Inclusion of diprotonated [2.2.2]cryptand in the cavity of uranyl-complexed p-phenyl­tetra­homodioxacalix[4]arene

In the title compound, 4,7,13,16,21,24-hexa­oxa-1,10-diazo­nia­bicyclo­[8.8.8]hexa­cosane dioxo[7,13,21,27-tetra­phenyl-3,17-di­oxa­penta­cyclo­[23.3.1.1^5,9.1^11,15.1^19,23]ditriaconta-1(29),5,7,9(30),11(31),12,14,19(32),20,22,25,27-dodeca­ene-29,30,31,32-tetra­olato]uranium dimethyl sulfoxide tri­solvate, (C₁₈H₃₈N₂O₆)[U(C₅₄H₄₀O₆)O₂]·3C₂H₆OS, the uranyl ion is bound to the four phenoxide groups of the deprotonated p-phenyl­tetra­homodioxacalix[4]arene ligand in a cone conformation, resulting in a dianionic complex. The diprotonated [2.2.2]cryptand counter-ion is located in the cavity defined by the eight aromatic rings of the homooxacalixarene, where it is held by cation–anion, cation–π and possibly C—H...π inter­actions. Dimerization in the packing leads to the formation of sandwich assemblages in which two diprotonated [2.2.2]cryptands are encompassed by two uranyl complexes.

S1. Comment

The uranyl complexes of calixarenes and their derivatives homo-, homooxa- and homoazacalixarenes have been widely investigated in the past few years (Harrowfield, 1997; Thuéry, Nierlich, Harrowfield & Ogden, 2001). It has been shown in particular that uranyl complexes of homooxacalixarenes, in which at least one methylene bridge is replaced by a –CH₂—O—CH₂– link (Masci, 2001), could be used to build supramolecular architectures. The presence both of a hydrophobic cavity surrounded by aromatic rings, which can be involved in various weak interactions (cation–π and C—H···π), and of oxo (uranyl), ether and phenoxide groups directed either inside or outside the cavity provide several sites for counter-ion bonding. Primary, secondary and tertiary ammonium ions can thus give extended assemblages through hydrogen bonds and interactions with the aromatic rings (Masci et al., 2002, 2002a,b), whereas alkali metal counter-ions can bind to the uranyl oxo groups to give dimers or infinite chains (Thuéry & Masci, 2003, 2004). We have reported previously the synthesis and crystal structure of mono-anionic uranyl complexes with p-R-hexahomotrioxacalix[3]arene (R = tert-butyl or phenyl), with protonated [2.2.2]cryptand as counter-ion (Masci et al., 2002b). Depending on the stoichiometry, it is possible to obtain two different arrangements, with either the mono-protonated [2.2.2]cryptand nested in the cavity of one complex molecule or its di-protonated form sandwiched by two complexes facing each other. We report here the structure of the analogous complex with the larger p-phenyltetrahomodioxacalix[4]arene. This ligand, as well as the p-methyl and p-tert-butyl derivatives, is known to complex one uranyl ion with its four phenoxide groups, the ether O atoms being non-coordinating (Thuéry, Nierlich, Vicens et al., 2001; Masci et al., 2002; Thuéry & Masci, 2003).

The asymmetric unit in (I) contains one complex dianion, one dihydro[2.2.2]cryptand and three solvent dimethyl sulfoxide molecules. A view of the dianion and the cryptand is shown in Fig. 1. The uranyl ion lies at the centre of the homooxacalixarene, in a cone conformation, and it is bound to all four phenoxide O atoms with a mean U—O bond length of 2.278 (15) Å, as in the previously reported complexes with similar ligands. Ether atoms O3 and O6 are non-bonding, at 3.863 (5) and 3.846 (4) Å from the metal centre, respectively. The O—U—O angles involving successive phenoxide groups are larger by about 8–13° for the groups separated by an ether link. The U atom is located 0.059 (2) Å from the mean plane defined by the four phenoxide groups (r.m.s. deviation 0.027 Å), and ether atoms O3 and O6 are 1.784 (7) and 1.679 (7) Å from this plane, respectively. The four phenol rings make dihedral angles of 38.2 (2), 37.4 (2), 48.3 (2) and 43.0 (2)° with the O₄ mean plane and would define a shallow cavity, similar to those observed in the previous compounds but for the presence of the p-phenyl substituents, which give it additional depth. These phenyl rings are differently oriented with respect to the phenol rings to which they are attached, with dihedral angles of 29.4 (3), 44.13 (17), 13.9 (4) and 49.5 (3)° for rings bearing atoms O1, O2, O4 and O5, respectively. The torsion angles in the ether bridges are all anti [164.3 (5)–170.5 (5)°], as usual in this family of complexes.

