(Dibenzyl sulfoxide-κO)bis(1,3-diphenylpropane-1,3-dionato-κ²O,O′)dioxouranium(VI)

In the title compound, [UO₂(C₁₅H₁₁O₂)₂(C₁₄H₁₄OS)], the U^VI atom is coordinated by seven O atoms in a distorted pentagonal–bipyramidal geometry. Both di­phenyl­propane-1,3-dionate systems are nearly planar. The sulfoxide moiety is in a distorted tetrahedral geometry, while its two aromatic rings are nearly orthogonal to one another. The crystal packing is stabilized by two bifurcated hydrogen-bonding interactions involving both uranyl O atoms.

S1. Comment

The chemistry of adducts of uranyl bis(β-diketonates) with neutral donor ligands is important for understanding the nature of the species extracted during the solvent-extraction separation of the uranyl ion using mixtures of β-diketones and neutral ligands (Ramakrishna & Patil, 1984).

We and several other research groups have isolated many of these compounds in the solid state, and these compounds have been characterized by spectroscopic and elemental analysis methods (Subramaniam & Viswanatha, 1969; Lu et al., 1977; Taylor & Waugh, 1977; Kramer et al., 1980; Nagar et al., 1989; Kannan & Venugopal, 1995; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001a,b; Kannan & Ferguson, 1997; Kannan, 2000). We have also carried out extensive studies on the structures of these compounds using single-crystal X-ray diffraction methods and their relations with spectroscopic results Please clarify (Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001a,b; Kannan & Ferguson, 1997).

Recently, we have prepared adducts of uranyl bis(β-diketonates) with sulfoxide ligands, and found a stronger shielding effect due to the CH₂ H atoms in diphenylmethylene sulfoxide compared with that in methyl-phenylmethylene sulfoxide. However, there are no structural studies to support this spectroscopic observation. As part of our systematic study, we have undertaken the X-ray structure determination of the title compound, (I), at 183 K, and the result is reported here. \sch

The bond lengths and angles in (I) (Fig. 1) are within the normal ranges (Allen et al., 1987). The structure of the molecule shows that the U^VI ion is surrounded by seven O atoms in a pentagonal-bipyramidal geometry. Four O atoms (O3, O4, O5 and O6) of the diphenylpropane-1,3-dionato-O,O' (DBM) moieties, together with atom O7 of the sulfoxide, form a pentagon, while the two uranyl O atoms occupy the apices.

The pentagonal plane O3/O4/O5/O6/O7 is distorted from planarity towards a twisted conformation, with a local twofold axis passing through atom O7 and O3···O6. Atom U1 is displaced by 0.0574 (3) Å from the O3/O4/O5/O6/O7 mean plane. The O—U—O bond angles for the pentagon are in the range 70.5 (2)–74.0 (2)°, while the O_pentagon—U—O_apex angle is 90.0 (3)°. The average U—O_uranyl distance is 1.792 Å, and the average U—O_diketonate distance is 2.344 Å. These values are acceptable, and agree with the values reported earlier (U—O_uranyl and U—O_diketonate in the ranges 1.727–1.788 Å and 2.308–2.417%A, respectively; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997, 2000, 2001b; Kannan & Ferguson, 1997). The U—O_sulfoxide bond distance [2.421 (6) Å] is also comparable with that reported earlier for uranyl bis(β-diketonate) sulfoxide complexes [2.375 Å (Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996) and 2.427 Å (Kannan et al., 2000)].

Both diphenylpropane-1,3-dionato-O,O' (DBM) systems in (I) are nearly planar, with their two phenyl rings having slightly different configurations, corresponding to dihedral angles of 13.3 (5) and 30.9 (4)° between them in the two DBM systems. The planarity of the DBM system is due to the C═O and C—C conjugation in the propane-1,3-dionato-O,O' moiety joining the two phenyl rings.

The propane-1,3-dionato-O,O' moieties, with the U, also form six-membered rings, O5/O6/C7/C8/C9/U1 and O3/O4/C22/C23/C24/U1, in which atom U1 is displaced by 0.2082 (3) and 0.3121 (3) Å from the O5/O6/C7/C8/C9 and O3/O4/C22/C23/C24 planes, respectively.

The configuration of the two phenylmethylene moieties is conditioned by the distorted tetrahedral geometry of the sulfoxide moiety. The angles subtended at atom S1 are 97.1 (4), 104.8 (4), and 104.9 (4)°, with S1—O7, S1—C37 and S1—C38 distances of 1.527 (6), 1.817 (9) and 1.831 (9) Å, respectively. The O7···C37, O7···C38 and C37···C38 distances are 2.66 (1), 2.67 (1) and 2.73 (1) Å, respectively. The aromatic rings of the two phenylmethylene moieties are nearly orthogonal, with a dihedral angle of 83.2 (4)°.

