I—C00T—H00T	120.0
C00I—P007—C00G	104.38 (15)	C00X—C00T—C00I	119.9 (3)
U001—O008—H008	119.4 (13)	C00X—C00T—H00T	120.0
C00D—O008—U001	128.95 (19)	C00P—C00U—C00Q	120.2 (4)
C00D—O008—H008	110.5 (13)	C00P—C00U—H00U	119.9
C00E—C00B—P005	117.8 (3)	C00Q—C00U—H00U	119.9
C00F—C00B—P005	122.3 (3)	C00R—C00V—H00V	120.0
C00F—C00B—C00E	119.3 (3)	C00R—C00V—C00X	120.0 (4)
C00H—C00C—P005	120.0 (2)	C00X—C00V—H00V	120.0
C00K—C00C—P005	121.0 (3)	C00Y—C00W—H00W	120.0
C00K—C00C—C00H	119.0 (3)	C00Z—C00W—H00W	120.0
O008—C00D—H00A	109.8	C00Z—C00W—C00Y	120.0 (4)
O008—C00D—H00B	109.8	C00T—C00X—H00X	119.7
O008—C00D—H00C	108.5	C00V—C00X—C00T	120.6 (3)
O008—C00D—H00D	108.5	C00V—C00X—H00X	119.7
O008—C00D—C010	109.2 (5)	C00S—C00Y—H00Y	120.0
H00A—C00D—H00B	108.3	C00W—C00Y—C00S	120.0 (4)
H00C—C00D—H00D	107.5	C00W—C00Y—H00Y	120.0
C010—C00D—H00A	109.8	C00M—C00Z—H00Z	119.4
C010—C00D—H00B	109.8	C00W—C00Z—C00M	121.2 (4)
C0—C00D—O008	115.3 (5)	C00W—C00Z—H00Z	119.4
C0—C00D—H00C	108.5	C00D—C010—H01A	109.5
C0—C00D—H00D	108.5	C00D—C010—H01B	109.5
C00B—C00E—H00E	120.0	C00D—C010—H01C	109.5
C00L—C00E—C00B	119.9 (4)	H01A—C010—H01B	109.5
C00L—C00E—H00E	120.0	H01A—C010—H01C	109.5
C00B—C00F—H00F	119.7	H01B—C010—H01C	109.5
C00B—C00F—C00O	120.5 (4)	C00D—C0—H0A	109.5
C00O—C00F—H00F	119.7	C00D—C0—H0B	109.5
C00M—C00G—P007	122.0 (3)	C00D—C0—H0C	109.5
C00M—C00G—C00S	120.1 (3)	H0A—C0—H0B	109.5
C00S—C00G—P007	117.8 (2)	H0A—C0—H0C	109.5
C00C—C00H—H00H	119.7	H0B—C0—H0C	109.5

(IV)

Crystal data

C30H22F12O3P2S4U·C2H6O	Dx = 1.872 Mg m^−3
Mr = 1132.75	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pca21	Cell parameters from 4125 reflections
a = 16.5607 (6) Å	θ = 5.4–70.7°
b = 8.1303 (3) Å	µ = 14.90 mm^−1
c = 59.7044 (13) Å	T = 173 K
V = 8038.8 (5) Å^3	Plate, clear yellow
Z = 8	0.16 × 0.1 × 0.02 mm
F(000) = 4368

Data collection

SuperNova, Dual, Cu at home/near, AtlasS2 diffractometer	11827 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	9865 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.061
Detector resolution: 10.4273 pixels mm^-1	θmax = 71.6°, θmin = 4.4°
ω scans	h = −20→9
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −9→7
Tmin = 0.675, Tmax = 1.000	l = −68→72
19109 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.067	w = 1/[σ^2(Fo^2) + (0.090P)^2 + 51.522P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.178	(Δ/σ)max = 0.014
S = 1.04	Δρmax = 6.20 e Å^−3
11827 reflections	Δρmin = −2.11 e Å^−3
1018 parameters	Absolute structure: Flack x determined using 2747 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
238 restraints	Absolute structure parameter: 0.147 (10)
Primary atom site location: dual

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
U1	0.49022 (4)	0.91342 (10)	0.62177 (2)	0.0348 (2)
U2	0.75773 (4)	0.41835 (10)	0.37663 (2)	0.0364 (2)
S4	0.6133 (3)	0.7646 (8)	0.59452 (8)	0.0342 (12)
P2	0.5720 (3)	0.8953 (8)	0.56810 (9)	0.0302 (11)
S8	0.6343 (3)	0.2671 (8)	0.40388 (9)	0.0355 (12)
S7	0.7708 (4)	0.5310 (12)	0.42119 (15)	0.0476 (18)
P4	0.6758 (3)	0.3955 (8)	0.43041 (10)	0.0319 (12)
S3	0.4742 (5)	1.0265 (10)	0.57667 (11)	0.0413 (17)
P1	0.5296 (4)	0.7648 (10)	0.67560 (9)	0.0466 (17)
S2	0.5792 (5)	0.6775 (12)	0.64741 (10)	0.058 (2)
S5	0.7989 (6)	0.4501 (16)	0.33033 (13)	0.077 (3)
P3	0.7178 (4)	0.2759 (11)	0.32244 (11)	0.0490 (17)
S6	0.6647 (5)	0.1933 (13)	0.35068 (12)	0.071 (3)
S1	0.4448 (5)	0.9324 (15)	0.66781 (13)	0.069 (3)
F23	0.744 (2)	0.468 (3)	0.5052 (4)	0.086 (7)
