Bis(1,3-di­phenyl­propane-1,3-dionato-O,O')(di­phenyl sulfoxide-O)dioxouranium(VI)

In the title complex, [UO₂(dbm)₂(PhSOPh)] or [UO₂(C₁₅H₁₁O₂)(C₁₂H₁₀OS)], where dbm is 1,3-di­phenyl­propane-1,3-dionate, the U atom is surrounded by seven O atoms to give a distorted pentagonal bipyramidal geometry. The U-O_uranyl and U-O_dbm distances (dbm is 1,3-di­phenyl­propane-1,3-dionate) are in the ranges 1.760 (6)-1.776 (5) and 2.308 (4)-2.417 (4) Å, respectively, while the U-O_sulfoxide distance is 2.427 (4) Å.

S1. Comment

An enhancement in solvent extraction separation of the uranium(VI) ion from nitric acid medium using a mixture of dibenzoylmethane (Hdbm) and diphenyl sulfoxide has been reported (Subramanian & Vrswanatha, 1969). The species responsible for synergism has been isolated in the solid state and characterized by spectroscopy and elemental analyses (Subramanian & Vrswanatha, 1969). However, there is no report on the structural characterization of the complex responsible for this extraction. As part of our systematic work on synergistic complexes (the species responsible for enhancement) of uranyl bis(β-diketonates) with neutral donor ligands (Kannan & Venugopal, 1995; Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997; Kannan, 2000), we report here the structure of the title complex, (I).

The uranium(VI) ion is surrounded by seven O atoms (four dbm-O, two uranyl-O and one sulfoxide-O atom) to give pentagonal bipyramidal geometry. The four dbm O atoms and the sulfoxide O atom form a planar pentagon. Two uranyl oxygen atoms occupy the apices. A pseudo-twofold axis passes through the U1, O1 and S1 atoms. The U—O bond distances [U—O_uranyl 1.760 (6) and 1.776 (5) Å; U—O_diketonate 2.308 (4), 2.329 (3), 2.345 (4) and 2.417 (4) Å] are within accepted ranges (Kannan, Venugopal, Pillai, Droege & Barnes, 1996; Kannan, Venugopal, Pillai, Droege, Barnes & Schlember, 1996; Kannan et al., 1997). The U—O_sulfoxide distance of 2.427 (4) Å is slightly longer than observed in [UO₂(dbm)₂(PHCH₂SOCH₃)] [2.375 (6) Å; Kannan, Venugopal, Pillai, Droege & Barnes, 1996]. This may be due to a steric effect caused by the bulkier phenyl group of PhSOPh in the title complex compared with the CH₂ or CH₃ group of PhCH₂SOCH₃ in [UO₂(dbm)₂(PHCH₂SOCH₃)]. The O—U—O angles are close to the regular pentagon value of 72°. The C—C—C angles of the β-diketonate group agree with the reported values of 124.4 (8) and 124.5 (8)° (Uchida et al., 1977). The aromatic rings attached to S makes a dihedral angle of 79.3 (4)° with each other. Overall bond angles and distances show that the U atom has distorted pentagonal bipyramidal geometry.

This structural observation is in agreement with the IR spectral results that Δν_S═O[ν(free ligand) – ν(in complex)] of the title complex is lower (42 cm⁻¹) compared to that of [UO₂(dbm)₂(PHCH₂SOCH₃)] (50 cm⁻¹). This further indicates that the PhCH₂SOCH₃ forms stronger bond with [UO₂(dbm)₂] than PhSOPh. The molecular packing is stabilized extensively by intermolecular π···π interaction [Cg4···Cg6(x + 1, y, z) = 3.777 (4) Å] and C—H···π interactions involving the aromatic rings (Table 2; Cg1–Cg6 are the centroids of the aromatic rings C1–C, C7–C12, C13–C18, C22–C27, C28–C33 and C37–C42 respectively). Because of these interactions the exterior O—C—C angles, take low values, while their opposite C—C—C angles take higher values. In the solid state, the molecules are translated along the ac plane connected by C—H···π interactions.