In the crystal structure of (I), there are hydrogen-bonding interactions involving the two uranyl O atoms, namely C19—H19A···O1, C28—H28A···O1, C38—H38B···O2 and C43—H43A···O2 (Table 2). These interactions link the molecules into a three-dimensional network (Fig. 2) and, along with dipole-dipole and van der Waals interactions, stabilize the noncentrosymmetric crystal packing.

S2. Experimental

The title compound was prepared and characterized using the method reported by Kannan, Venugopal, Pillai, Droege, Barnes & Schlember (1996). Crystals of (I) suitable for X-ray diffraction analysis were obtained from slow evaporation of a chloform-toluene solution.

S3. Refinement

The Friedel opposites were not merged and the choice of absolute structure was determined by the Flack parameter (Flack, 1983; Flack & Bernardinelli, 1999, 2000). All six phenyl groups were fitted as regular aromatic rings with C—C distances of 1.390 Å and were refined anistropically. All H atoms were geometrically fixed and allowed to ride on their attached parent C atoms, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of (I) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing diagram for (I) viewed along the a axis.

(Dibenzylsulfoxido-κO)bis(1,3-diphenylpropane-1,3-dionato- κ²O,O')dioxouranium(VI)

Crystal data

[U(C15H11O2)2(C14H14OS)O2]	Dx = 1.607 Mg m^−3
Mr = 946.82	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 8192 reflections
a = 12.3178 (1) Å	θ = 2.6–28.3°
b = 15.5281 (1) Å	µ = 4.25 mm^−1
c = 20.4617 (1) Å	T = 183 K
V = 3913.75 (4) Å^3	Block, red
Z = 4	0.34 × 0.16 × 0.16 mm
F(000) = 1856