C15	0.6562 (17)	1.022 (3)	0.5587 (4)	0.031 (4)
O7	0.8699 (8)	0.600 (2)	0.3759 (4)	0.045 (4)
H7	0.9110	0.5591	0.3707	0.067*
F7	0.7925 (12)	0.735 (3)	0.5669 (3)	0.071 (5)
F9	0.6961 (9)	0.702 (2)	0.5440 (3)	0.057 (4)
O3	0.3793 (9)	1.0921 (19)	0.6222 (4)	0.049 (4)
H3	0.3323	1.0638	0.6242	0.074*
F11	0.6143 (12)	0.965 (3)	0.5097 (4)	0.070 (6)
F8	0.8109 (10)	0.787 (2)	0.5319 (3)	0.061 (4)
F19	0.4521 (10)	0.237 (2)	0.4318 (3)	0.064 (4)
O6	0.8279 (9)	0.269 (3)	0.3814 (4)	0.065 (6)
O2	0.4190 (9)	0.755 (2)	0.6157 (3)	0.040 (4)
F2	0.5266 (16)	0.970 (4)	0.7483 (4)	0.092 (9)
F21	0.5505 (9)	0.203 (2)	0.4548 (3)	0.057 (4)
F16	0.5899 (15)	0.054 (4)	0.3065 (7)	0.125 (12)
O5	0.6893 (11)	0.582 (2)	0.3717 (2)	0.037 (4)
O4	0.2399 (17)	0.964 (4)	0.6253 (8)	0.094 (10)
H4A	0.2243	0.9559	0.6123	0.141*
F20	0.4352 (12)	0.288 (2)	0.4664 (3)	0.072 (5)
C8	0.4822 (11)	0.589 (3)	0.6908 (4)	0.050 (6)
C9	0.3984 (11)	0.593 (3)	0.6918 (4)	0.089 (12)
H9	0.3703	0.6822	0.6861	0.107*
C10	0.3566 (9)	0.462 (4)	0.7014 (5)	0.120 (16)
H10	0.3005	0.4647	0.7021	0.144*
C11	0.3986 (16)	0.328 (3)	0.7100 (5)	0.121 (16)
H11	0.3706	0.2412	0.7164	0.145*
C12	0.4824 (16)	0.325 (2)	0.7090 (5)	0.101 (14)
H12	0.5105	0.2352	0.7147	0.121*
C13	0.5242 (9)	0.455 (3)	0.6993 (4)	0.056 (6)
C3	0.740 (3)	0.964 (5)	0.6939 (8)	0.066 (10)
H3A	0.7879	0.9850	0.6864	0.079*
F10	0.5189 (14)	1.078 (2)	0.5261 (3)	0.061 (5)
C55	0.7371 (19)	0.100 (3)	0.4441 (5)	0.043 (5)
H55	0.7313	0.0772	0.4289	0.052*
F22	0.6300 (17)	0.458 (3)	0.4903 (5)	0.087 (6)
F1	0.4584 (11)	0.886 (3)	0.7194 (3)	0.064 (5)
F15	0.7331 (16)	0.226 (3)	0.2607 (4)	0.095 (7)
F24	0.7252 (15)	0.578 (2)	0.4731 (3)	0.065 (5)
C22	0.5335 (13)	0.751 (3)	0.5464 (3)	0.034 (5)
C24	0.473 (2)	0.479 (4)	0.5413 (7)	0.050 (7)
H24	0.4590	0.3776	0.5473	0.060*
F14	0.7944 (11)	0.396 (3)	0.2794 (3)	0.065 (5)
C20	0.7294 (18)	0.976 (4)	0.5530 (4)	0.037 (5)
C25	0.4573 (17)	0.514 (4)	0.5194 (6)	0.043 (7)
H25	0.4317	0.4365	0.5104	0.052*
F3	0.5270 (14)	0.714 (3)	0.7384 (4)	0.087 (7)
C51	0.4542 (17)	0.595 (4)	0.4494 (4)	0.046 (5)
H51	0.4041	0.5624	0.4548	0.055*
C27	0.5178 (13)	0.789 (3)	0.5238 (4)	0.035 (5)
C4	0.736 (3)	1.000 (4)	0.7160 (10)	0.070 (12)
H4	0.7804	1.0484	0.7230	0.084*
C1	0.6067 (14)	0.856 (3)	0.6940 (4)	0.034 (5)
C2	0.6770 (16)	0.898 (3)	0.6819 (5)	0.046 (6)
H2	0.6806	0.8818	0.6665	0.056*
C59	0.7301 (16)	0.288 (4)	0.4742 (4)	0.042 (5)
C52	0.5105 (16)	0.484 (3)	0.4466 (6)	0.042 (6)
C28	0.5371 (16)	0.953 (5)	0.5132 (4)	0.044 (6)
C17	0.702 (2)	1.304 (4)	0.5586 (6)	0.060 (7)
H17	0.6921	1.4155	0.5610	0.072*
F13	0.7381 (19)	0.481 (5)	0.2511 (5)	0.113 (11)
C58	0.7689 (19)	0.169 (4)	0.4877 (4)	0.051 (6)
H58	0.7848	0.1970	0.5021	0.061*
F12	0.4961 (19)	0.972 (3)	0.4941 (4)	0.087 (8)
C21	0.7623 (17)	0.798 (4)	0.5490 (5)	0.048 (5)
O1	0.5549 (10)	1.070 (3)	0.6276 (3)	0.053 (5)
C6	0.6008 (17)	0.899 (3)	0.7161 (5)	0.043 (6)
C5	0.666 (2)	0.966 (5)	0.7281 (6)	0.058 (8)
H5	0.6629	0.9856	0.7435	0.070*
C23	0.5108 (16)	0.600 (3)	0.5548 (4)	0.038 (6)
H23	0.5206	0.5765	0.5698	0.046*
C53	0.4904 (12)	0.307 (4)	0.4497 (5)	0.042 (5)
C54	0.7139 (13)	0.251 (3)	0.4519 (4)	0.033 (4)
C16	0.6442 (18)	1.195 (3)	0.5613 (5)	0.048 (5)
H16	0.5929	1.2325	0.5651	0.057*
F18	0.613 (2)	−0.193 (4)	0.3114 (6)	0.141 (10)
C31	0.2326 (19)	0.805 (5)	0.6364 (5)	0.071 (10)
H31A	0.1893	0.8100	0.6473	0.085*
H31B	0.2823	0.7811	0.6444	0.085*
C50	0.466 (2)	0.759 (4)	0.4446 (7)	0.070 (9)
H50	0.4227	0.8310	0.4442	0.084*
C29	0.383 (2)	1.273 (3)	0.6198 (4)	0.066 (8)
H29A	0.3421	1.3097	0.6093	0.079*
