Bis{bis­[5-tert-butyl-2-oxido-3-(1-pyridinio­methyl)­phenyl]­methane}­dioxouranium bis­(tri­fluoro­methane­sulfonate) pyridine disolvate: a uranyl bis­(diphenoxide) complex resulting from homooxacalixarene cleavage

The title compound, [UO₂(C₃₃H₃₈N₂O₂)₂](CF₃SO₃)₂·2C₅H₅N, has been obtained by reaction of U^IV tri­fluoro­methane­sulfonate with p-tert-butyl­tetrahomodioxacalix­[4]­arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square-planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety.

S1. Comment

In their polyphenoxide form, homooxacalixarenes (Masci, 2001), as well as the more widespread calixarenes, are ligands well suited to uranyl ion [dioxouranium(VI)] complexation (Thuéry et al., 2001). In order to extend the investigation of uranium complexes of homooxacalixarenes to lower oxidation states of this cation, we have recently studied the reaction of UCl₄ with p-tert-butyltetrahomodioxacalix[4]arene, p-tert-butylhexahomotrioxacalix[6]arene and p-tert-butyloctahomotetraoxacalix[8]arene in pyridine, with the unexpected result of homooxacalixarene cleavage to give the diphenoxide species bis[5-tert-butyl-2-oxido-3-(1-pyridiniomethyl)-phenyl]methane (L), and subsequent isolation of the 1:1 or 1:2 U^IV/L complexes (Salmon et al., 2003). The proposed mechanism involves nucleophilic attack of pyridine on the ether bridges, likely assisted by initial U coordination to the ether O atoms. In the course of a similar study with U(OSO₂CF₃)₄ and p-tert-butyltetrahomodioxacalix[4]arene as starting materials, further oxidation of the metal centre, due either to oxygen contamination or the presence of water released by the cleavage reaction, resulted in the isolation of the present uranyl complex, (I), and its structure is presented here. \sch

The asymmetric unit in (I) contains half a complex molecule, with the U atom located on a centre of symmetry, and a trifluoromethanesulfonate counterion and a pyridine solvent molecule. The U atom is bound (Fig. 1, Table 1) to two phenoxide O atoms from each neutral doubly zwitterionic ligand, with a mean U—O bond length of 2.256 (6) Å, typical of such phenoxide complexes (Thuéry et al., 2001). The O(phenoxide)-U—O(phenoxide) and O(oxo)-U—O(phenoxide) angles are close to 90° [87.85 (14)–92.15 (14)°], and the equatorial environment of the uranyl ion is thus a rather regular square.

We have previously reported the crystal structure of the 1:2 uranyl complex of another diphenoxide species, in which the cationic pyridiniomethyl groups present in L are replaced by neutral hydroxymethyl substituents. That structure comprises three independent molecules, either centrosymmetric or pseudo-centrosymmetric, in which the U environment is close to that of (I); in one of these molecules, however, this environment is somewhat less regular, due to the presence of an intramolecular O(hydroxyl)···O(phenoxide) hydrogen bond between the two ligands (Thuéry et al., 2002). The two phenoxide rings in (I), as well as in the previous complex, adopt a `butterfly' conformation and are located on either side of the uranyl equatorial plane. The dihedral angles in (I) between the two phenoxide rings of each ligand and this plane are 43.94 (14) and 25.8 (2)° and, between the two phenoxide rings, 69.66 (17)°, whereas the corresponding values in the previous complex are 36.9 (6)–52.4 (5)° and 71.4 (6)–79.6 (7)°, respectively. The ligand L in its 1:1 and 1:2 U^IV complexes adopts a similar conformation, with dihedral angles between the two aromatic rings larger than in (I), at 76.3 (2) and 76.2 (4)°. Even if these diphenoxide species give complexes with comparable overall arrangements, the differences in finer geometric details evidence the flexibility of these ligands and their ability to adapt themselves to differing coordination requirements [as between U^IV and U^VI cations] or differing weak interactions.

The two pyridiniomethyl arms of each ligand in (I) are directed away from the uranyl equatorial plane, i.e. towards the concave side of the diphenoxide ligand. The aromatic ring containing atom N2 is involved in two weak but significant π–π stacking interactions, one with its counterpart in the neighbouring molecule at (1 − x, 1 − y, 1 − z) [centroid-centroid distance 3.59 Å, interplanar spacing 3.38 Å, centroid offset 1.21 Å] and the other, weaker, with the solvent pyridine molecule [centroid-centroid distance 4.00 Å, interplanar spacing 3.58 Å, centroid offset 1.78 Å, dihedral angle between the two rings 10.51 (17)°, shortest interatomic contact C29···C36 = 3.368 (9) Å, equal to twice the out-of-plane van der Waals radius of C (1.7 Å)].