The [2.2.2]cryptand is doubly protonated in the so-called `in–in' conformation, with the two H atoms pointing inwards (endo protonation) and involved in trifurcated hydrogen bonds with the three proximal ether O atoms. This conformation, which is more stable than the `out–out' one, was also observed in the previous cases (Masci et al., 2002b) and precludes any cation–anion interaction through hydrogen bonding. The N1···N2 distance, 5.996 (9) Å, is much shorter than in the neutral (6.87 Å; Metz et al., 1976) or monoprotonated cryptand [6.787 (7) and 6.861 (6) Å; Masci et al., 2002b], and it is comparable to those in other diprotonated species with analogous geometry [5.710 (7) Å; Thuéry & Masci, 2002]. This shortening of the dication is a result of the presence of the six intramolecular hydrogen bonds. The O···O separations in each half-molecule are in the range 3.613 (7)–4.129 (7) Å, and the O9/O11/O13 and O10/O12/O14 planes are nearly parallel, with a dihedral angle of 1.69 (12)° between them. The N—C—C—O and O—C—C—O torsion angles are all gauche [in the range 45.3 (7)–66.9 (7)°], but three C—O—C—C angles are gauche instead of anti [67.6 (8), 68.2 (8) and 70.3 (7)°]. These values indicate slight distorsions with respect to the ideal geometry, as in the cases cited above.

The dihydro[2.2.2]cryptand moiety is included in the homooxacalixarene cavity in such a way that the angle between its principal axis (N1···N2 line) and the uranyl ion axis is 117°. This tilting is at variance with the nearly parallel arrangement found in the case of the narrower cavity of the uranyl complexes of hexahomotrioxacalix[3]arene derivatives. Electrostatic cation–anion interactions are likely to contribute to the cohesion of the assembly, but other weak interactions may be discerned as well. The presence of cation–π interactions (Ma & Dougherty, 1997) is suggested by the occurrence of short contacts between aromatic rings and the protonated N atoms or their α-C atoms (Masci et al., 2002b). The shortest contacts are between two of the C atoms bound to N1, C61 and C67, and the centroid of the phenol ring bearing O1, 3.77 and 4.00 Å, respectively, whereas the distance between N1 and this centroid is 4.47 Å. These distances agree with those measured in similar (Masci et al., 2002, 2002b) and different systems (Verdonk et al., 1993; Murayama & Aoki, 1997). The C atoms bound to N2 are farther from aromatic centroids, with the shortest contact at 4.35 Å between C66 and the p-phenyl ring attached to O4. Some C—H···π interactions may also be present, with the three shortest contacts reported in Table 2, Cg1, Cg2 and Cg3 being the centroids of the rings C1–C6, C41–C46 and C34–C39, respectively. Two C atoms of the dimethyl sulfoxide solvent molecules may also be involved in C—H···π interactions.

The packing brings together two cation–anion units related by the inversion centre at (1/2,1/2,0) in such a manner that the ensemble can be viewed as two homooxacalixarene uranyl complexes including two dihydro[2.2.2]cryptands (Fig. 2). After the 1:1 and 2:1 complex/cryptand stoichiometries previously encountered, the 2:2 dimeric assemblage described here is a new example of the versatility of such systems in supramolecular chemistry. However, by contrast with the previous cases in which the sandwich assemblages are held by cation–anion, cation–π and C—H···π interactions (with sufficient strength for the species characterized in the solid state to be stable in solution), the two halves of the dimer in (I) are likely to be held together by van der Waals forces alone.

S2. Experimental

p-Phenyltetrahomodioxacalix[4]arene was prepared as described by No (1999). For the synthesis of (I), a 0.20 M solution of UO₂(NO₃)₂·6H₂O (0.30 ml) in MeOH was added dropwise to a stirred and heated mixture of p-phenyltetrahomodioxacalix[4]arene (8.0 mg, 0.010 mmol) and [2.2.2]cryptand (4.1 mg, 0.011 mmol) in CHCl₃ (5 ml). Stirring and heating were continued for 10 min. The red powder obtained on complete solvent evaporation was recovered, washed with acetone and dissolved in gently heated Me₂SO. Red crystals of complex (I) formed in a few days.

S3. Refinement

The H atoms bound to N atoms were found in difference Fourier maps and refined with isotropic displacement parameters equal to 1.2U_eq of the parent atom. All other H atoms were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH), 0.97 (CH₂) or 0.96 Å (CH₃), and isotropic displacement parameters equal to 1.2U_eq (CH and CH₂) or 1.5U_eq (CH₃) of the parent atom. Restraints on displacement parameters were applied for atoms S2, O16, C73 and C77 of the badly resolved solvent molecules.

Computing details

Data collection: COLLECT (Hooft, 1998); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor, 1997); 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 (Bruker, 1999); PLATON (Spek, 2003).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. The solvent molecules and the H atoms not involved in hydrogen bonds have been omitted. Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the dimeric assemblage in (I). The solvent molecules and the H atoms have been omitted. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (') 1 − x, 1–y, 2–z.]