S2. Experimental

To a hot chloroform (10 ml) solution of UO₂(dbm)₂·2H₂O (300 mg, 0.399 mmol) was added diphenyl sulfoxide (80.6 mg, 0.399 mmol) and the resulting solution was then refluxed for 15 min. The solution was layered with dodecane (2 ml) and allowed to evaporate slowly. The crystals obtained were washed with hexane and dried (yield 315 mg, 86%, m.p. 498 K). Found: C 55.0, H 4.6%. Calculated for C₄₂H₃₂O₇SU: C 54.9, H 3.5%. IR (Nujol, ν, cm⁻¹): 1590, 1315, 993, 910. ¹H NMR (CDCl3, δ, p.p.m.): 7.26 (s, 2H, CH, dbm), 7.4–8.5 (m, 30H, C₆H₅, dbm + PhSOPh). A crystal suitable for X-ray analysis was obtained from a chloroform/dodecane mixture on slow evaporation.

S3. Refinement

All the Hatoms were fixed geometrically and were allowed to ride on their parent atoms.

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; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Bis(1,3-diphenylpropane-1,3-dionato-O,O')(diphenyl sulfoxide-S)dioxouranium(VI)

Crystal data

[UO2(C15H11O2)(C12H10OS)]	Z = 2
Mr = 918.77	F(000) = 896
Triclinic, P1	Dx = 1.718 Mg m^−3
a = 10.2673 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3671 (2) Å	Cell parameters from 8192 reflections
c = 17.3596 (1) Å	θ = 1.2–29.5°
α = 95.459 (1)°	µ = 4.68 mm^−1
β = 103.172 (1)°	T = 293 K
γ = 96.048 (1)°	Rectangular block, orange
V = 1775.57 (4) Å^3	0.40 × 0.36 × 0.28 mm

Data collection

Siemens SMART CCD area-detector diffractometer	8050 independent reflections
Radiation source: fine-focus sealed tube	6366 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 8.33 pixels mm^-1	θmax = 27.5°, θmin = 1.2°
ω scans	h = −11→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.170, Tmax = 0.270	l = −22→20
12473 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0101P)^2] where P = (Fo^2 + 2Fc^2)/3
8050 reflections	(Δ/σ)max = 0.001
460 parameters	Δρmax = 2.56 e Å^−3
0 restraints	Δρmin = −2.28 e Å^−3