The pyridine solvent molecule is located in the `cup' defined by the two phenoxide rings of the ligand (Fig. 2), in which it is held by two C—H···π interactions, the first between atom H35 and the aromatic ring C1—C6 bound to atom O1 [H35···centroid distance 2.90 Å, C35—H35···centroid angle 173°], and the second between atom H36 and the aromatic ring C12—C17 bound to atom O2 [H36···centroid distance 2.77 Å, C36–H36···centroid angle 148°]. In the previous uranyl ion complex with a diphenoxide species, a comparable position was occupied by a HDABCO cation (DABCO is 1,4-diazabicyclo[2.2.2]octane), but in that case the cation was primarily held by a strong N—H···O(oxo) hydrogen bond with the central uranyl ion and by cation···π interactions involving the phenoxide rings (Thuéry et al., 2002). Another weak CH···π interaction may be considered in (I), between an H atom of the tert-butyl group bound to the phenoxide ring bearing atom O2 and the pyridine molecule at (1 − x, 1 − y, −z) [H19C···centroid distance 2.89 Å, C19—H19C···centroid angle 155°].

The present result provides a new example of homooxacalixarene cleavage in the presence of pyridine and U^IV salts, UCl₄ being replaced in this case by U(OSO₂CF₃)₄. Further oxidation of the metal centre leads to the second example of a diphenoxide complex of the uranyl ion. However, we have also reported that some triphenols complex this ion in their diphenoxide form (Thuéry et al., 2002, and references therein). Direct reaction of uranyl salts with p-R-tetrahomodioxacalix[4]arene (where R is methyl, tert-butyl or phenyl), in the presence of bases such as amines or alkali metal hydroxides, does not result in homooxacalixarene cleavage, even in the presence of pyridine. In these cases, `internal' tetraphenoxide-coordinated uranyl complexes are obtained, which differ in their counterions, solvent environment and supramolecular arrangement (Thuéry & Masci, 2003, and references therein). The homooxacalixarene in all these complexes is in a cone conformation and, as a consequence, all the phenoxide rings are on the same side of the uranyl equatorial plane, which is at variance with the centrosymmetrical geometry of complex (I). In these homooxacalixarene complexes, the mean U—O(phenoxide) bond length of 2.28 (2) Å (eight compounds) appears slightly larger, albeit with little significance, than that in (I) or in the previous uranyl diphenoxide complex [2.25 (2) Å], which may be due to the geometrical constraints imposed by the cyclic nature of the homooxacalixarene. The range of O(phenoxide)-U—O(phenoxide) angles is also larger in the macrocyclic complexes [82.1 (3)–97.7 (3)°], in conjunction with very different O···O distances between adjacent phenoxide groups [mean values 3.10 (2) Å for groups separated by a methylenic link and 3.34 (3) Å for groups separated by an ether link, compared with O1···O2 3.171 (5) and O1···O2' 3.209 (5) Å in (I)], which is due to the presence of the two ether links, which act as spacers.

S2. Experimental

p-tert-Butyltetrahomodioxacalix[4]arene was synthesized using the method of Dhawan & Gutsche (1983), and U(OTf)₄ (OTf is OSO₂CF₃) was synthesized using the method of Berthet et al. (1999). Complex (I) was synthesized by reaction of p-tert-butyltetrahomodioxacalix[4]arene with one equivalent of U(OTf)₄ in pyridine. The oxidation of the metal centre from U^IV to U^VI, in the form of the uranyl ion, can be attributed either to adventitious traces of oxygen, possibly entering the reaction flask during prolonged heating at 383 K, or to the water molecules eliminated during the nucleophilic attack on the benzylic C atoms by pyridine. Single crystals of (I) were obtained by slow diffusion of tetrahydrofuran into the mother solution.

S3. Refinement

The H atoms were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH), 0.97 (CH₂) and 0.96 (CH₃)Å, and with U_iso(H) = 1.2 (CH or CH₂) or 1.5 (CH₃) times U_eq of the parent atom. Some restraints on displacement parameters were applied for two F atoms and for the C atoms of the pyridine molecule. The highest positive and negative electron-density residuals are located 0.87 and 0.95 Å, respectively, from the U atom.