4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane [7,13,21,27-tetraphenyl-3,17- dioxapentacyclo[23.3.1.1^5,9.1^11,15.1^9,23]ditriaconta- 1(29),5,7,9(30),11 (31),12,14,19 (32),20,22,25,27-dodecaene-29,30,31,32- tetraolato]dioxouranium dimethylsulfoxide trisolvate

Crystal data

(C18H38N2O6)[U(C54H40O6)O2]·3C2H6OS	F(000) = 3416
Mr = 1667.78	Dx = 1.525 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 190557 reflections
a = 14.8955 (5) Å	θ = 2.9–25.7°
b = 20.3681 (10) Å	µ = 2.39 mm^−1
c = 24.9276 (11) Å	T = 100 K
β = 106.169 (3)°	Irregular, translucent light orange
V = 7263.7 (5) Å^3	0.15 × 0.14 × 0.10 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	13724 independent reflections
Radiation source: fine-focus sealed tube	10606 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
two ϕ and three ω scans with 2° steps	θmax = 25.7°, θmin = 2.9°
Absorption correction: part of the refinement model (ΔF) [DELABS in PLATON (Spek, 2003)]	h = 0→18
Tmin = 0.603, Tmax = 0.787	k = 0→24
190557 measured reflections	l = −30→29

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0659P)^2 + 43.6206P] where P = (Fo^2 + 2Fc^2)/3
13724 reflections	(Δ/σ)max = 0.001
922 parameters	Δρmax = 2.54 e Å^−3
24 restraints	Δρmin = −1.26 e Å^−3