H29B	0.4355	1.3050	0.6141	0.079*
C61	0.878 (2)	0.775 (3)	0.3759 (6)	0.082 (10)
H61A	0.9266	0.8054	0.3839	0.098*	0.54 (6)
H61B	0.8323	0.8229	0.3838	0.098*	0.54 (6)
H61C	0.9187	0.8090	0.3653	0.098*	0.46 (6)
H61D	0.8936	0.8132	0.3907	0.098*	0.46 (6)
C60	0.710 (2)	0.445 (5)	0.4848 (5)	0.056 (6)
O8	1.0056 (16)	0.457 (5)	0.3729 (8)	0.095 (12)
H8	1.0489	0.5053	0.3732	0.143*
C48	0.607 (2)	0.691 (4)	0.4366 (5)	0.055 (6)
H48	0.6582	0.7258	0.4325	0.066*
C18	0.778 (2)	1.254 (4)	0.5523 (5)	0.057 (6)
H18	0.8184	1.3310	0.5500	0.069*
F4A	0.655 (2)	0.545 (4)	0.6931 (7)	0.058 (10)	0.63 (4)
C26	0.4804 (17)	0.671 (4)	0.5103 (5)	0.053 (7)
H26	0.4704	0.6946	0.4953	0.064*
C64	1.031 (3)	0.168 (6)	0.3784 (8)	0.095 (13)
H64A	1.0881	0.1516	0.3799	0.142*
H64B	1.0057	0.0674	0.3738	0.142*
H64C	1.0090	0.2031	0.3925	0.142*
C33	0.6411 (15)	0.376 (4)	0.3044 (5)	0.049 (6)
F17	0.611 (2)	−0.125 (6)	0.2805 (6)	0.148 (13)
C49	0.544 (2)	0.816 (4)	0.4402 (7)	0.071 (9)
H49	0.5560	0.9274	0.4396	0.085*
C39	0.727 (2)	0.380 (5)	0.2679 (5)	0.064 (6)
F5A	0.639 (3)	0.372 (6)	0.7175 (6)	0.107 (16)	0.63 (4)
C38	0.6501 (16)	0.412 (3)	0.2812 (5)	0.046 (5)
C19	0.7943 (16)	1.092 (4)	0.5494 (6)	0.052 (6)
H19	0.8456	1.0570	0.5453	0.063*
C34	0.566 (2)	0.415 (4)	0.3137 (7)	0.065 (7)
H34	0.5569	0.3886	0.3286	0.078*
C63	1.016 (2)	0.296 (5)	0.3613 (6)	0.074 (10)
H63A	0.9672	0.2701	0.3529	0.088*
H63B	1.0607	0.3022	0.3509	0.088*
F6A	0.628 (2)	0.303 (4)	0.6829 (7)	0.087 (11)	0.63 (4)
C40	0.7659 (13)	0.096 (3)	0.3084 (4)	0.056 (6)
C45	0.7244 (10)	−0.040 (3)	0.3003 (4)	0.064 (7)
C44	0.7667 (15)	−0.170 (3)	0.2907 (4)	0.088 (10)
H44	0.7390	−0.2608	0.2852	0.105*
C43	0.8504 (15)	−0.163 (3)	0.2892 (5)	0.088 (9)
H43	0.8787	−0.2501	0.2828	0.105*
C42	0.8918 (10)	−0.027 (3)	0.2973 (5)	0.095 (11)
H42	0.9479	−0.0227	0.2963	0.114*
C41	0.8496 (13)	0.103 (3)	0.3069 (4)	0.067 (7)
H41	0.8773	0.1939	0.3124	0.081*
C7	0.5268 (18)	0.867 (4)	0.7305 (4)	0.053 (8)
C14A	0.611 (2)	0.416 (4)	0.6979 (5)	0.048 (7)	0.63 (4)
C30	0.369 (4)	1.349 (6)	0.6423 (6)	0.106 (17)
H30A	0.3557	1.2649	0.6530	0.158*
H30B	0.3258	1.4269	0.6414	0.158*
H30C	0.4175	1.4044	0.6471	0.158*
C56	0.7690 (19)	−0.020 (4)	0.4581 (7)	0.047 (6)
H56	0.7803	−0.1237	0.4524	0.056*
C32	0.216 (2)	0.666 (5)	0.6201 (7)	0.083 (11)
H32A	0.1627	0.6803	0.6138	0.125*
H32B	0.2180	0.5628	0.6279	0.125*
H32C	0.2551	0.6675	0.6084	0.125*
C37	0.588 (3)	0.492 (4)	0.2707 (8)	0.060 (8)
H37	0.5964	0.5310	0.2563	0.072*
C62A	0.881 (4)	0.845 (8)	0.3523 (8)	0.09 (3)	0.54 (6)
H62A	0.9361	0.8477	0.3472	0.135*	0.54 (6)
H62B	0.8594	0.9546	0.3523	0.135*	0.54 (6)
H62C	0.8498	0.7770	0.3424	0.135*	0.54 (6)
C36	0.513 (2)	0.517 (5)	0.2805 (9)	0.063 (8)
H36	0.4692	0.5505	0.2719	0.075*
C57	0.784 (2)	0.011 (4)	0.4800 (6)	0.054 (7)
H57	0.8033	−0.0704	0.4895	0.064*
C35	0.506 (2)	0.491 (4)	0.3020 (7)	0.056 (7)
H35	0.4589	0.5249	0.3094	0.068*
C47	0.5932 (19)	0.532 (4)	0.4390 (5)	0.041 (5)
C46	0.632 (3)	−0.055 (5)	0.2990 (8)	0.077 (8)
F6B	0.644 (3)	0.546 (7)	0.7198 (6)	0.069 (15)	0.37 (4)
C14B	0.613 (3)	0.452 (5)	0.7035 (7)	0.049 (10)	0.37 (4)
F4B	0.653 (4)	0.504 (6)	0.6856 (6)	0.045 (11)	0.37 (4)
F5B	0.648 (4)	0.305 (5)	0.7060 (13)	0.10 (3)	0.37 (4)
C62B	0.795 (4)	0.848 (9)	0.3695 (18)	0.12 (2)	0.46 (6)
H62D	0.7805	0.8108	0.3548	0.176*	0.46 (6)
H62E	0.7989	0.9663	0.3695	0.176*	0.46 (6)
H62F	0.7554	0.8139	0.3801	0.176*	0.46 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.0227 (4)	0.0540 (4)	0.0278 (3)	0.0057 (3)	0.0006 (3)	−0.0059 (4)