Computing details

Data collection: EVALCCD (Duisenberg et al., 2003); cell refinement: EVALCCD; data reduction: EVALCCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of complex (I), with the counterions, H atoms and solvent molecules omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are at the symmetry position (2 − x, 1 − y, 1 − z).
	Fig. 2. A view of complex (I) including the pyridine solvent molecules. The π–π and CH···π interactions are represented as dashed lines. The counterions and H atoms (except those of the pyridine molecules) have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are at the symmetry position (2 − x, 1 − y, 1 − z).

Bis{bis[5-tert-butyl-2-oxido-3-(1-pyridiniomethyl)phenyl]methane}dioxouranium bis(trifluoromethanesulfonate) pyridine disolvate

Crystal data

[UO2(C33H38N2O2)2](CF3O3S)2·2C5H5N	Z = 1
Mr = 1715.68	F(000) = 870
Triclinic, P1	Dx = 1.511 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.7189 (9) Å	Cell parameters from 13391 reflections
b = 11.1479 (13) Å	θ = 2.5–25.7°
c = 17.0975 (16) Å	µ = 2.29 mm^−1
α = 102.472 (6)°	T = 100 K
β = 106.903 (6)°	Needle, light orange
γ = 94.800 (6)°	0.40 × 0.10 × 0.05 mm
V = 1885.0 (3) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	6934 independent reflections
Radiation source: fine-focus sealed tube	5444 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
ϕ and ω scans	θmax = 25.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.698, Tmax = 0.892	k = −13→12
13391 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0328P)^2] where P = (Fo^2 + 2Fc^2)/3
6934 reflections	(Δ/σ)max = 0.001
481 parameters	Δρmax = 1.54 e Å^−3
36 restraints	Δρmin = −2.30 e Å^−3