Special details

Experimental. crystal-to-detector distance 30 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. 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	0.133598 (17)	0.197090 (12)	0.733296 (10)	0.02805 (9)
O1	0.1595 (3)	0.2436 (2)	0.65541 (19)	0.0309 (10)
O2	0.2491 (3)	0.1270 (2)	0.72441 (19)	0.0300 (10)
O3	0.3193 (3)	0.1112 (2)	0.8521 (2)	0.0340 (11)
O4	0.1042 (3)	0.1428 (2)	0.80646 (19)	0.0326 (10)
O5	0.0179 (3)	0.2667 (2)	0.7371 (2)	0.0327 (10)
O6	0.1136 (3)	0.3802 (2)	0.69426 (19)	0.0304 (10)
O7	0.0498 (3)	0.1455 (2)	0.6863 (2)	0.0327 (10)
O8	0.2174 (3)	0.2492 (2)	0.77825 (19)	0.0303 (10)
O9	0.5468 (3)	0.4694 (2)	0.87159 (19)	0.0344 (11)
O10	0.5854 (3)	0.4563 (2)	0.9848 (2)	0.0385 (11)
O11	0.4547 (3)	0.3050 (2)	0.8434 (2)	0.0360 (11)
O12	0.5374 (4)	0.2580 (2)	0.9560 (2)	0.0402 (12)
O13	0.2757 (3)	0.4412 (2)	0.8601 (2)	0.0347 (11)
O14	0.3311 (3)	0.3800 (2)	0.9650 (2)	0.0367 (11)
N1	0.4032 (4)	0.4243 (3)	0.7919 (2)	0.0316 (12)
H1	0.417 (5)	0.413 (4)	0.829 (3)	0.038*
N2	0.5027 (4)	0.3527 (3)	1.0346 (3)	0.0370 (14)
H2	0.482 (5)	0.361 (4)	0.996 (3)	0.044*
C1	0.2074 (5)	0.3485 (3)	0.6339 (3)	0.0295 (14)
C2	0.2244 (5)	0.2813 (3)	0.6437 (3)	0.0326 (15)
C3	0.3077 (5)	0.2537 (3)	0.6364 (3)	0.0308 (14)
C4	0.3724 (5)	0.2945 (3)	0.6226 (3)	0.0315 (15)
H4	0.4274	0.2763	0.6185	0.038*
C5	0.3579 (5)	0.3623 (3)	0.6145 (3)	0.0330 (15)
C6	0.2723 (5)	0.3881 (3)	0.6195 (3)	0.0332 (15)
H6	0.2596	0.4325	0.6130	0.040*
C7	0.4276 (5)	0.4055 (4)	0.5981 (3)	0.0370 (16)
C8	0.4368 (5)	0.4713 (4)	0.6129 (3)	0.0440 (18)
H8	0.4001	0.4886	0.6342	0.053*
C9	0.4981 (6)	0.5115 (4)	0.5971 (4)	0.050 (2)
H9	0.5009	0.5558	0.6067	0.060*
C10	0.5557 (6)	0.4876 (4)	0.5673 (4)	0.057 (2)
H10	0.5981	0.5151	0.5571	0.068*
C11	0.5496 (6)	0.4216 (4)	0.5525 (4)	0.059 (2)
H11	0.5884	0.4050	0.5322	0.070*
C12	0.4878 (5)	0.3808 (4)	0.5671 (4)	0.047 (2)
H12	0.4848	0.3367	0.5569	0.057*
C13	0.3232 (5)	0.1800 (3)	0.6399 (3)	0.0316 (15)
H13A	0.2626	0.1588	0.6317	0.038*
H13B	0.3513	0.1674	0.6107	0.038*
C14	0.3832 (5)	0.1527 (3)	0.6944 (3)	0.0295 (14)
C15	0.3403 (5)	0.1266 (3)	0.7337 (3)	0.0302 (14)
C16	0.3987 (5)	0.0956 (3)	0.7823 (3)	0.0297 (14)
C17	0.4947 (5)	0.0936 (3)	0.7903 (3)	0.0310 (14)
H17	0.5320	0.0744	0.8227	0.037*
C18	0.5378 (5)	0.1195 (3)	0.7514 (3)	0.0317 (15)
C19	0.4805 (5)	0.1485 (3)	0.7043 (3)	0.0311 (14)
H19	0.5074	0.1660	0.6780	0.037*
C20	0.6403 (5)	0.1103 (3)	0.7599 (3)	0.0343 (15)
C21	0.6723 (5)	0.0895 (4)	0.7153 (3)	0.0401 (17)
H21	0.6299	0.0825	0.6805	0.048*
C22	0.7681 (5)	0.0790 (4)	0.7223 (4)	0.0440 (18)
H22	0.7890	0.0650	0.6924	0.053*
C23	0.8313 (5)	0.0895 (4)	0.7741 (3)	0.0443 (18)
H23	0.8949	0.0831	0.7790	0.053*
C24	0.8000 (5)	0.1093 (4)	0.8180 (3)	0.0428 (18)
H24	0.8426	0.1159	0.8527	0.051*
C25	0.7043 (5)	0.1199 (4)	0.8113 (3)	0.0362 (16)
H25	0.6839	0.1334	0.8416	0.043*
C26	0.3560 (5)	0.0631 (3)	0.8219 (3)	0.0309 (14)
H26A	0.3061	0.0343	0.8017	0.037*
H26B	0.4025	0.0366	0.8479	0.037*
C27	0.2587 (5)	0.0808 (3)	0.8806 (3)	0.0335 (15)
H27A	0.2958	0.0565	0.9126	0.040*
H27B	0.2176	0.0500	0.8557	0.040*
C28	0.2017 (4)	0.1313 (3)	0.8995 (3)	0.0308 (14)
C29	0.1240 (5)	0.1597 (3)	0.8601 (3)	0.0313 (15)
C30	0.0676 (5)	0.2032 (3)	0.8805 (3)	0.0310 (14)
C31	0.0915 (5)	0.2201 (3)	0.9360 (3)	0.0339 (15)
H31	0.0526	0.2486	0.9482	0.041*
C32	0.1724 (5)	0.1961 (3)	0.9754 (3)	0.0334 (15)
C33	0.2247 (5)	0.1503 (3)	0.9549 (3)	0.0326 (15)
H33	0.2773	0.1318	0.9796	0.039*
C34	0.2042 (5)	0.2203 (3)	1.0340 (3)	0.0338 (15)
C35	0.1487 (5)	0.2640 (4)	1.0547 (3)	0.0394 (17)
H35	0.0885	0.2738	1.0332	0.047*
C36	0.1827 (6)	0.2929 (4)	1.1070 (3)	0.047 (2)
H36	0.1454	0.3224	1.1195	0.056*
C37	0.2712 (6)	0.2783 (4)	1.1406 (3)	0.0463 (19)
H37	0.2943	0.2986	1.1751	0.056*
C38	0.3250 (5)	0.2328 (4)	1.1218 (3)	0.0403 (17)