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 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the 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	−0.357701 (19)	0.282103 (19)	−0.258643 (13)	0.03757 (9)
S1	−0.57778 (16)	0.50627 (16)	−0.21490 (10)	0.0496 (4)
O1	−0.4648 (4)	0.4795 (4)	−0.2529 (3)	0.0581 (13)
O2	−0.1937 (4)	0.4438 (4)	−0.1776 (3)	0.0573 (13)
O3	−0.1572 (4)	0.1947 (4)	−0.2166 (3)	0.0488 (11)
O4	−0.5909 (4)	0.2223 (4)	−0.3301 (3)	0.0456 (11)
O5	−0.3897 (5)	0.0672 (4)	−0.3155 (3)	0.0750 (18)
O6	−0.3107 (5)	0.3322 (5)	−0.3447 (3)	0.0564 (12)
O7	−0.4076 (5)	0.2374 (5)	−0.1733 (3)	0.0621 (13)
C1	−0.5142 (7)	0.6555 (7)	−0.1484 (4)	0.0528 (17)
C2	−0.4695 (8)	0.7691 (9)	−0.1752 (5)	0.072 (2)
H2A	−0.4744	0.7724	−0.2291	0.087*
C3	−0.4173 (9)	0.8783 (9)	−0.1199 (7)	0.088 (3)
H3A	−0.3844	0.9552	−0.1365	0.105*
C4	−0.4138 (10)	0.8735 (12)	−0.0409 (7)	0.097 (4)
H4A	−0.3820	0.9479	−0.0043	0.116*
C5	−0.4569 (10)	0.7591 (13)	−0.0160 (6)	0.094 (3)
H5A	−0.4493	0.7530	0.0379	0.113*
C6	−0.5118 (10)	0.6533 (10)	−0.0719 (5)	0.087 (3)
H6A	−0.5485	0.5777	−0.0556	0.104*
C7	−0.6996 (6)	0.5637 (6)	−0.2890 (4)	0.0465 (16)
C8	−0.6729 (6)	0.5966 (6)	−0.3595 (4)	0.0488 (16)
H8A	−0.5873	0.5963	−0.3688	0.059*
C9	−0.7805 (8)	0.6309 (7)	−0.4169 (5)	0.066 (2)
H9A	−0.7658	0.6546	−0.4648	0.079*
C10	−0.9051 (8)	0.6298 (8)	−0.4028 (6)	0.072 (2)
H10A	−0.9748	0.6533	−0.4412	0.086*
C11	−0.9301 (8)	0.5940 (9)	−0.3323 (6)	0.082 (3)
H11A	−1.0164	0.5920	−0.3237	0.099*
C12	−0.8287 (8)	0.5622 (8)	−0.2761 (5)	0.064 (2)
H12A	−0.8451	0.5390	−0.2284	0.077*
C13	−0.1022 (6)	0.6741 (5)	−0.0834 (4)	0.0461 (15)
H13A	−0.1927	0.6547	−0.1100	0.055*
C14	−0.0570 (8)	0.7922 (6)	−0.0337 (5)	0.0601 (19)
H14A	−0.1179	0.8501	−0.0269	0.072*
C15	0.0740 (7)	0.8227 (6)	0.0042 (4)	0.0539 (17)
H15A	0.1041	0.9025	0.0359	0.065*
C16	0.1632 (7)	0.7354 (7)	−0.0041 (4)	0.0564 (18)
H16A	0.2536	0.7555	0.0226	0.068*
C17	0.1190 (6)	0.6185 (6)	−0.0517 (4)	0.0455 (15)
H17A	0.1799	0.5596	−0.0562	0.055*
C18	−0.0144 (5)	0.5865 (5)	−0.0931 (3)	0.0340 (12)
C19	−0.0683 (5)	0.4572 (5)	−0.1431 (3)	0.0357 (12)
C20	0.0154 (5)	0.3614 (5)	−0.1500 (3)	0.0367 (13)
H20A	0.1080	0.3837	−0.1301	0.044*
C21	−0.0333 (5)	0.2334 (5)	−0.1855 (3)	0.0346 (12)
C22	0.0580 (5)	0.1310 (5)	−0.1843 (3)	0.0336 (12)
C23	0.1948 (6)	0.1594 (6)	−0.1812 (4)	0.0450 (15)
H23A	0.2320	0.2460	−0.1784	0.054*
C24	0.2765 (6)	0.0622 (6)	−0.1822 (4)	0.0486 (16)