Special details

Experimental. crystal-to-detector distance 28 mm

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

Refinement. Structure solved by Patterson map interpretation and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Some restraints on displacement parameters were applied for two F atoms and the C atoms of the pyridine molecule. All H atoms were introduced at calculated positions and were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH₂) or 1.5 (CH₃) times that of the parent atom. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
U	1.0000	0.5000	0.5000	0.01041 (11)
O1	1.0676 (3)	0.4168 (3)	0.3900 (2)	0.0123 (8)
O2	0.9008 (3)	0.6317 (3)	0.4274 (2)	0.0123 (8)
O3	0.8479 (3)	0.3940 (3)	0.4549 (2)	0.0115 (8)
N1	0.9121 (4)	0.1470 (4)	0.3543 (3)	0.0105 (10)
N2	0.5670 (4)	0.6292 (4)	0.4057 (3)	0.0096 (10)
C1	0.9924 (5)	0.2594 (5)	0.2609 (3)	0.0097 (12)
C2	1.0222 (5)	0.3862 (5)	0.3058 (3)	0.0115 (12)
C3	1.0089 (5)	0.4771 (5)	0.2585 (3)	0.0114 (12)
C4	0.9699 (5)	0.4384 (5)	0.1714 (3)	0.0127 (12)
H4	0.9641	0.4991	0.1413	0.015*
C5	0.9386 (5)	0.3140 (5)	0.1257 (3)	0.0133 (13)
C6	0.9517 (5)	0.2257 (5)	0.1734 (3)	0.0130 (12)
H6	0.9326	0.1417	0.1455	0.016*
C7	0.8939 (6)	0.2796 (5)	0.0294 (3)	0.0195 (14)
C8	0.7809 (6)	0.3475 (6)	−0.0053 (4)	0.0256 (15)
H8A	0.7063	0.3218	0.0109	0.038*
H8B	0.7567	0.3277	−0.0658	0.038*
H8C	0.8084	0.4355	0.0171	0.038*
C9	1.0096 (6)	0.3156 (6)	−0.0010 (4)	0.0296 (16)
H9A	0.9802	0.2971	−0.0616	0.044*
H9B	1.0791	0.2692	0.0176	0.044*
H9C	1.0418	0.4030	0.0218	0.044*
C10	0.8443 (8)	0.1388 (6)	−0.0080 (4)	0.0397 (18)
H10A	0.7699	0.1151	0.0090	0.067*
H10B	0.9137	0.0932	0.0123	0.067*
H10C	0.8183	0.1204	−0.0685	0.067*
C11	1.0353 (5)	0.6151 (5)	0.3038 (3)	0.0111 (12)
H11A	1.0833	0.6254	0.3631	0.013*
H11B	1.0907	0.6598	0.2802	0.013*
C12	0.9091 (5)	0.6715 (5)	0.2964 (3)	0.0099 (12)
C13	0.8485 (5)	0.6754 (5)	0.3596 (3)	0.0078 (11)
C14	0.7318 (5)	0.7288 (5)	0.3504 (3)	0.0091 (12)
C15	0.6783 (5)	0.7712 (5)	0.2791 (3)	0.0107 (12)
H15	0.6015	0.8061	0.2743	0.013*
C16	0.7338 (5)	0.7640 (5)	0.2146 (3)	0.0096 (12)
C17	0.8516 (5)	0.7152 (5)	0.2275 (3)	0.0109 (12)
H17	0.8939	0.7122	0.1869	0.013*
C18	0.6720 (5)	0.8006 (5)	0.1310 (3)	0.0135 (13)
C19	0.6329 (6)	0.6834 (5)	0.0582 (3)	0.0215 (14)
H19A	0.5685	0.6262	0.0662	0.032*
H19B	0.7095	0.6452	0.0569	0.032*
H19C	0.5962	0.7053	0.0059	0.032*
C20	0.7717 (6)	0.8914 (5)	0.1156 (4)	0.0199 (14)
H20A	0.7323	0.9118	0.0630	0.030*
H20B	0.8483	0.8538	0.1133	0.030*
H20C	0.7970	0.9659	0.1607	0.030*
C21	0.5499 (5)	0.8610 (5)	0.1314 (3)	0.0191 (14)
H21A	0.4834	0.8027	0.1366	0.029*
H21B	0.5165	0.8853	0.0796	0.029*
H21C	0.5727	0.9330	0.1782	0.029*