H38	0.3833	0.2208	1.1448	0.048*
C39	0.2928 (5)	0.2050 (3)	1.0693 (3)	0.0385 (16)
H39	0.3307	0.1756	1.0571	0.046*
C40	−0.0212 (5)	0.2319 (3)	0.8402 (3)	0.0342 (15)
H40A	−0.0394	0.2044	0.8071	0.041*
H40B	−0.0713	0.2305	0.8580	0.041*
C41	−0.0098 (4)	0.3020 (3)	0.8225 (3)	0.0309 (14)
C42	0.0088 (4)	0.3158 (3)	0.7709 (3)	0.0287 (14)
C43	0.0144 (4)	0.3821 (3)	0.7552 (3)	0.0295 (14)
C44	0.0043 (5)	0.4320 (3)	0.7914 (3)	0.0321 (15)
H44	0.0084	0.4753	0.7806	0.038*
C45	−0.0114 (5)	0.4204 (3)	0.8425 (3)	0.0327 (15)
C46	−0.0197 (4)	0.3535 (3)	0.8566 (3)	0.0306 (14)
H46	−0.0322	0.3439	0.8903	0.037*
C47	−0.0213 (5)	0.4727 (3)	0.8816 (3)	0.0333 (15)
C48	0.0452 (5)	0.5230 (4)	0.8967 (3)	0.0409 (17)
H48	0.0964	0.5238	0.8823	0.049*
C49	0.0338 (6)	0.5718 (4)	0.9335 (3)	0.0410 (18)
H49	0.0769	0.6060	0.9423	0.049*
C50	−0.0392 (6)	0.5709 (4)	0.9571 (3)	0.0418 (18)
H50	−0.0442	0.6031	0.9826	0.050*
C51	−0.1053 (6)	0.5215 (4)	0.9426 (3)	0.0418 (17)
H51	−0.1556	0.5207	0.9578	0.050*
C52	−0.0966 (5)	0.4727 (4)	0.9049 (3)	0.0376 (16)
H52	−0.1414	0.4398	0.8952	0.045*
C53	0.0234 (5)	0.3969 (3)	0.6982 (3)	0.0325 (15)
H53A	−0.0232	0.3722	0.6706	0.039*
H53B	0.0121	0.4432	0.6902	0.039*
C54	0.1159 (5)	0.3771 (3)	0.6374 (3)	0.0314 (15)
H54A	0.1083	0.4208	0.6213	0.038*
H54B	0.0647	0.3501	0.6161	0.038*
C55	0.4382 (5)	0.4925 (3)	0.7859 (3)	0.0346 (15)
H55A	0.4011	0.5243	0.7993	0.042*
H55B	0.4317	0.5016	0.7468	0.042*
C56	0.5394 (5)	0.4988 (3)	0.8187 (3)	0.0329 (15)
H56A	0.5793	0.4762	0.7998	0.039*
H56B	0.5577	0.5446	0.8232	0.039*
C57	0.6411 (5)	0.4597 (4)	0.9036 (3)	0.0414 (17)
H57A	0.6719	0.5017	0.9137	0.050*
H57B	0.6749	0.4352	0.8821	0.050*
C58	0.6401 (5)	0.4224 (4)	0.9552 (3)	0.0413 (17)
H58A	0.6142	0.3790	0.9449	0.050*
H58B	0.7035	0.4173	0.9789	0.050*
C59	0.6141 (5)	0.4482 (4)	1.0441 (3)	0.0395 (17)
H59A	0.5790	0.4782	1.0608	0.047*
H59B	0.6798	0.4593	1.0582	0.047*
C60	0.5992 (5)	0.3788 (4)	1.0613 (3)	0.0417 (18)
H60A	0.6444	0.3503	1.0515	0.050*
H60B	0.6109	0.3774	1.1015	0.050*
C61	0.4524 (5)	0.3741 (3)	0.7667 (3)	0.0351 (16)
H61A	0.5190	0.3831	0.7782	0.042*
H61B	0.4310	0.3775	0.7264	0.042*
C62	0.4355 (5)	0.3051 (3)	0.7841 (3)	0.0344 (15)
H62A	0.3712	0.2923	0.7669	0.041*
H62B	0.4762	0.2744	0.7725	0.041*
C63	0.4423 (6)	0.2394 (3)	0.8621 (3)	0.0388 (17)
H63A	0.4915	0.2111	0.8568	0.047*
H63B	0.3828	0.2219	0.8402	0.047*
C64	0.4450 (5)	0.2404 (4)	0.9226 (3)	0.0369 (16)
H64A	0.3999	0.2719	0.9285	0.044*
H64B	0.4284	0.1974	0.9336	0.044*
C65	0.5535 (6)	0.2407 (4)	1.0129 (3)	0.0437 (18)
H65A	0.6193	0.2468	1.0318	0.052*
H65B	0.5392	0.1945	1.0152	0.052*
C66	0.4960 (6)	0.2804 (3)	1.0429 (3)	0.0407 (17)
H66A	0.4310	0.2671	1.0294	0.049*
H66B	0.5171	0.2707	1.0825	0.049*
C67	0.2984 (5)	0.4204 (4)	0.7684 (3)	0.0352 (16)
H67A	0.2790	0.3748	0.7673	0.042*
H67B	0.2808	0.4370	0.7304	0.042*
C68	0.2480 (5)	0.4596 (3)	0.8030 (3)	0.0338 (15)
H68A	0.2607	0.5059	0.7999	0.041*
H68B	0.1811	0.4529	0.7882	0.041*
C69	0.2430 (5)	0.3770 (3)	0.8696 (3)	0.0368 (16)
H69A	0.2852	0.3438	0.8629	0.044*
H69B	0.1815	0.3694	0.8442	0.044*
C70	0.2384 (5)	0.3727 (4)	0.9287 (3)	0.0381 (16)
H70A	0.1983	0.4071	0.9361	0.046*
H70B	0.2127	0.3306	0.9351	0.046*
C71	0.3332 (5)	0.3732 (4)	1.0223 (3)	0.0370 (16)
H71A	0.3168	0.3288	1.0299	0.044*
H71B	0.2891	0.4032	1.0315	0.044*
C72	0.4311 (5)	0.3890 (4)	1.0561 (3)	0.0395 (17)
H72A	0.4387	0.3771	1.0948	0.047*
H72B	0.4416	0.4359	1.0546	0.047*
S1	0.73142 (17)	0.35714 (13)	0.75263 (11)	0.0609 (6)
S2	0.3033 (2)	0.22662 (13)	0.47080 (12)	0.0747 (8)
S3	0.90902 (15)	0.48657 (10)	0.56530 (9)	0.0476 (5)
O15	0.6919 (4)	0.3921 (3)	0.7943 (2)	0.0563 (15)
O16	0.3995 (7)	0.2231 (5)	0.4860 (4)	0.113 (3)
O17	0.9189 (4)	0.4341 (3)	0.5261 (3)	0.0543 (15)
C73	0.6319 (9)	0.3254 (7)	0.7019 (6)	0.100 (4)
H73A	0.6065	0.2892	0.7175	0.150*