H24A	0.3675	0.0831	−0.1804	0.058*
C25	0.2222 (7)	−0.0659 (7)	−0.1859 (4)	0.0555 (18)
H25A	0.2769	−0.1318	−0.1869	0.067*
C26	0.0862 (7)	−0.0979 (6)	−0.1883 (4)	0.0535 (17)
H26A	0.0496	−0.1844	−0.1902	0.064*
C27	0.0069 (6)	0.0011 (5)	−0.1878 (4)	0.0427 (14)
H27A	−0.0842	−0.0202	−0.1898	0.051*
C28	−0.4794 (6)	−0.2066 (6)	−0.4666 (4)	0.0434 (14)
H28A	−0.5470	−0.1766	−0.5033	0.052*
C29	−0.4304 (8)	−0.3212 (7)	−0.4871 (5)	0.0600 (19)
H29A	−0.4638	−0.3668	−0.5377	0.072*
C30	−0.3329 (8)	−0.3676 (7)	−0.4330 (5)	0.065 (2)
H30A	−0.3024	−0.4460	−0.4467	0.078*
C31	−0.2788 (7)	−0.2984 (7)	−0.3574 (5)	0.069 (2)
H31A	−0.2128	−0.3299	−0.3204	0.083*
C32	−0.3255 (6)	−0.1822 (6)	−0.3387 (4)	0.0548 (18)
H32A	−0.2875	−0.1334	−0.2893	0.066*
C33	−0.4282 (5)	−0.1364 (5)	−0.3920 (4)	0.0386 (13)
C34	−0.4784 (6)	−0.0129 (5)	−0.3666 (4)	0.0399 (13)
C35	−0.6097 (5)	0.0072 (5)	−0.3921 (3)	0.0390 (13)
H35A	−0.6677	−0.0576	−0.4283	0.047*
C36	−0.6637 (6)	0.1189 (6)	−0.3675 (3)	0.0384 (13)
C37	−0.8120 (5)	0.1186 (5)	−0.3846 (3)	0.0354 (12)
C38	−0.8661 (6)	0.2354 (6)	−0.3875 (4)	0.0456 (15)
H38A	−0.8093	0.3134	−0.3825	0.055*
C39	−1.0051 (7)	0.2376 (7)	−0.3977 (4)	0.0574 (19)
H39A	−1.0409	0.3163	−0.4002	0.069*
C40	−1.0879 (6)	0.1222 (8)	−0.4039 (4)	0.0564 (18)
H40A	−1.1801	0.1228	−0.4093	0.068*
C41	−1.0357 (6)	0.0067 (7)	−0.4022 (4)	0.0536 (17)
H41A	−1.0928	−0.0712	−0.4078	0.064*
C42	−0.8992 (6)	0.0046 (6)	−0.3923 (4)	0.0445 (14)
H42A	−0.8650	−0.0749	−0.3908	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.02418 (12)	0.02839 (12)	0.05183 (16)	0.00718 (8)	−0.00491 (9)	−0.00649 (9)
S1	0.0441 (9)	0.0482 (9)	0.0605 (11)	0.0140 (7)	0.0138 (7)	0.0155 (8)
O1	0.032 (2)	0.051 (3)	0.085 (4)	0.015 (2)	0.004 (2)	−0.008 (2)
O2	0.031 (2)	0.033 (2)	0.090 (4)	0.0091 (18)	−0.015 (2)	−0.019 (2)
O3	0.024 (2)	0.035 (2)	0.074 (3)	0.0074 (17)	−0.0112 (18)	−0.007 (2)
O4	0.025 (2)	0.037 (2)	0.064 (3)	0.0080 (17)	−0.0079 (18)	−0.0065 (19)
O5	0.040 (3)	0.036 (2)	0.121 (5)	0.011 (2)	−0.025 (3)	−0.030 (3)
O6	0.052 (3)	0.062 (3)	0.053 (3)	0.010 (2)	0.008 (2)	0.006 (2)
O7	0.044 (3)	0.067 (3)	0.064 (3)	0.006 (2)	−0.006 (2)	−0.003 (2)
C1	0.050 (4)	0.060 (4)	0.050 (4)	0.029 (3)	0.006 (3)	0.006 (3)
C2	0.061 (5)	0.083 (6)	0.065 (5)	0.017 (4)	0.005 (4)	−0.012 (5)
C3	0.057 (5)	0.074 (6)	0.124 (9)	0.024 (5)	0.006 (5)	−0.002 (6)
C4	0.072 (6)	0.116 (9)	0.086 (8)	0.033 (6)	0.003 (5)	−0.045 (7)
C5	0.082 (7)	0.139 (10)	0.048 (5)	0.006 (7)	0.005 (4)	−0.016 (6)