Data collection

Siemens SMART CCD area-detector diffractometer	9217 independent reflections
Radiation source: fine-focus sealed tube	7611 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.6°
ω scans	h = −16→15
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −20→14
Tmin = 0.300, Tmax = 0.507	l = −26→26
23363 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0423P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
9217 reflections	Δρmax = 2.01 e Å^−3
352 parameters	Δρmin = −3.10 e Å^−3
0 restraints	Absolute structure: Flack (1983), 3842 Friedel reflections
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.023 (10)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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. 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
U1	0.37242 (2)	0.429082 (18)	−0.016628 (13)	0.01416 (8)
S1	0.13073 (19)	0.37490 (12)	0.05943 (9)	0.0178 (4)
O1	0.2597 (5)	0.4962 (4)	−0.0382 (3)	0.0255 (15)
O2	0.4814 (5)	0.3591 (4)	0.0066 (3)	0.0234 (14)
O3	0.4736 (5)	0.5562 (4)	−0.0096 (3)	0.0258 (14)
O4	0.3673 (5)	0.4807 (4)	0.0913 (3)	0.0231 (12)
O5	0.3001 (5)	0.3319 (4)	−0.0936 (3)	0.0269 (15)
O6	0.4637 (6)	0.4472 (5)	−0.1154 (3)	0.0375 (19)
O7	0.2435 (4)	0.3410 (4)	0.0425 (3)	0.0184 (12)
C1	0.1487 (5)	0.2229 (4)	−0.1436 (2)	0.026 (2)
H1	0.1640	0.2207	−0.0991	0.031*
C2	0.0590 (5)	0.1794 (4)	−0.1683 (3)	0.038 (3)
H2	0.0143	0.1482	−0.1404	0.046*
C3	0.0362 (4)	0.1826 (4)	−0.2348 (3)	0.033 (2)
H3	−0.0238	0.1535	−0.2514	0.039*
C4	0.1030 (5)	0.2292 (4)	−0.2766 (2)	0.044 (3)
H4	0.0877	0.2314	−0.3210	0.053*
C5	0.1927 (5)	0.2727 (4)	−0.2518 (2)	0.0230 (19)
H5	0.2375	0.3039	−0.2798	0.028*
C6	0.2156 (4)	0.2695 (3)	−0.1854 (3)	0.0140 (16)
C7	0.3007 (6)	0.3221 (5)	−0.1558 (4)	0.0164 (17)
C8	0.3774 (9)	0.3580 (5)	−0.1955 (4)	0.0268 (19)
H8	0.3763	0.3424	−0.2394	0.032*
C9	0.4602 (7)	0.4184 (6)	−0.1750 (4)	0.0197 (18)
C10	0.5455 (4)	0.4557 (4)	−0.2209 (3)	0.023 (2)
C11	0.5379 (5)	0.4442 (5)	−0.2882 (3)	0.048 (2)
H11	0.4790	0.4148	−0.3058	0.057*
C12	0.6182 (6)	0.4768 (5)	−0.3290 (2)	0.048 (2)
H12	0.6131	0.4691	−0.3740	0.057*
C13	0.7062 (5)	0.5208 (5)	−0.3026 (3)	0.054 (4)
H13	0.7599	0.5426	−0.3299	0.064*
C14	0.7138 (4)	0.5322 (4)	−0.2354 (4)	0.047 (3)
H14	0.7726	0.5617	−0.2177	0.056*
C15	0.6335 (5)	0.4997 (4)	−0.1945 (2)	0.032 (2)
H15	0.6386	0.5073	−0.1496	0.038*
C16	0.5828 (7)	0.6955 (5)	−0.0592 (3)	0.068 (2)
H16	0.5464	0.6575	−0.0867	0.081*
C17	0.6447 (8)	0.7618 (5)	−0.0855 (3)	0.068 (2)
H17	0.6498	0.7682	−0.1306	0.081*
C18	0.6990 (7)	0.8187 (5)	−0.0444 (4)	0.058 (4)
H18	0.7404	0.8630	−0.0620	0.070*
C19	0.6913 (7)	0.8092 (5)	0.0230 (3)	0.068 (2)
H19	0.7277	0.8472	0.0505	0.081*
C20	0.6294 (8)	0.7428 (5)	0.0493 (2)	0.0678 (3)