H73B	0.6500	0.3107	0.6698	0.150*
H73C	0.5854	0.3592	0.6909	0.150*
C74	0.7603 (8)	0.4178 (6)	0.7100 (4)	0.077 (3)
H74A	0.7075	0.4462	0.6957	0.116*
H74B	0.7769	0.3973	0.6794	0.116*
H74C	0.8122	0.4432	0.7316	0.116*
C75	0.2515 (7)	0.2116 (4)	0.3979 (4)	0.059 (2)
H75A	0.2766	0.2419	0.3764	0.088*
H75B	0.1851	0.2174	0.3893	0.088*
H75C	0.2652	0.1675	0.3891	0.088*
C76	0.2664 (7)	0.3096 (5)	0.4696 (4)	0.063 (3)
H76A	0.2790	0.3257	0.5071	0.095*
H76B	0.2006	0.3122	0.4516	0.095*
H76C	0.2997	0.3357	0.4494	0.095*
C77	0.7908 (7)	0.4913 (6)	0.5635 (5)	0.076 (3)
H77A	0.7535	0.4964	0.5256	0.114*
H77B	0.7813	0.5284	0.5851	0.114*
H77C	0.7728	0.4518	0.5789	0.114*
C78	0.9180 (8)	0.5643 (5)	0.5352 (5)	0.069 (3)
H78A	0.9792	0.5690	0.5300	0.103*
H78B	0.9080	0.5983	0.5596	0.103*
H78C	0.8717	0.5676	0.4998	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.03056 (14)	0.02163 (13)	0.03134 (14)	−0.00021 (10)	0.00758 (10)	−0.00186 (11)
O1	0.031 (2)	0.030 (2)	0.033 (2)	−0.0069 (19)	0.010 (2)	−0.001 (2)
O2	0.031 (2)	0.023 (2)	0.034 (2)	0.0076 (18)	0.008 (2)	−0.0026 (19)
O3	0.039 (3)	0.024 (2)	0.043 (3)	−0.0015 (19)	0.019 (2)	−0.002 (2)
O4	0.037 (3)	0.028 (2)	0.034 (3)	−0.004 (2)	0.014 (2)	−0.001 (2)
O5	0.029 (2)	0.027 (2)	0.041 (3)	0.0067 (19)	0.006 (2)	−0.004 (2)
O6	0.037 (3)	0.020 (2)	0.034 (2)	−0.0029 (19)	0.009 (2)	0.0034 (19)
O7	0.031 (2)	0.028 (2)	0.038 (3)	0.0005 (19)	0.008 (2)	−0.002 (2)
O8	0.033 (2)	0.025 (2)	0.033 (2)	0.0010 (19)	0.010 (2)	0.0000 (19)
O9	0.036 (3)	0.033 (3)	0.034 (3)	−0.001 (2)	0.010 (2)	0.002 (2)
O10	0.044 (3)	0.035 (3)	0.035 (3)	0.003 (2)	0.009 (2)	0.002 (2)
O11	0.044 (3)	0.025 (2)	0.038 (3)	−0.005 (2)	0.009 (2)	−0.003 (2)
O12	0.045 (3)	0.036 (3)	0.036 (3)	−0.003 (2)	0.006 (2)	0.001 (2)
O13	0.036 (3)	0.031 (3)	0.037 (3)	−0.008 (2)	0.009 (2)	0.000 (2)
O14	0.036 (3)	0.041 (3)	0.032 (3)	−0.003 (2)	0.007 (2)	0.001 (2)
N1	0.036 (3)	0.027 (3)	0.032 (3)	−0.005 (2)	0.008 (3)	−0.003 (2)
N2	0.048 (4)	0.026 (3)	0.033 (3)	−0.001 (3)	0.006 (3)	−0.002 (2)
C1	0.038 (4)	0.027 (3)	0.024 (3)	−0.002 (3)	0.009 (3)	−0.005 (3)
C2	0.038 (4)	0.033 (4)	0.028 (3)	−0.005 (3)	0.011 (3)	−0.001 (3)
C3	0.030 (3)	0.038 (4)	0.024 (3)	0.001 (3)	0.007 (3)	0.001 (3)
C4	0.030 (3)	0.028 (4)	0.036 (4)	0.008 (3)	0.009 (3)	−0.001 (3)
C5	0.036 (4)	0.031 (4)	0.034 (4)	−0.001 (3)	0.013 (3)	−0.004 (3)
C6	0.044 (4)	0.022 (3)	0.033 (4)	0.002 (3)	0.009 (3)	−0.005 (3)
C7	0.033 (4)	0.039 (4)	0.039 (4)	0.002 (3)	0.010 (3)	0.000 (3)
C8	0.044 (4)	0.036 (4)	0.055 (5)	0.007 (3)	0.018 (4)	0.001 (4)
C9	0.046 (4)	0.029 (4)	0.081 (6)	−0.001 (3)	0.027 (4)	−0.005 (4)
C10	0.052 (5)	0.039 (5)	0.090 (7)	−0.008 (4)	0.038 (5)	0.000 (4)
C11	0.061 (5)	0.043 (5)	0.088 (7)	0.006 (4)	0.048 (5)	−0.004 (5)
C12	0.047 (4)	0.032 (4)	0.071 (6)	−0.002 (3)	0.030 (4)	−0.002 (4)
C13	0.037 (4)	0.030 (4)	0.026 (3)	0.004 (3)	0.008 (3)	−0.002 (3)
C14	0.034 (4)	0.021 (3)	0.033 (3)	0.001 (3)	0.008 (3)	−0.004 (3)
C15	0.032 (4)	0.023 (3)	0.037 (4)	0.003 (3)	0.011 (3)	0.000 (3)
C16	0.037 (4)	0.018 (3)	0.036 (4)	0.001 (3)	0.012 (3)	−0.004 (3)
C17	0.037 (4)	0.022 (3)	0.033 (4)	0.005 (3)	0.009 (3)	0.000 (3)
C18	0.036 (4)	0.025 (3)	0.036 (4)	0.001 (3)	0.013 (3)	−0.002 (3)
C19	0.037 (4)	0.023 (3)	0.035 (4)	0.003 (3)	0.012 (3)	−0.001 (3)
C20	0.039 (4)	0.021 (3)	0.043 (4)	0.001 (3)	0.013 (3)	0.001 (3)
C21	0.037 (4)	0.044 (4)	0.041 (4)	−0.001 (3)	0.014 (3)	0.000 (3)
C22	0.045 (4)	0.038 (4)	0.053 (5)	0.010 (3)	0.021 (4)	0.004 (4)
C23	0.035 (4)	0.039 (4)	0.061 (5)	0.004 (3)	0.017 (4)	0.000 (4)
C24	0.034 (4)	0.045 (5)	0.047 (4)	−0.002 (3)	0.009 (3)	0.002 (4)
C25	0.035 (4)	0.034 (4)	0.041 (4)	0.004 (3)	0.013 (3)	−0.003 (3)
C26	0.031 (3)	0.025 (3)	0.034 (4)	0.004 (3)	0.005 (3)	−0.001 (3)
C27	0.036 (4)	0.027 (4)	0.042 (4)	0.001 (3)	0.016 (3)	0.003 (3)