C22	1.0116 (5)	0.1625 (5)	0.3101 (3)	0.0156 (13)
H22A	1.0087	0.0833	0.2719	0.019*
H22B	1.0988	0.1841	0.3518	0.019*
C23	0.7839 (5)	0.1447 (5)	0.3147 (3)	0.0156 (13)
H23	0.7579	0.1598	0.2613	0.019*
C24	0.6898 (5)	0.1201 (5)	0.3521 (4)	0.0147 (13)
H24	0.6006	0.1152	0.3234	0.018*
C25	0.7301 (5)	0.1030 (5)	0.4329 (4)	0.0156 (13)
H25	0.6684	0.0883	0.4598	0.019*
C26	0.8632 (5)	0.1079 (5)	0.4733 (3)	0.0149 (13)
H26	0.8919	0.0968	0.5277	0.018*
C27	0.9526 (5)	0.1294 (5)	0.4324 (3)	0.0133 (12)
H27	1.0420	0.1317	0.4592	0.016*
C28	0.6676 (5)	0.7416 (5)	0.4187 (3)	0.0097 (12)
H28A	0.6244	0.8148	0.4203	0.012*
H28B	0.7354	0.7540	0.4729	0.012*
C29	0.6002 (5)	0.5153 (5)	0.3915 (3)	0.0139 (13)
H29	0.6831	0.5057	0.3864	0.017*
C30	0.5136 (5)	0.4123 (5)	0.3842 (3)	0.0163 (13)
H30	0.5385	0.3337	0.3755	0.020*
C31	0.3907 (5)	0.4258 (5)	0.3900 (3)	0.0161 (13)
H31	0.3306	0.3569	0.3844	0.019*
C32	0.3576 (5)	0.5433 (6)	0.4042 (4)	0.0197 (14)
H32	0.2745	0.5539	0.4085	0.024*
C33	0.4464 (5)	0.6452 (5)	0.4120 (3)	0.0149 (13)
H33	0.4236	0.7245	0.4215	0.018*
S	0.33942 (13)	1.01717 (13)	0.37917 (9)	0.0139 (3)
O4	0.4118 (4)	1.1382 (3)	0.3915 (3)	0.0257 (10)
O5	0.4192 (4)	0.9245 (4)	0.4012 (2)	0.0252 (10)
O6	0.2238 (4)	1.0181 (4)	0.4055 (2)	0.0235 (10)
F1	0.1907 (5)	0.8577 (4)	0.2408 (3)	0.0635 (13)
F2	0.2045 (3)	1.0451 (4)	0.2305 (2)	0.0411 (10)
F3	0.3672 (3)	0.9471 (3)	0.2296 (2)	0.0338 (9)
C34	0.2720 (6)	0.9630 (6)	0.2643 (4)	0.0244 (15)
N3	0.5516 (6)	0.2339 (6)	0.1749 (4)	0.0473 (17)
C35	0.6116 (8)	0.3440 (8)	0.1833 (4)	0.045 (2)
H35	0.7016	0.3534	0.1906	0.054*
C36	0.5528 (9)	0.4447 (8)	0.1822 (5)	0.054 (2)
H36	0.6013	0.5206	0.1870	0.064*
C37	0.4240 (9)	0.4369 (8)	0.1742 (5)	0.059 (2)
H37	0.3822	0.5068	0.1747	0.071*
C38	0.3539 (8)	0.3192 (9)	0.1650 (5)	0.060 (2)
H38	0.2642	0.3075	0.1585	0.072*
C39	0.4256 (8)	0.2230 (8)	0.1663 (5)	0.052 (2)
H39	0.3816	0.1446	0.1607	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U	0.00956 (18)	0.01204 (19)	0.01036 (18)	0.00416 (13)	0.00436 (14)	0.00172 (13)
O1	0.012 (2)	0.014 (2)	0.013 (2)	0.0070 (16)	0.0060 (17)	0.0028 (17)
O2	0.011 (2)	0.020 (2)	0.010 (2)	0.0086 (17)	0.0079 (17)	0.0045 (17)
O3	0.0098 (19)	0.012 (2)	0.016 (2)	0.0038 (16)	0.0076 (17)	0.0055 (17)
N1	0.009 (2)	0.008 (2)	0.015 (3)	0.0048 (19)	0.006 (2)	0.000 (2)
N2	0.006 (2)	0.014 (3)	0.009 (2)	0.0027 (19)	0.002 (2)	0.002 (2)
C1	0.009 (3)	0.013 (3)	0.015 (3)	0.007 (2)	0.009 (2)	0.009 (2)
C2	0.006 (3)	0.020 (3)	0.010 (3)	0.003 (2)	0.005 (2)	0.001 (2)
C3	0.012 (3)	0.010 (3)	0.017 (3)	0.005 (2)	0.010 (3)	0.006 (2)
C4	0.017 (3)	0.013 (3)	0.015 (3)	0.009 (2)	0.011 (3)	0.007 (2)
C5	0.014 (3)	0.019 (3)	0.010 (3)	0.002 (3)	0.009 (3)	0.003 (3)
C6	0.014 (3)	0.012 (3)	0.017 (3)	0.006 (2)	0.010 (3)	0.003 (2)