H20	0.6243	0.7365	0.0944	0.081*
C21	0.5751 (7)	0.6860 (5)	0.0082 (3)	0.068 (2)
C22	0.5089 (6)	0.6089 (6)	0.0325 (4)	0.0176 (16)
C23	0.4930 (8)	0.5974 (5)	0.1000 (4)	0.023 (2)
H23	0.5280	0.6349	0.1285	0.027*
C24	0.4281 (7)	0.5332 (5)	0.1264 (4)	0.0191 (18)
C25	0.4162 (4)	0.5231 (4)	0.19876 (19)	0.0204 (19)
C26	0.5006 (4)	0.5468 (4)	0.2401 (3)	0.024 (2)
H26	0.5644	0.5694	0.2228	0.029*
C27	0.4898 (4)	0.5367 (4)	0.3073 (2)	0.031 (2)
H27	0.5463	0.5525	0.3349	0.037*
C28	0.3945 (5)	0.5029 (4)	0.3331 (2)	0.046 (3)
H28	0.3873	0.4961	0.3781	0.055*
C29	0.3101 (4)	0.4792 (4)	0.2918 (3)	0.028 (2)
H29	0.2464	0.4566	0.3091	0.034*
C30	0.3209 (4)	0.4893 (4)	0.2246 (3)	0.025 (2)
H30	0.2644	0.4735	0.1969	0.030*
C31	0.2081 (5)	0.2365 (4)	0.1874 (3)	0.036 (2)
H31	0.2445	0.2093	0.1533	0.044*
C32	0.2473 (5)	0.2299 (5)	0.2509 (4)	0.061 (4)
H32	0.3098	0.1983	0.2593	0.073*
C33	0.1930 (7)	0.2707 (6)	0.3018 (3)	0.066 (3)
H33	0.2192	0.2663	0.3443	0.079*
C34	0.0995 (7)	0.3180 (6)	0.2891 (3)	0.066 (3)
H34	0.0632	0.3453	0.3232	0.079*
C35	0.0604 (5)	0.3246 (5)	0.2256 (3)	0.0657 (16)
H35	−0.0022	0.3563	0.2172	0.079*
C36	0.1147 (5)	0.2839 (4)	0.1747 (2)	0.0204 (16)
C37	0.0682 (8)	0.2891 (7)	0.1064 (4)	0.029 (2)
H37A	−0.0094	0.2990	0.1091	0.035*
H37B	0.0797	0.2346	0.0843	0.035*
C38	0.0515 (7)	0.3604 (6)	−0.0155 (5)	0.0234 (18)
H38A	0.0941	0.3794	−0.0527	0.028*
H38B	0.0356	0.2997	−0.0214	0.028*
C39	−0.0535 (3)	0.4105 (3)	−0.0132 (3)	0.0217 (18)
C40	−0.0537 (4)	0.5000 (3)	−0.0150 (3)	0.032 (2)
H40	0.0116	0.5301	−0.0157	0.038*
C41	−0.1516 (5)	0.5446 (3)	−0.0159 (4)	0.062 (4)
H41	−0.1517	0.6044	−0.0171	0.074*
C42	−0.2492 (4)	0.4997 (4)	−0.0149 (4)	0.0501 (18)
H42	−0.3146	0.5295	−0.0155	0.060*
C43	−0.2489 (3)	0.4102 (4)	−0.0131 (4)	0.0501 (18)
H43	−0.3142	0.3801	−0.0125	0.060*
C44	−0.1511 (4)	0.3656 (3)	−0.0123 (4)	0.0501 (18)
H44	−0.1509	0.3057	−0.0111	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.01510 (13)	0.01480 (12)	0.01259 (12)	−0.00337 (13)	−0.00159 (13)	−0.00205 (13)
S1	0.0176 (9)	0.0194 (9)	0.0163 (9)	0.0005 (9)	−0.0004 (9)	−0.0012 (7)
O1	0.016 (3)	0.024 (3)	0.037 (4)	−0.008 (3)	−0.012 (3)	0.014 (3)
O2	0.021 (3)	0.021 (3)	0.029 (4)	−0.001 (2)	−0.007 (3)	0.000 (3)
O3	0.030 (3)	0.026 (3)	0.022 (3)	−0.018 (3)	−0.001 (3)	−0.010 (3)
O4	0.025 (3)	0.026 (3)	0.018 (3)	−0.007 (3)	−0.002 (3)	−0.003 (2)
O5	0.027 (4)	0.035 (4)	0.019 (3)	−0.018 (3)	0.004 (3)	−0.001 (3)
O6	0.048 (4)	0.046 (5)	0.019 (3)	−0.028 (4)	0.010 (3)	−0.009 (3)
O7	0.005 (3)	0.025 (3)	0.025 (3)	−0.001 (2)	0.001 (2)	0.000 (3)
C1	0.035 (6)	0.019 (4)	0.025 (4)	−0.013 (4)	0.005 (4)	−0.012 (4)
C2	0.051 (7)	0.031 (6)	0.032 (6)	−0.017 (5)	0.012 (5)	−0.004 (5)
C3	0.031 (6)	0.027 (5)	0.041 (6)	−0.012 (4)	−0.013 (5)	−0.006 (5)