C6	0.094 (7)	0.099 (7)	0.057 (6)	0.004 (6)	0.001 (5)	0.012 (5)
C7	0.044 (4)	0.034 (3)	0.057 (4)	0.017 (3)	0.000 (3)	−0.004 (3)
C8	0.039 (3)	0.050 (4)	0.057 (4)	0.007 (3)	0.012 (3)	0.005 (3)
C9	0.067 (5)	0.066 (5)	0.060 (5)	0.010 (4)	0.004 (4)	0.016 (4)
C10	0.057 (5)	0.067 (5)	0.087 (6)	0.027 (4)	−0.002 (4)	0.009 (5)
C11	0.038 (4)	0.081 (6)	0.126 (8)	0.020 (4)	0.017 (5)	−0.009 (6)
C12	0.066 (5)	0.069 (5)	0.069 (5)	0.018 (4)	0.034 (4)	0.008 (4)
C13	0.037 (3)	0.030 (3)	0.068 (4)	0.001 (2)	0.011 (3)	0.000 (3)
C14	0.058 (5)	0.042 (4)	0.081 (5)	0.008 (3)	0.022 (4)	−0.006 (3)
C15	0.064 (5)	0.038 (3)	0.052 (4)	−0.013 (3)	0.013 (3)	−0.008 (3)
C16	0.048 (4)	0.050 (4)	0.056 (4)	−0.011 (3)	−0.005 (3)	−0.006 (3)
C17	0.037 (3)	0.044 (3)	0.050 (4)	0.005 (3)	0.003 (3)	−0.003 (3)
C18	0.033 (3)	0.029 (3)	0.039 (3)	0.000 (2)	0.009 (2)	0.006 (2)
C19	0.031 (3)	0.029 (3)	0.043 (3)	0.001 (2)	0.001 (2)	0.006 (2)
C20	0.020 (3)	0.036 (3)	0.049 (3)	0.001 (2)	0.001 (2)	0.003 (3)
C21	0.029 (3)	0.034 (3)	0.039 (3)	0.006 (2)	0.003 (2)	0.008 (2)
C22	0.031 (3)	0.034 (3)	0.035 (3)	0.008 (2)	0.005 (2)	−0.001 (2)
C23	0.032 (3)	0.047 (3)	0.055 (4)	0.010 (3)	0.006 (3)	0.005 (3)
C24	0.027 (3)	0.061 (4)	0.054 (4)	0.013 (3)	0.002 (3)	0.001 (3)
C25	0.049 (4)	0.059 (4)	0.060 (4)	0.033 (3)	0.006 (3)	0.005 (3)
C26	0.060 (4)	0.039 (3)	0.066 (5)	0.019 (3)	0.018 (3)	0.010 (3)
C27	0.038 (3)	0.028 (3)	0.062 (4)	0.005 (2)	0.012 (3)	0.003 (3)
C28	0.049 (4)	0.038 (3)	0.045 (4)	0.006 (3)	0.013 (3)	0.005 (3)
C29	0.073 (5)	0.047 (4)	0.064 (5)	0.007 (4)	0.028 (4)	−0.006 (3)
C30	0.064 (5)	0.046 (4)	0.090 (6)	0.018 (4)	0.029 (4)	−0.005 (4)
C31	0.040 (4)	0.059 (4)	0.105 (7)	0.023 (3)	0.007 (4)	−0.004 (4)
C32	0.035 (3)	0.052 (4)	0.069 (5)	0.009 (3)	0.004 (3)	−0.015 (3)
C33	0.030 (3)	0.032 (3)	0.057 (4)	0.002 (2)	0.018 (3)	0.003 (3)
C34	0.038 (3)	0.028 (3)	0.049 (4)	−0.001 (2)	0.006 (3)	0.001 (2)
C35	0.024 (3)	0.040 (3)	0.045 (3)	0.002 (2)	−0.001 (2)	−0.007 (3)
C36	0.032 (3)	0.044 (3)	0.037 (3)	0.003 (2)	0.004 (2)	0.002 (3)
C37	0.032 (3)	0.042 (3)	0.027 (3)	0.003 (2)	−0.001 (2)	0.001 (2)
C38	0.034 (3)	0.042 (3)	0.053 (4)	0.004 (3)	0.000 (3)	−0.003 (3)
C39	0.046 (4)	0.061 (4)	0.060 (4)	0.024 (3)	−0.005 (3)	0.006 (3)
C40	0.027 (3)	0.088 (5)	0.048 (4)	0.008 (3)	0.003 (3)	−0.007 (4)
C41	0.038 (4)	0.059 (4)	0.060 (4)	−0.006 (3)	0.011 (3)	−0.001 (3)
C42	0.039 (3)	0.039 (3)	0.052 (4)	−0.001 (3)	0.009 (3)	0.000 (3)