C7	0.025 (3)	0.020 (3)	0.011 (3)	0.002 (3)	0.005 (3)	0.002 (3)
C8	0.026 (4)	0.033 (4)	0.015 (3)	0.004 (3)	0.003 (3)	0.004 (3)
C9	0.031 (4)	0.049 (5)	0.012 (3)	0.018 (3)	0.009 (3)	0.007 (3)
C10	0.060 (4)	0.031 (3)	0.019 (3)	0.001 (3)	0.002 (3)	0.004 (3)
C11	0.012 (3)	0.014 (3)	0.007 (3)	0.000 (2)	0.004 (2)	0.000 (2)
C12	0.009 (3)	0.007 (3)	0.013 (3)	0.000 (2)	0.006 (2)	−0.002 (2)
C13	0.006 (3)	0.006 (3)	0.010 (3)	−0.002 (2)	0.002 (2)	−0.001 (2)
C14	0.007 (3)	0.007 (3)	0.013 (3)	0.000 (2)	0.004 (2)	0.002 (2)
C15	0.007 (3)	0.012 (3)	0.018 (3)	0.006 (2)	0.007 (3)	0.006 (2)
C16	0.010 (3)	0.006 (3)	0.012 (3)	0.000 (2)	0.005 (2)	−0.001 (2)
C17	0.012 (3)	0.011 (3)	0.012 (3)	0.000 (2)	0.009 (3)	0.001 (2)
C18	0.015 (3)	0.015 (3)	0.012 (3)	0.003 (2)	0.006 (3)	0.002 (2)
C19	0.022 (3)	0.026 (4)	0.015 (3)	0.004 (3)	0.002 (3)	0.006 (3)
C20	0.026 (3)	0.023 (4)	0.019 (3)	0.009 (3)	0.012 (3)	0.012 (3)
C21	0.017 (3)	0.027 (4)	0.012 (3)	0.009 (3)	0.000 (3)	0.006 (3)
C22	0.017 (3)	0.017 (3)	0.017 (3)	0.003 (3)	0.014 (3)	0.002 (3)
C23	0.021 (3)	0.015 (3)	0.014 (3)	0.008 (3)	0.009 (3)	0.001 (3)
C24	0.010 (3)	0.009 (3)	0.021 (3)	−0.001 (2)	0.004 (3)	−0.004 (3)
C25	0.019 (3)	0.011 (3)	0.021 (3)	0.004 (3)	0.014 (3)	0.002 (3)
C26	0.023 (3)	0.013 (3)	0.015 (3)	0.006 (3)	0.012 (3)	0.006 (2)
C27	0.015 (3)	0.012 (3)	0.013 (3)	0.000 (2)	0.007 (3)	0.001 (2)
C28	0.010 (3)	0.007 (3)	0.010 (3)	−0.001 (2)	0.003 (3)	0.000 (2)
C29	0.010 (3)	0.015 (3)	0.021 (3)	0.009 (2)	0.007 (3)	0.009 (3)
C30	0.019 (3)	0.015 (3)	0.017 (3)	0.004 (3)	0.010 (3)	0.004 (3)
C31	0.012 (3)	0.021 (3)	0.017 (3)	0.000 (3)	0.004 (3)	0.008 (3)
C32	0.010 (3)	0.029 (4)	0.024 (3)	0.004 (3)	0.009 (3)	0.010 (3)
C33	0.010 (3)	0.022 (3)	0.015 (3)	0.011 (3)	0.002 (3)	0.008 (3)
S	0.0143 (8)	0.0141 (8)	0.0174 (8)	0.0054 (6)	0.0094 (7)	0.0054 (6)
O4	0.033 (2)	0.013 (2)	0.034 (3)	−0.0023 (19)	0.018 (2)	0.0048 (19)
O5	0.028 (2)	0.026 (3)	0.026 (2)	0.019 (2)	0.007 (2)	0.010 (2)
O6	0.020 (2)	0.038 (3)	0.024 (2)	0.010 (2)	0.016 (2)	0.017 (2)
F1	0.073 (3)	0.065 (3)	0.033 (2)	−0.033 (2)	0.008 (2)	0.002 (2)
F2	0.038 (2)	0.074 (3)	0.027 (2)	0.034 (2)	0.0172 (17)	0.0258 (19)
F3	0.033 (2)	0.052 (3)	0.024 (2)	0.0226 (19)	0.0198 (18)	0.0046 (18)
C34	0.023 (3)	0.023 (4)	0.034 (4)	−0.001 (3)	0.018 (3)	0.009 (3)
N3	0.043 (4)	0.040 (4)	0.050 (4)	0.002 (3)	−0.002 (4)	0.018 (3)
C35	0.040 (5)	0.067 (6)	0.026 (4)	0.004 (4)	0.013 (4)	0.005 (4)
C36	0.074 (4)	0.047 (4)	0.037 (4)	−0.003 (3)	0.014 (3)	0.014 (3)
C37	0.084 (4)	0.062 (4)	0.032 (4)	0.047 (4)	0.011 (3)	0.010 (3)
C38	0.044 (4)	0.095 (5)	0.041 (4)	0.014 (4)	0.012 (3)	0.018 (4)
C39	0.055 (4)	0.054 (4)	0.044 (4)	−0.014 (3)	0.008 (3)	0.026 (3)