C28	0.029 (3)	0.026 (3)	0.039 (4)	−0.001 (3)	0.013 (3)	0.004 (3)
C29	0.036 (4)	0.023 (3)	0.042 (4)	−0.007 (3)	0.021 (3)	0.001 (3)
C30	0.034 (3)	0.018 (3)	0.043 (4)	0.000 (3)	0.013 (3)	0.001 (3)
C31	0.036 (4)	0.024 (3)	0.044 (4)	0.001 (3)	0.015 (3)	0.000 (3)
C32	0.035 (4)	0.029 (3)	0.037 (4)	0.003 (3)	0.011 (3)	0.004 (3)
C33	0.036 (4)	0.026 (3)	0.037 (4)	0.000 (3)	0.012 (3)	0.005 (3)
C34	0.041 (4)	0.023 (3)	0.040 (4)	−0.002 (3)	0.016 (3)	0.002 (3)
C35	0.043 (4)	0.038 (4)	0.039 (4)	0.005 (3)	0.013 (3)	0.003 (3)
C36	0.060 (5)	0.041 (5)	0.041 (4)	0.016 (4)	0.016 (4)	0.001 (3)
C37	0.064 (5)	0.032 (4)	0.040 (4)	0.008 (4)	0.009 (4)	0.001 (3)
C38	0.037 (4)	0.035 (4)	0.045 (4)	0.008 (3)	0.006 (3)	0.004 (3)
C39	0.042 (4)	0.028 (4)	0.044 (4)	0.003 (3)	0.010 (3)	0.001 (3)
C40	0.036 (4)	0.029 (4)	0.041 (4)	0.000 (3)	0.015 (3)	−0.001 (3)
C41	0.029 (3)	0.025 (3)	0.037 (4)	0.003 (3)	0.008 (3)	−0.001 (3)
C42	0.022 (3)	0.028 (4)	0.035 (4)	0.001 (2)	0.007 (3)	0.000 (3)
C43	0.030 (3)	0.019 (3)	0.036 (4)	0.006 (3)	0.004 (3)	0.003 (3)
C44	0.036 (4)	0.022 (3)	0.037 (4)	−0.002 (3)	0.008 (3)	0.003 (3)
C45	0.031 (3)	0.026 (4)	0.042 (4)	0.001 (3)	0.011 (3)	0.000 (3)
C46	0.030 (3)	0.023 (3)	0.040 (4)	0.001 (3)	0.011 (3)	0.004 (3)
C47	0.041 (4)	0.025 (3)	0.034 (4)	0.006 (3)	0.010 (3)	0.001 (3)
C48	0.048 (4)	0.035 (4)	0.043 (4)	−0.003 (3)	0.016 (4)	0.000 (3)
C49	0.061 (5)	0.026 (4)	0.036 (4)	−0.005 (3)	0.014 (4)	0.000 (3)
C50	0.058 (5)	0.028 (4)	0.038 (4)	0.009 (3)	0.010 (4)	−0.004 (3)
C51	0.048 (4)	0.039 (4)	0.043 (4)	0.009 (3)	0.019 (4)	0.000 (3)
C52	0.036 (4)	0.034 (4)	0.044 (4)	0.005 (3)	0.013 (3)	0.002 (3)
C53	0.033 (4)	0.031 (4)	0.033 (4)	−0.003 (3)	0.007 (3)	−0.006 (3)
C54	0.044 (4)	0.014 (3)	0.036 (4)	0.006 (3)	0.012 (3)	−0.001 (3)
C55	0.041 (4)	0.025 (4)	0.038 (4)	−0.003 (3)	0.011 (3)	0.001 (3)
C56	0.036 (4)	0.027 (4)	0.036 (4)	−0.002 (3)	0.011 (3)	−0.001 (3)
C57	0.036 (4)	0.042 (4)	0.046 (4)	−0.002 (3)	0.011 (3)	−0.006 (3)
C58	0.042 (4)	0.038 (4)	0.042 (4)	0.003 (3)	0.011 (3)	−0.001 (3)
C59	0.046 (4)	0.036 (4)	0.036 (4)	−0.003 (3)	0.010 (3)	−0.004 (3)
C60	0.050 (5)	0.038 (4)	0.033 (4)	−0.001 (3)	0.005 (3)	−0.001 (3)
C61	0.036 (4)	0.033 (4)	0.036 (4)	0.005 (3)	0.010 (3)	−0.002 (3)
C62	0.037 (4)	0.032 (4)	0.034 (4)	0.001 (3)	0.010 (3)	−0.005 (3)
C63	0.052 (4)	0.022 (3)	0.038 (4)	0.002 (3)	0.006 (3)	0.002 (3)
C64	0.042 (4)	0.028 (4)	0.036 (4)	−0.002 (3)	0.005 (3)	−0.003 (3)
C65	0.054 (5)	0.035 (4)	0.038 (4)	0.004 (3)	0.005 (4)	0.002 (3)
C66	0.056 (5)	0.024 (4)	0.039 (4)	−0.003 (3)	0.009 (4)	0.002 (3)
C67	0.029 (4)	0.033 (4)	0.041 (4)	0.001 (3)	0.004 (3)	−0.002 (3)
C68	0.035 (4)	0.030 (4)	0.037 (4)	0.001 (3)	0.012 (3)	0.001 (3)
C69	0.047 (4)	0.027 (4)	0.033 (4)	0.000 (3)	0.006 (3)	−0.006 (3)
C70	0.036 (4)	0.034 (4)	0.041 (4)	0.001 (3)	0.006 (3)	0.002 (3)
C71	0.041 (4)	0.032 (4)	0.037 (4)	0.000 (3)	0.009 (3)	−0.001 (3)
C72	0.051 (4)	0.033 (4)	0.030 (4)	0.004 (3)	0.003 (3)	−0.002 (3)
S1	0.0542 (13)	0.0646 (15)	0.0661 (15)	0.0134 (11)	0.0205 (11)	−0.0112 (12)
S2	0.0722 (16)	0.0530 (14)	0.0792 (17)	0.0167 (12)	−0.0115 (13)	−0.0111 (12)
S3	0.0528 (12)	0.0385 (11)	0.0481 (11)	−0.0042 (9)	0.0084 (9)	−0.0026 (9)
O15	0.054 (4)	0.063 (4)	0.052 (3)	0.010 (3)	0.017 (3)	−0.008 (3)
O16	0.107 (5)	0.113 (5)	0.118 (5)	0.000 (4)	0.029 (4)	0.002 (4)
O17	0.053 (3)	0.050 (4)	0.062 (4)	−0.009 (3)	0.018 (3)	−0.011 (3)
C73	0.096 (6)	0.107 (6)	0.103 (6)	−0.006 (4)	0.035 (4)	−0.024 (4)
C74	0.080 (7)	0.093 (9)	0.063 (6)	0.015 (6)	0.027 (6)	−0.010 (6)
C75	0.069 (6)	0.040 (5)	0.073 (6)	−0.006 (4)	0.030 (5)	−0.012 (4)
C76	0.082 (7)	0.057 (6)	0.040 (5)	0.012 (5)	0.001 (5)	−0.007 (4)
C77	0.076 (5)	0.075 (5)	0.084 (5)	−0.008 (4)	0.033 (4)	−0.014 (4)
C78	0.089 (7)	0.043 (5)	0.085 (7)	0.013 (5)	0.041 (6)	0.013 (5)