U2	0.0200 (4)	0.0541 (5)	0.0350 (4)	−0.0039 (3)	−0.0019 (3)	0.0038 (5)
S4	0.027 (2)	0.048 (3)	0.027 (2)	0.007 (2)	−0.001 (2)	0.005 (2)
P2	0.018 (2)	0.045 (3)	0.028 (2)	0.000 (2)	−0.002 (2)	−0.002 (2)
S8	0.028 (2)	0.049 (3)	0.029 (2)	−0.008 (2)	−0.001 (2)	−0.001 (2)
S7	0.028 (3)	0.067 (4)	0.049 (4)	−0.005 (3)	−0.012 (3)	0.011 (4)
P4	0.023 (3)	0.043 (3)	0.030 (3)	−0.002 (2)	−0.003 (2)	−0.003 (2)
S3	0.041 (3)	0.060 (4)	0.023 (3)	0.030 (3)	0.002 (3)	0.006 (3)
P1	0.035 (3)	0.076 (5)	0.029 (3)	0.026 (3)	0.005 (2)	−0.001 (3)
S2	0.050 (4)	0.090 (5)	0.033 (3)	0.033 (4)	0.007 (3)	−0.006 (3)
S5	0.061 (5)	0.137 (8)	0.033 (3)	−0.064 (6)	0.010 (4)	−0.011 (5)
P3	0.034 (3)	0.074 (5)	0.039 (3)	−0.018 (3)	0.003 (3)	−0.006 (3)
S6	0.057 (4)	0.111 (7)	0.046 (3)	−0.053 (5)	0.016 (3)	−0.005 (4)
S1	0.048 (4)	0.124 (8)	0.036 (4)	0.041 (5)	0.001 (3)	−0.005 (5)
F23	0.136 (19)	0.080 (13)	0.040 (9)	0.023 (15)	−0.017 (12)	−0.013 (9)
C15	0.039 (8)	0.038 (8)	0.017 (8)	−0.008 (7)	−0.010 (8)	0.013 (7)
O7	0.020 (7)	0.059 (9)	0.055 (9)	−0.022 (7)	0.004 (8)	0.007 (10)
F7	0.057 (10)	0.085 (12)	0.070 (9)	0.021 (10)	−0.005 (8)	0.019 (10)
F9	0.024 (6)	0.056 (9)	0.090 (11)	0.004 (6)	0.005 (7)	−0.005 (9)
O3	0.041 (9)	0.046 (8)	0.061 (10)	0.023 (7)	0.004 (10)	0.002 (9)
F11	0.038 (9)	0.106 (14)	0.065 (12)	−0.014 (10)	0.012 (8)	0.030 (12)
F8	0.035 (7)	0.081 (12)	0.068 (8)	0.012 (8)	0.020 (7)	0.015 (9)
F19	0.045 (9)	0.064 (10)	0.083 (10)	−0.017 (8)	−0.007 (8)	−0.027 (10)
O6	0.012 (7)	0.100 (16)	0.084 (15)	0.022 (9)	−0.002 (8)	0.012 (14)
O2	0.027 (7)	0.041 (8)	0.052 (10)	0.008 (7)	−0.006 (7)	−0.009 (8)
F2	0.064 (14)	0.16 (2)	0.051 (12)	−0.009 (16)	0.026 (11)	−0.052 (14)
F21	0.033 (7)	0.054 (9)	0.083 (11)	0.000 (6)	0.007 (7)	0.024 (9)
F16	0.049 (11)	0.098 (14)	0.23 (4)	−0.001 (12)	−0.006 (18)	−0.082 (19)
O5	0.034 (5)	0.039 (5)	0.039 (5)	−0.002 (2)	−0.003 (2)	0.003 (2)
O4	0.040 (13)	0.12 (2)	0.12 (3)	0.011 (16)	0.00 (2)	0.02 (3)
F20	0.056 (10)	0.075 (12)	0.084 (10)	−0.009 (9)	0.035 (9)	−0.009 (10)
C8	0.028 (10)	0.078 (17)	0.045 (16)	0.008 (10)	0.010 (11)	−0.014 (12)
C9	0.025 (10)	0.20 (4)	0.047 (15)	0.003 (15)	0.004 (13)	0.02 (2)
C10	0.033 (15)	0.17 (4)	0.16 (5)	−0.043 (15)	0.02 (2)	−0.05 (3)
C11	0.088 (19)	0.09 (2)	0.18 (5)	−0.064 (19)	0.06 (3)	−0.05 (2)
C12	0.087 (17)	0.058 (19)	0.16 (4)	−0.026 (16)	0.04 (3)	−0.01 (2)
C13	0.039 (8)	0.062 (14)	0.067 (19)	−0.014 (8)	0.009 (10)	−0.006 (14)
C3	0.06 (2)	0.058 (17)	0.08 (2)	−0.021 (17)	0.02 (2)	0.001 (19)
F10	0.071 (12)	0.061 (11)	0.051 (10)	−0.001 (9)	−0.003 (10)	0.006 (8)
C55	0.043 (13)	0.036 (10)	0.050 (12)	−0.019 (10)	−0.004 (12)	0.008 (8)
F22	0.081 (12)	0.100 (15)	0.081 (15)	0.026 (12)	0.031 (11)	−0.008 (14)
F1	0.046 (10)	0.107 (15)	0.040 (8)	−0.004 (10)	0.008 (8)	−0.009 (9)
F15	0.086 (15)	0.119 (14)	0.080 (12)	0.029 (13)	−0.003 (12)	−0.055 (11)
F24	0.088 (15)	0.055 (9)	0.052 (9)	0.000 (9)	−0.010 (10)	−0.005 (7)
C22	0.023 (9)	0.046 (12)	0.032 (10)	−0.006 (10)	0.012 (8)	−0.008 (10)
C24	0.033 (14)	0.049 (15)	0.067 (19)	−0.021 (12)	−0.003 (15)	−0.002 (15)
F14	0.038 (8)	0.103 (14)	0.054 (9)	−0.005 (9)	0.013 (7)	0.000 (9)
C20	0.038 (12)	0.053 (8)	0.019 (11)	−0.013 (7)	−0.001 (10)	0.014 (8)
C25	0.020 (11)	0.063 (17)	0.047 (15)	0.004 (11)	−0.003 (11)	−0.023 (13)
F3	0.069 (13)	0.109 (17)	0.084 (13)	−0.011 (13)	0.018 (11)	0.040 (13)
C51	0.033 (11)	0.063 (11)	0.042 (12)	0.020 (9)	−0.016 (10)	−0.004 (12)
C27	0.018 (9)	0.046 (13)	0.039 (11)	0.002 (9)	−0.003 (9)	−0.003 (10)