C4	0.089 (10)	0.018 (5)	0.025 (5)	−0.007 (5)	−0.019 (6)	−0.001 (4)
C5	0.025 (5)	0.019 (5)	0.025 (5)	−0.006 (4)	−0.002 (4)	−0.001 (4)
C6	0.011 (4)	0.012 (4)	0.018 (4)	0.000 (3)	−0.002 (3)	−0.003 (3)
C7	0.013 (4)	0.017 (4)	0.019 (4)	0.002 (3)	−0.002 (3)	−0.002 (3)
C8	0.038 (5)	0.027 (5)	0.015 (4)	−0.009 (5)	0.002 (5)	−0.008 (3)
C9	0.021 (4)	0.015 (4)	0.022 (4)	0.004 (4)	−0.001 (3)	−0.001 (4)
C10	0.017 (4)	0.025 (5)	0.026 (5)	0.004 (3)	0.001 (4)	0.000 (4)
C11	0.064 (6)	0.058 (6)	0.021 (4)	−0.005 (5)	0.010 (4)	0.008 (4)
C12	0.064 (6)	0.058 (6)	0.021 (4)	−0.005 (5)	0.010 (4)	0.008 (4)
C13	0.014 (5)	0.071 (9)	0.077 (9)	−0.001 (5)	0.016 (6)	0.019 (8)
C14	0.020 (6)	0.059 (8)	0.061 (8)	−0.015 (5)	0.014 (5)	−0.004 (7)
C15	0.032 (5)	0.028 (5)	0.036 (5)	−0.013 (5)	0.013 (5)	0.001 (4)
C16	0.120 (6)	0.052 (4)	0.031 (3)	−0.049 (4)	−0.001 (4)	0.004 (3)
C17	0.120 (6)	0.052 (4)	0.031 (3)	−0.049 (4)	−0.001 (4)	0.004 (3)
C18	0.081 (9)	0.038 (7)	0.056 (8)	−0.040 (6)	0.006 (7)	−0.002 (6)
C19	0.120 (6)	0.052 (4)	0.031 (3)	−0.049 (4)	−0.001 (4)	0.004 (3)
C20	0.1198 (6)	0.0524 (6)	0.0313 (4)	−0.049 (4)	−0.001 (4)	0.004 (3)
C21	0.120 (6)	0.052 (4)	0.031 (3)	−0.049 (4)	−0.001 (4)	0.004 (3)
C22	0.015 (3)	0.021 (4)	0.017 (4)	0.001 (3)	0.001 (3)	0.001 (3)
C23	0.033 (5)	0.017 (4)	0.019 (4)	−0.012 (4)	0.000 (4)	−0.004 (3)
C24	0.025 (5)	0.011 (4)	0.021 (4)	−0.001 (3)	−0.001 (4)	−0.003 (3)
C25	0.028 (5)	0.016 (4)	0.017 (4)	0.003 (3)	−0.003 (3)	−0.003 (4)
C26	0.014 (4)	0.034 (6)	0.024 (5)	−0.007 (3)	−0.001 (3)	−0.003 (4)
C27	0.033 (6)	0.041 (6)	0.019 (5)	0.002 (4)	−0.008 (4)	−0.005 (4)
C28	0.090 (10)	0.026 (5)	0.021 (5)	0.005 (6)	0.027 (6)	−0.008 (4)
C29	0.029 (5)	0.027 (5)	0.028 (5)	0.001 (4)	0.011 (4)	−0.001 (4)
C30	0.031 (5)	0.019 (5)	0.026 (5)	−0.003 (4)	0.005 (4)	−0.004 (4)
C31	0.025 (5)	0.039 (6)	0.045 (6)	0.002 (4)	−0.007 (5)	−0.003 (5)
C32	0.039 (7)	0.065 (9)	0.078 (9)	0.002 (7)	−0.027 (7)	0.017 (8)
C33	0.080 (8)	0.082 (8)	0.035 (5)	−0.025 (6)	−0.001 (5)	0.000 (5)
C34	0.080 (8)	0.082 (8)	0.035 (5)	−0.025 (6)	−0.001 (5)	0.000 (5)
C35	0.080 (4)	0.082 (4)	0.035 (3)	−0.025 (4)	−0.001 (3)	0.000 (3)
C36	0.028 (4)	0.019 (4)	0.015 (3)	−0.010 (4)	0.000 (3)	0.006 (3)
C37	0.031 (5)	0.035 (6)	0.020 (5)	−0.019 (4)	−0.002 (4)	0.009 (4)
C38	0.028 (5)	0.026 (5)	0.016 (4)	−0.004 (3)	0.000 (4)	−0.006 (4)
C39	0.015 (4)	0.031 (5)	0.019 (4)	0.004 (3)	−0.005 (4)	0.000 (4)
C40	0.044 (6)	0.026 (5)	0.025 (5)	−0.001 (4)	0.008 (5)	0.004 (5)
C41	0.100 (11)	0.048 (7)	0.037 (6)	0.038 (7)	0.000 (8)	0.002 (6)
C42	0.015 (3)	0.075 (5)	0.060 (4)	0.002 (3)	−0.003 (3)	0.004 (4)
C43	0.015 (3)	0.075 (5)	0.060 (4)	0.002 (3)	−0.003 (3)	0.004 (4)
C44	0.015 (3)	0.075 (5)	0.060 (4)	0.002 (3)	−0.003 (3)	0.004 (4)