Geometric parameters (Å, º)

U1—O7	1.760 (6)	C15—C16	1.374 (10)
U1—O6	1.776 (5)	C16—C17	1.371 (8)
U1—O5	2.308 (4)	C17—C18	1.383 (8)
U1—O3	2.329 (3)	C18—C19	1.504 (7)
U1—O2	2.345 (4)	C19—C20	1.394 (7)
U1—O4	2.417 (4)	C20—C21	1.398 (7)
U1—O1	2.427 (4)	C21—C22	1.486 (7)
S1—O1	1.496 (5)	C22—C27	1.384 (8)
S1—C7	1.773 (6)	C22—C23	1.392 (8)
S1—C1	1.804 (7)	C23—C24	1.379 (8)
O2—C19	1.277 (6)	C24—C25	1.375 (10)
O3—C21	1.269 (6)	C25—C26	1.392 (10)
O4—C36	1.268 (6)	C26—C27	1.376 (8)
O5—C34	1.280 (6)	C28—C33	1.383 (8)
C1—C6	1.325 (11)	C28—C29	1.384 (9)
C1—C2	1.378 (11)	C29—C30	1.370 (11)
C2—C3	1.386 (12)	C30—C31	1.397 (11)
C3—C4	1.368 (14)	C31—C32	1.380 (9)
C4—C5	1.365 (14)	C32—C33	1.393 (8)
C5—C6	1.371 (12)	C33—C34	1.496 (7)
C7—C8	1.379 (9)	C34—C35	1.365 (7)
C7—C12	1.393 (10)	C35—C36	1.407 (8)
C8—C9	1.410 (9)	C36—C37	1.483 (8)
C9—C10	1.355 (12)	C37—C42	1.381 (8)
C10—C11	1.383 (12)	C37—C38	1.385 (8)
C11—C12	1.347 (11)	C38—C39	1.401 (9)
C13—C18	1.370 (8)	C39—C40	1.374 (10)
C13—C14	1.398 (9)	C40—C41	1.362 (9)
C14—C15	1.345 (10)	C41—C42	1.376 (8)
O7—U1—O6	177.91 (19)	C15—C14—C13	120.5 (6)
O7—U1—O5	91.8 (2)	C14—C15—C16	119.7 (6)
O6—U1—O5	89.8 (2)	C17—C16—C15	120.1 (6)
O7—U1—O3	89.3 (2)	C16—C17—C18	121.3 (6)
O6—U1—O3	92.45 (19)	C13—C18—C17	117.8 (5)
O5—U1—O3	72.0 (1)	C13—C18—C19	119.0 (5)
O7—U1—O2	89.5 (2)	C17—C18—C19	123.0 (5)
O6—U1—O2	90.1 (2)	O2—C19—C20	124.0 (5)
O5—U1—O2	142.32 (14)	O2—C19—C18	114.9 (5)
O3—U1—O2	70.4 (1)	C20—C19—C18	121.0 (5)
O7—U1—O4	87.01 (18)	C19—C20—C21	123.1 (5)
O6—U1—O4	92.24 (18)	O3—C21—C20	123.2 (5)
O5—U1—O4	70.6 (1)	O3—C21—C22	115.5 (5)
O3—U1—O4	142.22 (13)	C20—C21—C22	121.2 (5)
O2—U1—O4	147.06 (13)	C27—C22—C23	117.4 (5)
O7—U1—O1	91.1 (2)	C27—C22—C21	119.9 (5)
O6—U1—O1	86.8 (2)	C23—C22—C21	122.8 (5)
O5—U1—O1	143.64 (14)	C24—C23—C22	121.6 (6)
O3—U1—O1	144.29 (14)	C25—C24—C23	119.5 (6)
O2—U1—O1	73.9 (1)	C24—C25—C26	120.6 (6)
O4—U1—O1	73.4 (1)	C27—C26—C25	118.7 (6)
O1—S1—C7	105.8 (3)	C26—C27—C22	122.3 (6)
O1—S1—C1	104.6 (3)	C33—C28—C29	120.3 (6)
C7—S1—C1	100.3 (3)	C30—C29—C28	120.3 (7)
S1—O1—U1	128.3 (3)	C29—C30—C31	120.5 (6)