C4	0.049 (19)	0.05 (2)	0.11 (4)	0.007 (14)	−0.01 (2)	−0.012 (18)
C1	0.027 (10)	0.029 (10)	0.047 (12)	0.008 (9)	0.018 (10)	0.004 (10)
C2	0.036 (13)	0.048 (14)	0.055 (14)	0.000 (11)	0.012 (12)	0.011 (13)
C59	0.039 (13)	0.059 (10)	0.030 (9)	0.008 (10)	−0.002 (9)	0.010 (8)
C52	0.020 (10)	0.046 (8)	0.059 (18)	0.003 (7)	−0.017 (10)	−0.008 (10)
C28	0.030 (11)	0.09 (2)	0.017 (10)	−0.016 (14)	−0.005 (9)	−0.002 (12)
C17	0.060 (14)	0.037 (11)	0.08 (2)	−0.013 (9)	−0.008 (15)	0.029 (14)
F13	0.078 (16)	0.18 (2)	0.083 (17)	0.052 (18)	0.032 (12)	0.053 (18)
C58	0.055 (16)	0.065 (13)	0.033 (11)	0.006 (14)	−0.001 (11)	0.014 (10)
F12	0.116 (19)	0.098 (15)	0.047 (11)	−0.029 (15)	−0.058 (13)	0.022 (11)
C21	0.042 (13)	0.058 (10)	0.043 (11)	−0.010 (8)	0.012 (8)	0.006 (11)
O1	0.020 (7)	0.077 (12)	0.061 (11)	0.004 (8)	−0.020 (8)	−0.031 (10)
C6	0.039 (13)	0.043 (13)	0.048 (13)	0.003 (11)	0.013 (12)	0.004 (11)
C5	0.049 (17)	0.08 (2)	0.043 (15)	−0.008 (17)	−0.015 (13)	0.004 (16)
C23	0.030 (11)	0.047 (13)	0.037 (12)	−0.020 (11)	−0.015 (11)	0.013 (10)
C53	0.012 (9)	0.052 (9)	0.062 (13)	−0.001 (7)	0.008 (8)	−0.016 (11)
C54	0.025 (9)	0.035 (9)	0.041 (9)	−0.013 (8)	−0.009 (8)	0.011 (8)
C16	0.048 (11)	0.034 (10)	0.062 (15)	−0.010 (8)	−0.020 (12)	0.017 (11)
F18	0.116 (17)	0.120 (15)	0.189 (19)	−0.026 (14)	0.027 (17)	0.023 (16)
C31	0.034 (14)	0.12 (3)	0.056 (15)	−0.004 (19)	0.002 (14)	0.01 (2)
C50	0.063 (13)	0.053 (11)	0.10 (3)	0.025 (13)	−0.018 (19)	−0.021 (17)
C29	0.09 (2)	0.060 (12)	0.048 (12)	0.010 (16)	−0.016 (16)	0.021 (13)
C61	0.078 (19)	0.066 (14)	0.10 (2)	−0.019 (18)	−0.01 (2)	0.04 (2)
C60	0.063 (14)	0.062 (12)	0.044 (13)	0.011 (15)	0.000 (12)	0.003 (10)
O8	0.021 (9)	0.12 (3)	0.15 (3)	−0.003 (14)	−0.018 (17)	−0.02 (2)
C48	0.064 (14)	0.046 (11)	0.056 (15)	0.002 (10)	0.015 (14)	0.008 (13)
C18	0.057 (12)	0.060 (11)	0.054 (16)	−0.020 (12)	−0.012 (14)	0.017 (15)
F4A	0.024 (10)	0.050 (14)	0.10 (3)	0.001 (12)	−0.018 (19)	0.015 (15)
C26	0.041 (14)	0.069 (19)	0.049 (14)	0.000 (14)	−0.004 (12)	−0.017 (14)
C64	0.08 (2)	0.10 (3)	0.11 (3)	−0.01 (2)	0.01 (3)	0.04 (3)
C33	0.029 (10)	0.067 (17)	0.051 (10)	−0.014 (10)	−0.001 (9)	−0.029 (12)
F17	0.09 (2)	0.23 (4)	0.125 (16)	0.01 (2)	−0.023 (19)	−0.083 (18)
C49	0.075 (16)	0.032 (12)	0.11 (3)	0.008 (10)	−0.03 (2)	−0.014 (16)
C39	0.062 (13)	0.096 (16)	0.035 (12)	0.011 (17)	0.003 (9)	−0.015 (11)
F5A	0.10 (3)	0.15 (4)	0.076 (17)	0.01 (3)	−0.02 (2)	0.050 (19)
C38	0.033 (9)	0.051 (14)	0.055 (11)	−0.012 (9)	−0.007 (8)	−0.024 (11)
C19	0.024 (10)	0.060 (11)	0.072 (18)	−0.011 (9)	−0.013 (11)	0.027 (14)
C34	0.048 (15)	0.07 (2)	0.079 (16)	0.000 (14)	0.017 (12)	−0.020 (16)
C63	0.057 (19)	0.09 (3)	0.07 (2)	−0.01 (2)	0.000 (18)	0.02 (2)
F6A	0.087 (18)	0.063 (15)	0.111 (19)	0.015 (13)	0.010 (16)	−0.025 (14)
C40	0.044 (11)	0.080 (17)	0.045 (15)	0.003 (11)	−0.013 (11)	0.029 (12)
C45	0.061 (10)	0.065 (15)	0.07 (2)	0.018 (9)	−0.007 (13)	0.014 (14)
C44	0.080 (14)	0.09 (2)	0.09 (3)	0.019 (15)	0.03 (2)	0.00 (2)
C43	0.072 (15)	0.085 (19)	0.11 (3)	0.031 (15)	0.00 (2)	0.027 (18)
C42	0.084 (13)	0.105 (14)	0.095 (16)	0.021 (10)	0.001 (12)	0.004 (11)
C41	0.044 (12)	0.087 (17)	0.070 (19)	0.012 (12)	0.008 (14)	0.033 (14)
C7	0.050 (16)	0.08 (2)	0.032 (11)	−0.035 (16)	0.010 (12)	−0.002 (13)
C14A	0.055 (13)	0.035 (17)	0.053 (18)	0.013 (12)	0.007 (19)	0.012 (15)
C30	0.16 (5)	0.08 (2)	0.07 (2)	0.00 (3)	−0.01 (3)	−0.020 (19)
C56	0.032 (14)	0.041 (12)	0.067 (15)	0.004 (11)	−0.004 (14)	0.004 (11)