Geometric parameters (Å, º)

U1—O1	1.791 (6)	C19—C20	1.3900
U1—O2	1.792 (6)	C19—H19	0.9300
U1—O6	2.330 (6)	C20—C21	1.3900
U1—O3	2.339 (5)	C20—H20	0.9300
U1—O4	2.351 (5)	C21—C22	1.532 (9)
U1—O5	2.357 (6)	C22—C23	1.405 (11)
U1—O7	2.420 (6)	C23—C24	1.387 (11)
S1—O7	1.525 (6)	C23—H23	0.9300
S1—C37	1.815 (9)	C24—C25	1.495 (9)
S1—C38	1.832 (9)	C25—C26	1.3900
O3—C22	1.265 (9)	C25—C30	1.3900
O4—C24	1.320 (9)	C26—C27	1.3900
O5—C7	1.280 (10)	C26—H26	0.9300
O6—C9	1.300 (10)	C27—C28	1.3900
C1—C2	1.3900	C27—H27	0.9300
C1—C6	1.3900	C28—C29	1.3900
C1—H1	0.9300	C28—H28	0.9300
C2—C3	1.3900	C29—C30	1.3900
C2—H2	0.9300	C29—H29	0.9300
C3—C4	1.3900	C30—H30	0.9300
C3—H3	0.9300	C31—C32	1.3900
C4—C5	1.3900	C31—C36	1.3900
C4—H4	0.9300	C31—H31	0.9300
C5—C6	1.3900	C32—C33	1.3900
C5—H5	0.9300	C32—H32	0.9300
C6—C7	1.461 (9)	C33—C34	1.3900
C7—C8	1.365 (12)	C33—H33	0.9300
C8—C9	1.447 (12)	C34—C35	1.3900
C8—H8	0.9300	C34—H34	0.9300
C9—C10	1.524 (9)	C35—C36	1.3900
C10—C11	1.3900	C35—H35	0.9300
C10—C15	1.3900	C36—C37	1.512 (9)
C11—C12	1.3900	C37—H37A	0.9700
C11—H11	0.9300	C37—H37B	0.9700
C12—C13	1.3900	C38—C39	1.510 (9)
C12—H12	0.9300	C38—H38A	0.9700
C13—C14	1.3900	C38—H38B	0.9700
C13—H13	0.9300	C39—C40	1.3900
C14—C15	1.3900	C39—C44	1.3900
C14—H14	0.9300	C40—C41	1.3900
C15—H15	0.9300	C40—H40	0.9300
C16—C17	1.3900	C41—C42	1.3900
C16—C21	1.3900	C41—H41	0.9300
C16—H16	0.9300	C42—C43	1.3900
C17—C18	1.3900	C42—H42	0.9300
C17—H17	0.9300	C43—C44	1.3900
C18—C19	1.3900	C43—H43	0.9300
C18—H18	0.9300	C44—H44	0.9300
O1—U1—O2	177.7 (3)	C18—C19—H19	120.0
O1—U1—O6	95.1 (3)	C20—C19—H19	120.0
O2—U1—O6	86.7 (3)	C21—C20—C19	120.0
O1—U1—O3	86.4 (2)	C21—C20—H20	120.0
O2—U1—O3	95.5 (2)	C19—C20—H20	120.0
O6—U1—O3	72.2 (2)	C20—C21—C16	120.0
O1—U1—O4	90.7 (3)	C20—C21—C22	123.8 (6)
O2—U1—O4	88.7 (3)	C16—C21—C22	116.2 (6)
O6—U1—O4	141.9 (2)	O3—C22—C23	122.6 (8)
O3—U1—O4	70.6 (2)	O3—C22—C21	117.9 (7)
O1—U1—O5	85.1 (3)	C23—C22—C21	119.5 (7)
O2—U1—O5	94.1 (3)	C24—C23—C22	123.7 (8)
O6—U1—O5	71.3 (2)	C24—C23—H23	118.1
O3—U1—O5	141.6 (2)	C22—C23—H23	118.1
O4—U1—O5	146.8 (2)	O4—C24—C23	123.9 (8)
O1—U1—O7	86.8 (2)	O4—C24—C25	114.7 (7)
O2—U1—O7	90.9 (2)	C23—C24—C25	121.2 (7)
O6—U1—O7	145.0 (2)	C26—C25—C30	120.0
O3—U1—O7	142.7 (2)	C26—C25—C24	120.1 (5)
O4—U1—O7	72.8 (2)	C30—C25—C24	119.9 (5)
O5—U1—O7	74.0 (2)	C25—C26—C27	120.0
O7—S1—C37	104.7 (4)	C25—C26—H26	120.0
O7—S1—C38	104.7 (4)	C27—C26—H26	120.0
C37—S1—C38	97.3 (4)	C28—C27—C26	120.0
C22—O3—U1	140.5 (5)	C28—C27—H27	120.0
C24—O4—U1	135.0 (5)	C26—C27—H27	120.0