Geometric parameters (Å, º)

U—O1	2.252 (3)	C19—H19A	0.9600
U—O2	2.260 (3)	C19—H19B	0.9600
U—O3	1.790 (3)	C19—H19C	0.9600
O1—C2	1.334 (6)	C20—H20A	0.9600
O2—C13	1.344 (6)	C20—H20B	0.9600
N1—C23	1.340 (6)	C20—H20C	0.9600
N1—C27	1.343 (7)	C21—H21A	0.9600
N1—C22	1.493 (6)	C21—H21B	0.9600
N2—C29	1.338 (6)	C21—H21C	0.9600
N2—C33	1.351 (6)	C22—H22A	0.9700
N2—C28	1.516 (6)	C22—H22B	0.9700
C1—C6	1.386 (7)	C23—C24	1.381 (7)
C1—C2	1.415 (7)	C23—H23	0.9300
C1—C22	1.499 (7)	C24—C25	1.383 (8)
C2—C3	1.418 (7)	C24—H24	0.9300
C3—C4	1.382 (7)	C25—C26	1.383 (7)
C3—C11	1.527 (7)	C25—H25	0.9300
C4—C5	1.396 (7)	C26—C27	1.374 (7)
C4—H4	0.9300	C26—H26	0.9300
C5—C6	1.399 (7)	C27—H27	0.9300
C5—C7	1.525 (7)	C28—H28A	0.9700
C6—H6	0.9300	C28—H28B	0.9700
C7—C8	1.524 (8)	C29—C30	1.375 (7)
C7—C9	1.533 (8)	C29—H29	0.9300
C7—C10	1.545 (8)	C30—C31	1.368 (7)
C8—H8A	0.9600	C30—H30	0.9300
C8—H8B	0.9600	C31—C32	1.374 (8)
C8—H8C	0.9600	C31—H31	0.9300
C9—H9A	0.9600	C32—C33	1.376 (8)
C9—H9B	0.9600	C32—H32	0.9300
C9—H9C	0.9600	C33—H33	0.9300
C10—H10A	0.9600	S—O6	1.436 (4)
C10—H10B	0.9600	S—O5	1.439 (4)
C10—H10C	0.9600	S—O4	1.440 (4)
C11—C12	1.523 (7)	S—C34	1.825 (6)
C11—H11A	0.9700	F1—C34	1.311 (7)
C11—H11B	0.9700	F2—C34	1.339 (7)
C12—C17	1.371 (7)	F3—C34	1.328 (7)
C12—C13	1.409 (7)	N3—C35	1.296 (9)
C13—C14	1.413 (7)	N3—C39	1.307 (10)
C14—C15	1.386 (7)	C35—C36	1.334 (10)
C14—C28	1.508 (7)	C35—H35	0.9300
C15—C16	1.388 (7)	C36—C37	1.341 (11)
C15—H15	0.9300	C36—H36	0.9300
C16—C17	1.394 (7)	C37—C38	1.410 (12)
C16—C18	1.547 (7)	C37—H37	0.9300
C17—H17	0.9300	C38—C39	1.371 (11)
C18—C21	1.523 (7)	C38—H38	0.9300
C18—C19	1.527 (7)	C39—H39	0.9300
C18—C20	1.528 (8)
O1—U—O2	89.33 (12)	C19—C18—C16	108.7 (4)
O1—U—O2^i	90.67 (12)	C20—C18—C16	110.6 (4)
O1—U—O3	90.75 (14)	C18—C19—H19A	109.5
O2—U—O3	87.85 (14)	C18—C19—H19B	109.5
O1—U—O3^i	89.25 (14)	H19A—C19—H19B	109.5
O2—U—O3^i	92.15 (14)	C18—C19—H19C	109.5
O3—U—O2^i	92.15 (14)	H19A—C19—H19C	109.5
O3^i—U—O3	180.00	H19B—C19—H19C	109.5
O3—U—O1^i	89.25 (14)	C18—C20—H20A	109.5
O1—U—O1^i	180.00	C18—C20—H20B	109.5
O1^i—U—O2	90.67 (12)	H20A—C20—H20B	109.5
O2—U—O2^i	180.00	C18—C20—H20C	109.5
C2—O1—U	139.0 (3)	H20A—C20—H20C	109.5
C13—O2—U	157.2 (3)	H20B—C20—H20C	109.5
C23—N1—C27	120.7 (5)	C18—C21—H21A	109.5
C23—N1—C22	120.3 (4)	C18—C21—H21B	109.5
C27—N1—C22	118.9 (4)	H21A—C21—H21B	109.5
C29—N2—C33	120.6 (5)	C18—C21—H21C	109.5
C29—N2—C28	119.7 (4)	H21A—C21—H21C	109.5
C33—N2—C28	119.7 (4)	H21B—C21—H21C	109.5
C6—C1—C2	120.7 (5)	N1—C22—C1	114.6 (4)
C6—C1—C22	120.7 (5)	N1—C22—H22A	108.6
C2—C1—C22	118.6 (5)	C1—C22—H22A	108.6
O1—C2—C1	119.8 (5)	N1—C22—H22B	108.6