C32	0.047 (17)	0.10 (2)	0.10 (3)	0.030 (19)	0.00 (2)	0.00 (3)
C37	0.055 (15)	0.056 (19)	0.068 (17)	0.008 (13)	0.008 (12)	−0.005 (14)
C62A	0.08 (5)	0.09 (4)	0.10 (3)	−0.03 (4)	−0.06 (4)	0.05 (4)
C36	0.034 (13)	0.07 (2)	0.085 (17)	−0.006 (13)	0.000 (15)	−0.028 (16)
C57	0.043 (17)	0.068 (14)	0.050 (12)	0.016 (13)	0.014 (14)	0.015 (12)
C35	0.024 (11)	0.057 (18)	0.088 (17)	−0.023 (10)	0.008 (12)	−0.029 (15)
C47	0.042 (11)	0.045 (9)	0.038 (13)	0.006 (10)	0.002 (11)	0.012 (12)
C46	0.062 (12)	0.074 (18)	0.10 (2)	−0.008 (14)	0.01 (2)	−0.027 (14)
F6B	0.07 (3)	0.10 (4)	0.041 (16)	0.01 (3)	−0.03 (2)	0.01 (2)
C14B	0.054 (16)	0.04 (3)	0.05 (2)	0.00 (2)	−0.02 (3)	0.02 (3)
F4B	0.027 (14)	0.06 (2)	0.051 (16)	−0.012 (18)	−0.013 (15)	0.000 (15)
F5B	0.07 (2)	0.04 (2)	0.21 (8)	0.00 (2)	0.03 (5)	0.05 (3)
C62B	0.11 (3)	0.11 (3)	0.13 (4)	0.04 (2)	−0.01 (2)	0.01 (2)

Geometric parameters (Å, º)

U1—S4	2.875 (5)	C59—C58	1.41 (4)
U1—S3	2.858 (7)	C59—C54	1.39 (3)
U1—S2	2.862 (8)	C59—C60	1.46 (5)
U1—S1	2.854 (8)	C52—C53	1.49 (4)
U1—O3	2.342 (13)	C52—C47	1.49 (4)
U1—O2	1.782 (17)	C28—F12	1.34 (3)
U1—O1	1.701 (18)	C17—H17	0.9300
U2—S8	2.887 (6)	C17—C16	1.32 (4)
U2—S7	2.822 (9)	C17—C18	1.37 (5)
U2—S5	2.859 (8)	F13—C39	1.31 (5)
U2—S6	2.850 (8)	C58—H58	0.9300
U2—O7	2.376 (13)	C58—C57	1.38 (5)
U2—O6	1.704 (19)	C6—C5	1.41 (5)
U2—O5	1.773 (18)	C6—C7	1.52 (4)
S4—P2	2.021 (8)	C5—H5	0.9300
P2—S3	2.005 (9)	C23—H23	0.9300
P2—C15	1.82 (3)	C16—H16	0.9300
P2—C22	1.86 (2)	F18—C46	1.38 (5)
S8—P4	2.018 (8)	C31—H31A	0.9700
S7—P4	1.998 (10)	C31—H31B	0.9700
P4—C54	1.85 (2)	C31—C32	1.51 (5)
P4—C47	1.83 (3)	C50—H50	0.9300
P1—S2	2.003 (9)	C50—C49	1.40 (6)
P1—S1	2.011 (11)	C29—H29A	0.9700
P1—C8	1.865 (19)	C29—H29B	0.9700
P1—C1	1.84 (3)	C29—C30	1.50 (2)
S5—P3	2.008 (11)	C61—H61A	0.9700
P3—S6	2.017 (10)	C61—H61B	0.9700
P3—C33	1.85 (3)	C61—H61C	0.9700
P3—C40	1.86 (2)	C61—H61D	0.9700
F23—C60	1.36 (4)	C61—C62A	1.523 (18)
C15—C20	1.31 (4)	C61—C62B	1.54 (3)
C15—C16	1.43 (4)	O8—H8	0.8200
O7—H7	0.8200	O8—C63	1.48 (5)
O7—C61	1.43 (2)	C48—H48	0.9300
F7—C21	1.28 (3)	C48—C49	1.46 (5)
F9—C21	1.37 (3)	C48—C47	1.32 (4)
O3—H3	0.8200	C18—H18	0.9300
O3—C29	1.48 (2)	C18—C19	1.35 (5)
F11—C28	1.30 (3)	F4A—C14A	1.31 (3)
F8—C21	1.31 (3)	C26—H26	0.9300
F19—C53	1.36 (3)	C64—H64A	0.9600
F2—C7	1.35 (4)	C64—H64B	0.9600
F21—C53	1.34 (3)	C64—H64C	0.9600
F16—C46	1.21 (5)	C64—C63	1.48 (5)
O4—H4A	0.8200	C33—C38	1.42 (4)
O4—C31	1.46 (5)	C33—C34	1.39 (4)
F20—C53	1.36 (3)	F17—C46	1.30 (5)
C8—C9	1.3900	C49—H49	0.9300
C8—C13	1.3900	C39—C38	1.52 (4)
C9—H9	0.9300	F5A—C14A	1.31 (3)
C9—C10	1.3900	C38—C37	1.37 (5)
C10—H10	0.9300	C19—H19	0.9300
C10—C11	1.3900	C34—H34	0.9300
C11—H11	0.9300	C34—C35	1.37 (5)
C11—C12	1.3900	C63—H63A	0.9700
C12—H12	0.9300	C63—H63B	0.9700
C12—C13	1.3900	F6A—C14A	1.31 (3)
C13—C14A	1.47 (4)	C40—C45	1.3900
C13—C14B	1.50 (4)	C40—C41	1.3900
C3—H3A	0.9300	C45—C44	1.3900
C3—C4	1.35 (7)	C45—C46	1.54 (5)
C3—C2	1.37 (5)	C44—H44	0.9300
F10—C28	1.31 (4)	C44—C43	1.3900
C55—H55	0.9300	C43—H43	0.9300
C55—C54	1.37 (4)	C43—C42	1.3900
C55—C56	1.39 (4)	C42—H42	0.9300
F22—C60	1.36 (5)	C42—C41	1.3900
F1—C7	1.32 (4)	C41—H41	0.9300
F15—C39	1.33 (4)	C30—H30A	0.9600
F24—C60	1.32 (4)	C30—H30B	0.9600
C22—C27	1.41 (3)	C30—H30C	0.9600
C22—C23	1.38 (3)	C56—H56	0.9300
C24—H24	0.9300	C56—C57	1.35 (5)
C24—C25	1.36 (5)	C32—H32A	0.9600
C24—C23	1.42 (4)	C32—H32B	0.9600
F14—C39	1.32 (4)	C32—H32C	0.9600
C20—C21	1.57 (4)	C37—H37	0.9300
C20—C19	1.45 (4)	C37—C36	1.38 (6)
C25—H25	0.9300	C62A—H62A	0.9600