C19—O2—U1	138.2 (3)	C32—C31—C30	118.5 (7)
C21—O3—U1	139.2 (3)	C31—C32—C33	121.4 (6)
C36—O4—U1	136.2 (3)	C28—C33—C32	118.8 (5)
C34—O5—U1	139.5 (4)	C28—C33—C34	122.6 (5)
C6—C1—C2	120.2 (8)	C32—C33—C34	118.7 (5)
C6—C1—S1	117.8 (7)	O5—C34—C35	123.7 (5)
C2—C1—S1	122.0 (6)	O5—C34—C33	114.0 (5)
C1—C2—C3	118.5 (9)	C35—C34—C33	122.2 (5)
C4—C3—C2	120.4 (10)	C34—C35—C36	124.6 (5)
C5—C4—C3	119.8 (9)	O4—C36—C35	123.0 (5)
C4—C5—C6	118.9 (10)	O4—C36—C37	117.1 (5)
C1—C6—C5	122.0 (10)	C35—C36—C37	119.9 (5)
C8—C7—C12	120.9 (6)	C42—C37—C38	118.0 (5)
C8—C7—S1	122.3 (5)	C42—C37—C36	121.7 (5)
C12—C7—S1	116.5 (6)	C38—C37—C36	120.1 (5)
C7—C8—C9	117.4 (6)	C37—C38—C39	120.9 (6)
C10—C9—C8	120.7 (8)	C40—C39—C38	119.2 (6)
C9—C10—C11	120.9 (7)	C41—C40—C39	120.3 (6)
C12—C11—C10	119.6 (8)	C40—C41—C42	120.5 (6)
C11—C12—C7	120.5 (8)	C41—C42—C37	121.2 (6)
C18—C13—C14	120.6 (6)
C7—S1—O1—U1	−128.6 (3)	C14—C13—C18—C17	0.7 (9)
C1—S1—O1—U1	125.9 (3)	C14—C13—C18—C19	176.4 (6)
O7—U1—O1—S1	−23.8 (3)	C16—C17—C18—C13	−1.7 (10)
O6—U1—O1—S1	156.0 (3)	C16—C17—C18—C19	−177.3 (6)
O5—U1—O1—S1	70.8 (5)	U1—O2—C19—C20	3.2 (10)
O3—U1—O1—S1	−114.2 (4)	U1—O2—C19—C18	−177.0 (4)
O2—U1—O1—S1	−113.0 (4)	C13—C18—C19—O2	4.8 (8)
O4—U1—O1—S1	62.7 (3)	C17—C18—C19—O2	−179.7 (6)
O7—U1—O2—C19	95.3 (7)	C13—C18—C19—C20	−175.3 (6)
O6—U1—O2—C19	−86.8 (7)	C17—C18—C19—C20	0.2 (9)
O5—U1—O2—C19	2.9 (8)	O2—C19—C20—C21	−10.2 (10)
O3—U1—O2—C19	5.8 (6)	C18—C19—C20—C21	170.0 (5)
O4—U1—O2—C19	179.0 (5)	U1—O3—C21—C20	14.3 (10)
O1—U1—O2—C19	−173.5 (7)	U1—O3—C21—C22	−169.4 (4)
O7—U1—O3—C21	−104.7 (6)	C19—C20—C21—O3	2.3 (9)
O6—U1—O3—C21	74.2 (6)	C19—C20—C21—C22	−173.7 (6)
O5—U1—O3—C21	163.1 (7)	O3—C21—C22—C27	−23.5 (8)
O2—U1—O3—C21	−15.0 (6)	C20—C21—C22—C27	152.8 (6)
O4—U1—O3—C21	171.0 (5)	O3—C21—C22—C23	155.3 (6)
O1—U1—O3—C21	−13.8 (8)	C20—C21—C22—C23	−28.4 (9)
O7—U1—O4—C36	−88.6 (6)	C27—C22—C23—C24	0.5 (9)
O6—U1—O4—C36	93.4 (6)	C21—C22—C23—C24	−178.3 (6)
O5—U1—O4—C36	4.4 (6)	C22—C23—C24—C25	−0.3 (10)
O3—U1—O4—C36	−3.6 (7)	C23—C24—C25—C26	−0.3 (10)
O2—U1—O4—C36	−173.0 (5)	C24—C25—C26—C27	0.8 (10)