C7—O5—U1	137.5 (5)	C27—C28—C29	120.0
C9—O6—U1	139.2 (6)	C27—C28—H28	120.0
S1—O7—U1	121.1 (3)	C29—C28—H28	120.0
C2—C1—C6	120.0	C28—C29—C30	120.0
C2—C1—H1	120.0	C28—C29—H29	120.0
C6—C1—H1	120.0	C30—C29—H29	120.0
C1—C2—C3	120.0	C29—C30—C25	120.0
C1—C2—H2	120.0	C29—C30—H30	120.0
C3—C2—H2	120.0	C25—C30—H30	120.0
C4—C3—C2	120.0	C32—C31—C36	120.0
C4—C3—H3	120.0	C32—C31—H31	120.0
C2—C3—H3	120.0	C36—C31—H31	120.0
C5—C4—C3	120.0	C31—C32—C33	120.0
C5—C4—H4	120.0	C31—C32—H32	120.0
C3—C4—H4	120.0	C33—C32—H32	120.0
C4—C5—C6	120.0	C34—C33—C32	120.0
C4—C5—H5	120.0	C34—C33—H33	120.0
C6—C5—H5	120.0	C32—C33—H33	120.0
C5—C6—C1	120.0	C33—C34—C35	120.0
C5—C6—C7	122.1 (5)	C33—C34—H34	120.0
C1—C6—C7	117.5 (5)	C35—C34—H34	120.0
O5—C7—C8	123.2 (8)	C36—C35—C34	120.0
O5—C7—C6	118.2 (7)	C36—C35—H35	120.0
C8—C7—C6	118.5 (7)	C34—C35—H35	120.0
C7—C8—C9	125.4 (7)	C35—C36—C31	120.0
C7—C8—H8	117.3	C35—C36—C37	119.1 (6)
C9—C8—H8	117.3	C31—C36—C37	120.9 (6)
O6—C9—C8	121.2 (8)	C36—C37—S1	111.6 (6)
O6—C9—C10	115.2 (7)	C36—C37—H37A	109.3
C8—C9—C10	123.6 (7)	S1—C37—H37A	109.3
C11—C10—C15	120.0	C36—C37—H37B	109.3
C11—C10—C9	121.0 (5)	S1—C37—H37B	109.3
C15—C10—C9	119.0 (5)	H37A—C37—H37B	108.0
C10—C11—C12	120.0	C39—C38—S1	111.5 (6)
C10—C11—H11	120.0	C39—C38—H38A	109.3
C12—C11—H11	120.0	S1—C38—H38A	109.3
C13—C12—C11	120.0	C39—C38—H38B	109.3
C13—C12—H12	120.0	S1—C38—H38B	109.3
C11—C12—H12	120.0	H38A—C38—H38B	108.0
C14—C13—C12	120.0	C40—C39—C44	120.0
C14—C13—H13	120.0	C40—C39—C38	121.1 (5)
C12—C13—H13	120.0	C44—C39—C38	118.8 (5)
C13—C14—C15	120.0	C41—C40—C39	120.0
C13—C14—H14	120.0	C41—C40—H40	120.0
C15—C14—H14	120.0	C39—C40—H40	120.0
C14—C15—C10	120.0	C40—C41—C42	120.0
C14—C15—H15	120.0	C40—C41—H41	120.0
C10—C15—H15	120.0	C42—C41—H41	120.0
C17—C16—C21	120.0	C41—C42—C43	120.0
C17—C16—H16	120.0	C41—C42—H42	120.0
C21—C16—H16	120.0	C43—C42—H42	120.0
C16—C17—C18	120.0	C44—C43—C42	120.0
C16—C17—H17	120.0	C44—C43—H43	120.0
C18—C17—H17	120.0	C42—C43—H43	120.0
C19—C18—C17	120.0	C43—C44—C39	120.0
C19—C18—H18	120.0	C43—C44—H44	120.0
C17—C18—H18	120.0	C39—C44—H44	120.0
C18—C19—C20	120.0
O1—U1—O3—C22	99.6 (9)	C12—C13—C14—C15	0.0
O2—U1—O3—C22	−79.1 (9)	C13—C14—C15—C10	0.0
O6—U1—O3—C22	−163.8 (9)	C11—C10—C15—C14	0.0
O4—U1—O3—C22	7.6 (8)	C9—C10—C15—C14	178.3 (6)
O5—U1—O3—C22	177.1 (8)	C21—C16—C17—C18	0.0
O7—U1—O3—C22	19.8 (11)	C16—C17—C18—C19	0.0
O1—U1—O4—C24	−106.9 (8)	C17—C18—C19—C20	0.0
O2—U1—O4—C24	75.4 (8)	C18—C19—C20—C21	0.0
O6—U1—O4—C24	−7.6 (9)	C19—C20—C21—C16	0.0
O3—U1—O4—C24	−21.0 (7)	C19—C20—C21—C22	177.4 (9)