C25—C26	1.44 (5)	C62A—H62B	0.9600
F3—C7	1.33 (4)	C62A—H62C	0.9600
C51—H51	0.9300	C36—H36	0.9300
C51—C52	1.31 (4)	C36—C35	1.31 (7)
C51—C50	1.37 (5)	C57—H57	0.9300
C27—C28	1.51 (4)	C35—H35	0.9300
C27—C26	1.40 (4)	F6B—C14B	1.34 (3)
C4—H4	0.9300	C14B—F4B	1.33 (3)
C4—C5	1.40 (6)	C14B—F5B	1.33 (3)
C1—C2	1.41 (3)	C62B—H62D	0.9600
C1—C6	1.37 (4)	C62B—H62E	0.9600
C2—H2	0.9300	C62B—H62F	0.9600
S3—U1—S4	70.60 (17)	F21—C53—F19	105 (2)
S3—U1—S2	140.11 (18)	F21—C53—F20	105 (2)
S2—U1—S4	69.87 (16)	F21—C53—C52	118 (2)
S1—U1—S4	138.98 (19)	F20—C53—F19	102.4 (19)
S1—U1—S3	150.0 (2)	F20—C53—C52	110 (2)
S1—U1—S2	69.9 (2)	C55—C54—P4	115.3 (18)
O3—U1—S4	145.4 (6)	C55—C54—C59	118 (2)
O3—U1—S3	74.8 (6)	C59—C54—P4	126 (2)
O3—U1—S2	144.5 (6)	C15—C16—H16	118.4
O3—U1—S1	75.5 (6)	C17—C16—C15	123 (3)
O2—U1—S4	92.9 (5)	C17—C16—H16	118.4
O2—U1—S3	88.8 (6)	O4—C31—H31A	109.1
O2—U1—S2	88.0 (6)	O4—C31—H31B	109.1
O2—U1—S1	93.4 (6)	O4—C31—C32	113 (3)
O2—U1—O3	86.0 (7)	H31A—C31—H31B	107.8
O1—U1—S4	89.1 (6)	C32—C31—H31A	109.1
O1—U1—S3	90.6 (8)	C32—C31—H31B	109.1
O1—U1—S2	93.9 (7)	C51—C50—H50	120.2
O1—U1—S1	85.9 (8)	C51—C50—C49	120 (3)
O1—U1—O3	91.5 (8)	C49—C50—H50	120.2
O1—U1—O2	177.5 (8)	O3—C29—H29A	110.0
S7—U2—S8	70.21 (19)	O3—C29—H29B	110.0
S7—U2—S5	149.8 (2)	O3—C29—C30	109 (3)
S7—U2—S6	139.7 (2)	H29A—C29—H29B	108.3
S5—U2—S8	138.77 (19)	C30—C29—H29A	110.0
S6—U2—S8	69.51 (17)	C30—C29—H29B	110.0
S6—U2—S5	70.2 (2)	O7—C61—H61A	109.2
O7—U2—S8	146.0 (5)	O7—C61—H61B	109.2
O7—U2—S7	75.8 (5)	O7—C61—H61C	110.2
O7—U2—S5	74.9 (5)	O7—C61—H61D	110.2
O7—U2—S6	144.4 (5)	O7—C61—C62A	112 (3)
O6—U2—S8	94.9 (7)	O7—C61—C62B	108 (3)
O6—U2—S7	91.3 (8)	H61A—C61—H61B	107.9
O6—U2—S5	93.5 (8)	H61C—C61—H61D	108.5
O6—U2—S6	90.1 (8)	C62A—C61—H61A	109.2
O6—U2—O7	85.0 (9)	C62A—C61—H61B	109.2
O6—U2—O5	176.7 (10)	C62B—C61—H61C	110.2
O5—U2—S8	87.8 (6)	C62B—C61—H61D	110.2
O5—U2—S7	87.9 (5)	F23—C60—C59	114 (3)
O5—U2—S5	85.6 (6)	F22—C60—F23	100 (3)
O5—U2—S6	92.6 (6)	F22—C60—C59	114 (3)
O5—U2—O7	91.7 (7)	F24—C60—F23	106 (3)
P2—S4—U1	88.9 (2)	F24—C60—F22	105 (3)
S3—P2—S4	110.7 (4)	F24—C60—C59	117 (3)
C15—P2—S4	106.2 (8)	C63—O8—H8	109.5
C15—P2—S3	113.4 (10)	C49—C48—H48	118.6
C15—P2—C22	113.7 (11)	C47—C48—H48	118.6
C22—P2—S4	109.2 (9)	C47—C48—C49	123 (3)
C22—P2—S3	103.7 (8)	C17—C18—H18	119.6
P4—S8—U2	88.9 (3)	C19—C18—C17	121 (3)
P4—S7—U2	91.2 (3)	C19—C18—H18	119.6
S7—P4—S8	109.7 (4)	C25—C26—H26	119.8
C54—P4—S8	109.5 (8)	C27—C26—C25	120 (3)
C54—P4—S7	105.8 (7)	C27—C26—H26	119.8
C47—P4—S8	106.2 (11)	H64A—C64—H64B	109.5
C47—P4—S7	109.4 (11)	H64A—C64—H64C	109.5
C47—P4—C54	116.2 (12)	H64B—C64—H64C	109.5
P2—S3—U1	89.7 (3)	C63—C64—H64A	109.5
S2—P1—S1	109.4 (4)	C63—C64—H64B	109.5
C8—P1—S2	108.0 (8)	C63—C64—H64C	109.5
C8—P1—S1	109.7 (8)	C38—C33—P3	126 (2)
C1—P1—S2	111.2 (8)	C34—C33—P3	119 (3)
C1—P1—S1	110.4 (8)	C34—C33—C38	116 (3)
C1—P1—C8	108.2 (10)	C50—C49—C48	117 (3)
P1—S2—U1	90.1 (3)	C50—C49—H49	121.5
P3—S5—U2	90.2 (3)	C48—C49—H49	121.5
S5—P3—S6	109.3 (4)	F15—C39—C38	113 (3)
C33—P3—S5	106.5 (10)	F14—C39—F15	101 (3)
C33—P3—S6	109.5 (10)	F14—C39—C38	115 (2)
C33—P3—C40	112.1 (11)	F13—C39—F15	109 (3)
C40—P3—S5	111.9 (9)	F13—C39—F14	102 (3)
C40—P3—S6	107.6 (9)	F13—C39—C38	115 (3)
P3—S6—U2	90.3 (3)	C33—C38—C39	124 (3)
P1—S1—U1	90.1 (3)	C37—C38—C33	118 (3)
C20—C15—P2	129 (2)	C37—C38—C39	118 (3)
C20—C15—C16	116 (3)	C20—C19—H19	121.2
C16—C15—P2	114 (2)	C18—C19—C20	118 (3)
U2—O7—H7	113.6	C18—C19—H19	121.2
C61—O7—U2	133.7 (17)	C33—C34—H34	118.2
C61—O7—H7	109.5	C35—C34—C33	124 (4)