O1—U1—O4—C36	179.4 (6)	C25—C26—C27—C22	−0.6 (10)
O7—U1—O5—C34	98.4 (8)	C23—C22—C27—C26	0.0 (9)
O6—U1—O5—C34	−80.2 (8)	C21—C22—C27—C26	178.8 (6)
O3—U1—O5—C34	−172.9 (8)	C33—C28—C29—C30	1.5 (11)
O2—U1—O5—C34	−170.1 (7)	C28—C29—C30—C31	−1.8 (12)
O4—U1—O5—C34	12.2 (7)	C29—C30—C31—C32	−0.2 (13)
O1—U1—O5—C34	4.1 (10)	C30—C31—C32—C33	2.7 (12)
O1—S1—C1—C6	−122.7 (6)	C29—C28—C33—C32	1.0 (10)
C7—S1—C1—C6	127.8 (6)	C29—C28—C33—C34	−179.3 (6)
O1—S1—C1—C2	57.5 (6)	C31—C32—C33—C28	−3.1 (11)
C7—S1—C1—C2	−52.0 (7)	C31—C32—C33—C34	177.2 (7)
C6—C1—C2—C3	2.7 (11)	U1—O5—C34—C35	−16.7 (12)
S1—C1—C2—C3	−177.5 (6)	U1—O5—C34—C33	167.4 (5)
C1—C2—C3—C4	−1.7 (12)	C28—C33—C34—O5	−150.8 (6)
C2—C3—C4—C5	2.6 (14)	C32—C33—C34—O5	28.9 (9)
C3—C4—C5—C6	−4.5 (15)	C28—C33—C34—C35	33.3 (9)
C2—C1—C6—C5	−4.7 (13)	C32—C33—C34—C35	−147.0 (6)
S1—C1—C6—C5	175.5 (8)	O5—C34—C35—C36	1.7 (10)
C4—C5—C6—C1	5.6 (15)	C33—C34—C35—C36	177.3 (6)
O1—S1—C7—C8	−10.7 (6)	U1—O4—C36—C35	−15.1 (9)
C1—S1—C7—C8	97.9 (5)	U1—O4—C36—C37	164.3 (4)
O1—S1—C7—C12	163.3 (5)	C34—C35—C36—O4	12.9 (10)
C1—S1—C7—C12	−88.2 (6)	C34—C35—C36—C37	−166.6 (6)
C12—C7—C8—C9	1.2 (9)	O4—C36—C37—C42	−151.6 (6)
S1—C7—C8—C9	174.9 (5)	C35—C36—C37—C42	27.8 (8)
C7—C8—C9—C10	−0.7 (11)	O4—C36—C37—C38	23.6 (8)
C8—C9—C10—C11	−0.5 (13)	C35—C36—C37—C38	−157.0 (6)
C9—C10—C11—C12	1.2 (13)	C42—C37—C38—C39	0.1 (9)
C10—C11—C12—C7	−0.7 (13)	C36—C37—C38—C39	−175.3 (6)
C8—C7—C12—C11	−0.5 (11)	C37—C38—C39—C40	0.8 (10)
S1—C7—C12—C11	−174.6 (6)	C38—C39—C40—C41	−1.7 (10)
C18—C13—C14—C15	1.1 (11)	C39—C40—C41—C42	1.6 (10)
C13—C14—C15—C16	−1.9 (11)	C40—C41—C42—C37	−0.6 (10)
C14—C15—C16—C17	0.9 (11)	C38—C37—C42—C41	−0.3 (9)
C15—C16—C17—C18	0.9 (11)	C36—C37—C42—C41	175.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1	0.93	2.59	2.939 (8)	103
C13—H13A···O2	0.93	2.38	2.710 (7)	101
C8—H8A···Cg5^i	0.93	2.81	3.597 (8)	144
C13—H13A···Cg1	0.93	3.17	3.891 (8)	136
C25—H25A···Cg1^ii	0.93	3.12	3.917 (8)	144
C26—H26A···Cg3^iii	0.93	2.93	3.493 (8)	121
C38—H38A···Cg2	0.93	2.93	3.700 (7)	141

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