O5—U1—O4—C24	171.0 (6)	C17—C16—C21—C20	0.0
O7—U1—O4—C24	166.7 (8)	C17—C16—C21—C22	−177.6 (9)
O1—U1—O5—C7	80.7 (9)	U1—O3—C22—C23	2.4 (14)
O2—U1—O5—C7	−101.4 (9)	U1—O3—C22—C21	180.0 (6)
O6—U1—O5—C7	−16.4 (8)	C20—C21—C22—O3	−172.0 (7)
O3—U1—O5—C7	2.8 (11)	C16—C21—C22—O3	5.5 (11)
O4—U1—O5—C7	164.6 (7)	C20—C21—C22—C23	5.6 (12)
O7—U1—O5—C7	168.8 (9)	C16—C21—C22—C23	−176.9 (7)
O1—U1—O6—C9	−79.0 (10)	O3—C22—C23—C24	−7.2 (14)
O2—U1—O6—C9	99.6 (10)	C21—C22—C23—C24	175.3 (9)
O3—U1—O6—C9	−163.6 (10)	U1—O4—C24—C23	24.9 (13)
O4—U1—O6—C9	−176.8 (8)	U1—O4—C24—C25	−159.4 (5)
O5—U1—O6—C9	4.0 (9)	C22—C23—C24—O4	−5.8 (14)
O7—U1—O6—C9	12.7 (12)	C22—C23—C24—C25	178.8 (8)
C37—S1—O7—U1	−177.3 (4)	O4—C24—C25—C26	154.5 (6)
C38—S1—O7—U1	80.9 (4)	C23—C24—C25—C26	−29.7 (10)
O1—U1—O7—S1	−16.1 (4)	O4—C24—C25—C30	−24.9 (9)
O2—U1—O7—S1	164.0 (4)	C23—C24—C25—C30	150.9 (7)
O6—U1—O7—S1	−110.4 (5)	C30—C25—C26—C27	0.0
O3—U1—O7—S1	63.7 (5)	C24—C25—C26—C27	−179.4 (6)
O4—U1—O7—S1	75.7 (4)	C25—C26—C27—C28	0.0
O5—U1—O7—S1	−101.9 (4)	C26—C27—C28—C29	0.0
C6—C1—C2—C3	0.0	C27—C28—C29—C30	0.0
C1—C2—C3—C4	0.0	C28—C29—C30—C25	0.0
C2—C3—C4—C5	0.0	C26—C25—C30—C29	0.0
C3—C4—C5—C6	0.0	C24—C25—C30—C29	179.4 (6)
C4—C5—C6—C1	0.0	C36—C31—C32—C33	0.0
C4—C5—C6—C7	−172.4 (6)	C31—C32—C33—C34	0.0
C2—C1—C6—C5	0.0	C32—C33—C34—C35	0.0
C2—C1—C6—C7	172.8 (6)	C33—C34—C35—C36	0.0
U1—O5—C7—C8	20.8 (14)	C34—C35—C36—C31	0.0
U1—O5—C7—C6	−159.6 (5)	C34—C35—C36—C37	177.7 (7)
C5—C6—C7—O5	163.3 (6)	C32—C31—C36—C35	0.0
C1—C6—C7—O5	−9.3 (9)	C32—C31—C36—C37	−177.6 (7)
C5—C6—C7—C8	−17.1 (10)	C35—C36—C37—S1	96.2 (7)
C1—C6—C7—C8	170.2 (7)	C31—C36—C37—S1	−86.1 (7)
O5—C7—C8—C9	−6.9 (15)	O7—S1—C37—C36	74.1 (7)
C6—C7—C8—C9	173.5 (8)	C38—S1—C37—C36	−178.6 (7)
U1—O6—C9—C8	2.7 (15)	O7—S1—C38—C39	−165.7 (5)
U1—O6—C9—C10	−179.9 (6)	C37—S1—C38—C39	87.0 (6)
C7—C8—C9—O6	−3.9 (15)	S1—C38—C39—C40	68.7 (7)
C7—C8—C9—C10	178.9 (8)	S1—C38—C39—C44	−114.2 (5)
O6—C9—C10—C11	−166.9 (6)	C44—C39—C40—C41	0.0
C8—C9—C10—C11	10.5 (10)	C38—C39—C40—C41	177.1 (7)
O6—C9—C10—C15	14.9 (10)	C39—C40—C41—C42	0.0
C8—C9—C10—C15	−167.8 (7)	C40—C41—C42—C43	0.0
C15—C10—C11—C12	0.0	C41—C42—C43—C44	0.0
C9—C10—C11—C12	−178.2 (6)	C42—C43—C44—C39	0.0
C10—C11—C12—C13	0.0	C40—C39—C44—C43	0.0
C11—C12—C13—C14	0.0	C38—C39—C44—C43	−177.2 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O1^i	0.93	2.48	3.15 (1)	130
C28—H28···O1^ii	0.93	2.50	3.25 (1)	138
C38—H38B···O2^iii	0.97	2.57	3.52 (1)	166
C43—H43···O2^iv	0.93	2.57	3.44 (1)	156

Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, −y+1/2, −z; (iv) x−1, y, z.