U1—O3—H3	124.8	C35—C34—H34	118.2
C29—O3—U1	125.7 (16)	O8—C63—H63A	110.0
C29—O3—H3	109.5	O8—C63—H63B	110.0
C31—O4—H4A	109.5	C64—C63—O8	108 (4)
C9—C8—P1	115.2 (13)	C64—C63—H63A	110.0
C9—C8—C13	120.0	C64—C63—H63B	110.0
C13—C8—P1	124.6 (13)	H63A—C63—H63B	108.4
C8—C9—H9	120.0	C45—C40—P3	124.8 (13)
C10—C9—C8	120.0	C45—C40—C41	120.0
C10—C9—H9	120.0	C41—C40—P3	115.2 (13)
C9—C10—H10	120.0	C40—C45—C46	125 (2)
C9—C10—C11	120.0	C44—C45—C40	120.0
C11—C10—H10	120.0	C44—C45—C46	115 (2)
C10—C11—H11	120.0	C45—C44—H44	120.0
C12—C11—C10	120.00 (6)	C45—C44—C43	120.0
C12—C11—H11	120.0	C43—C44—H44	120.0
C11—C12—H12	120.0	C44—C43—H43	120.0
C11—C12—C13	120.0	C44—C43—C42	120.0
C13—C12—H12	120.0	C42—C43—H43	120.0
C8—C13—C14A	129.5 (18)	C43—C42—H42	120.0
C8—C13—C14B	125 (2)	C41—C42—C43	120.0
C12—C13—C8	120.0	C41—C42—H42	120.0
C12—C13—C14A	110.1 (18)	C40—C41—H41	120.0
C12—C13—C14B	114 (2)	C42—C41—C40	120.0
C4—C3—H3A	117.9	C42—C41—H41	120.0
C4—C3—C2	124 (4)	F2—C7—C6	110 (2)
C2—C3—H3A	117.9	F1—C7—F2	109 (3)
C54—C55—H55	118.9	F1—C7—F3	107 (2)
C54—C55—C56	122 (3)	F1—C7—C6	113 (2)
C56—C55—H55	118.9	F3—C7—F2	107 (3)
C27—C22—P2	126 (2)	F3—C7—C6	111 (3)
C23—C22—P2	113.6 (17)	F4A—C14A—C13	112 (3)
C23—C22—C27	120 (2)	F4A—C14A—F5A	102 (3)
C25—C24—H24	120.4	F4A—C14A—F6A	107 (3)
C25—C24—C23	119 (3)	F5A—C14A—C13	111 (3)
C23—C24—H24	120.4	F6A—C14A—C13	114 (3)
C15—C20—C21	128 (3)	F6A—C14A—F5A	110 (4)
C15—C20—C19	123 (3)	C29—C30—H30A	109.5
C19—C20—C21	109 (2)	C29—C30—H30B	109.5
C24—C25—H25	120.2	C29—C30—H30C	109.5
C24—C25—C26	120 (3)	H30A—C30—H30B	109.5
C26—C25—H25	120.2	H30A—C30—H30C	109.5
C52—C51—H51	118.7	H30B—C30—H30C	109.5
C52—C51—C50	123 (3)	C55—C56—H56	119.4
C50—C51—H51	118.7	C57—C56—C55	121 (3)
C22—C27—C28	124 (2)	C57—C56—H56	119.4
C26—C27—C22	119 (3)	C31—C32—H32A	109.5
C26—C27—C28	117 (2)	C31—C32—H32B	109.5
C3—C4—H4	120.0	C31—C32—H32C	109.5
C3—C4—C5	120 (4)	H32A—C32—H32B	109.5
C5—C4—H4	120.0	H32A—C32—H32C	109.5
C2—C1—P1	111 (2)	H32B—C32—H32C	109.5
C6—C1—P1	129.0 (19)	C38—C37—H37	118.3
C6—C1—C2	119 (3)	C38—C37—C36	123 (4)
C3—C2—C1	117 (3)	C36—C37—H37	118.3
C3—C2—H2	121.5	C61—C62A—H62A	109.5
C1—C2—H2	121.5	C61—C62A—H62B	109.5
C58—C59—C60	117 (2)	C61—C62A—H62C	109.5
C54—C59—C58	119 (3)	H62A—C62A—H62B	109.5
C54—C59—C60	124 (2)	H62A—C62A—H62C	109.5
C51—C52—C53	120 (3)	H62B—C62A—H62C	109.5
C51—C52—C47	121 (3)	C37—C36—H36	120.8
C53—C52—C47	120 (2)	C35—C36—C37	118 (4)
F11—C28—F10	106 (3)	C35—C36—H36	120.8
F11—C28—C27	110 (3)	C58—C57—H57	121.3
F11—C28—F12	111 (2)	C56—C57—C58	117 (3)
F10—C28—C27	113 (2)	C56—C57—H57	121.3
F10—C28—F12	107 (3)	C34—C35—H35	119.9
F12—C28—C27	110 (2)	C36—C35—C34	120 (4)
C16—C17—H17	120.1	C36—C35—H35	119.9
C16—C17—C18	120 (3)	C52—C47—P4	128 (2)
C18—C17—H17	120.1	C48—C47—P4	116 (2)
C59—C58—H58	119.0	C48—C47—C52	116 (3)
C57—C58—C59	122 (3)	F16—C46—F18	105 (4)
C57—C58—H58	119.0	F16—C46—F17	119 (4)
F7—C21—F9	106 (2)	F16—C46—C45	120 (3)
F7—C21—F8	113 (3)	F18—C46—C45	105 (4)
F7—C21—C20	112 (2)	F17—C46—F18	92 (4)
F9—C21—C20	106 (2)	F17—C46—C45	110 (3)
F8—C21—F9	107 (2)	F6B—C14B—C13	119 (4)
F8—C21—C20	113 (2)	F4B—C14B—C13	111 (4)
C1—C6—C5	122 (3)	F4B—C14B—F6B	103 (3)
C1—C6—C7	124 (3)	F4B—C14B—F5B	99 (3)
C5—C6—C7	113 (3)	F5B—C14B—C13	117 (5)
C4—C5—C6	117 (4)	F5B—C14B—F6B	106 (4)
C4—C5—H5	121.6	C61—C62B—H62D	109.5
C6—C5—H5	121.6	C61—C62B—H62E	109.5
C22—C23—C24	122 (2)	C61—C62B—H62F	109.5
C22—C23—H23	119.0	H62D—C62B—H62E	109.5
C24—C23—H23	119.0	H62D—C62B—H62F	109.5
F19—C53—C52	114 (3)	H62E—C62B—H62F	109.5