O1—C2—C3	122.1 (5)	C1—C22—H22B	108.6
C1—C2—C3	118.0 (5)	H22A—C22—H22B	107.6
C4—C3—C2	118.9 (5)	N1—C23—C24	120.8 (5)
C4—C3—C11	121.0 (5)	N1—C23—H23	119.6
C2—C3—C11	120.1 (5)	C24—C23—H23	119.6
C3—C4—C5	124.1 (5)	C23—C24—C25	119.1 (5)
C3—C4—H4	117.9	C23—C24—H24	120.5
C5—C4—H4	117.9	C25—C24—H24	120.5
C4—C5—C6	116.1 (5)	C26—C25—C24	119.2 (5)
C4—C5—C7	120.6 (5)	C26—C25—H25	120.4
C6—C5—C7	123.3 (5)	C24—C25—H25	120.4
C1—C6—C5	122.2 (5)	C27—C26—C25	119.5 (5)
C1—C6—H6	118.9	C27—C26—H26	120.3
C5—C6—H6	118.9	C25—C26—H26	120.3
C8—C7—C5	110.6 (5)	N1—C27—C26	120.7 (5)
C8—C7—C9	109.0 (5)	N1—C27—H27	119.6
C5—C7—C9	109.6 (5)	C26—C27—H27	119.6
C8—C7—C10	107.4 (5)	C14—C28—N2	112.9 (4)
C5—C7—C10	111.8 (5)	C14—C28—H28A	109.0
C9—C7—C10	108.4 (5)	N2—C28—H28A	109.0
C7—C8—H8A	109.5	C14—C28—H28B	109.0
C7—C8—H8B	109.5	N2—C28—H28B	109.0
H8A—C8—H8B	109.5	H28A—C28—H28B	107.8
C7—C8—H8C	109.5	N2—C29—C30	121.0 (5)
H8A—C8—H8C	109.5	N2—C29—H29	119.5
H8B—C8—H8C	109.5	C30—C29—H29	119.5
C7—C9—H9A	109.5	C31—C30—C29	119.6 (5)
C7—C9—H9B	109.5	C31—C30—H30	120.2
H9A—C9—H9B	109.5	C29—C30—H30	120.2
C7—C9—H9C	109.5	C30—C31—C32	118.8 (5)
H9A—C9—H9C	109.5	C30—C31—H31	120.6
H9B—C9—H9C	109.5	C32—C31—H31	120.6
C7—C10—H10A	109.5	C31—C32—C33	120.6 (5)
C7—C10—H10B	109.5	C31—C32—H32	119.7
H10A—C10—H10B	109.5	C33—C32—H32	119.7
C7—C10—H10C	109.5	N2—C33—C32	119.5 (5)
H10A—C10—H10C	109.5	N2—C33—H33	120.3
H10B—C10—H10C	109.5	C32—C33—H33	120.3
C12—C11—C3	112.7 (4)	O6—S—O5	115.3 (2)
C12—C11—H11A	109.1	O6—S—O4	114.9 (2)
C3—C11—H11A	109.1	O5—S—O4	115.2 (3)
C12—C11—H11B	109.1	O6—S—C34	103.4 (3)
C3—C11—H11B	109.1	O5—S—C34	102.7 (3)
H11A—C11—H11B	107.8	O4—S—C34	102.8 (3)
C17—C12—C13	119.6 (5)	F1—C34—F3	108.5 (5)
C17—C12—C11	120.7 (5)	F1—C34—F2	107.0 (5)
C13—C12—C11	119.7 (4)	F3—C34—F2	106.4 (5)
O2—C13—C12	121.3 (4)	F1—C34—S	111.6 (4)
O2—C13—C14	120.8 (5)	F3—C34—S	111.3 (4)
C12—C13—C14	117.8 (5)	F2—C34—S	111.7 (4)
C15—C14—C13	119.8 (5)	C35—N3—C39	116.9 (7)
C15—C14—C28	120.4 (4)	N3—C35—C36	124.3 (8)
C13—C14—C28	119.8 (4)	N3—C35—H35	117.8
C16—C15—C14	123.3 (5)	C36—C35—H35	117.8
C16—C15—H15	118.4	C35—C36—C37	120.2 (8)
C14—C15—H15	118.4	C35—C36—H36	119.9
C15—C16—C17	115.3 (5)	C37—C36—H36	119.9
C15—C16—C18	125.0 (4)	C36—C37—C38	117.8 (8)
C17—C16—C18	119.6 (5)	C36—C37—H37	121.1
C12—C17—C16	124.1 (5)	C38—C37—H37	121.1
C12—C17—H17	118.0	C39—C38—C37	116.2 (8)
C16—C17—H17	118.0	C39—C38—H38	121.9
C21—C18—C19	108.8 (5)	C37—C38—H38	121.9
C21—C18—C20	108.3 (5)	N3—C39—C38	124.6 (8)
C19—C18—C20	108.4 (5)	N3—C39—H39	117.7
C21—C18—C16	111.9 (4)	C38—C39—H39	117.7

Symmetry code: (i) −x+2, −y+1, −z+1.