Geometric parameters (Å, º)

U1—O1	2.288 (4)	C38—C39	1.384 (10)
U1—O2	2.292 (4)	C38—H38	0.9300
U1—O4	2.277 (5)	C39—H39	0.9300
U1—O5	2.254 (4)	C40—C41	1.518 (9)
U1—O7	1.794 (5)	C40—H40A	0.9700
U1—O8	1.778 (4)	C40—H40B	0.9700
O1—C2	1.329 (8)	C41—C46	1.385 (9)
O2—C15	1.314 (8)	C41—C42	1.417 (10)
O3—C26	1.433 (8)	C42—C43	1.415 (9)
O3—C27	1.434 (8)	C43—C44	1.395 (9)
O4—C29	1.333 (8)	C43—C53	1.494 (9)
O5—C42	1.338 (8)	C44—C45	1.376 (10)
O6—C53	1.415 (8)	C44—H44	0.9300
O6—C54	1.430 (8)	C45—C46	1.422 (9)
O9—C56	1.423 (8)	C45—C47	1.480 (10)
O9—C57	1.423 (9)	C46—H46	0.9300
O10—C58	1.422 (9)	C47—C52	1.399 (10)
O10—C59	1.430 (8)	C47—C48	1.401 (10)
O11—C62	1.425 (8)	C48—C49	1.395 (10)
O11—C63	1.444 (8)	C48—H48	0.9300
O12—C65	1.414 (9)	C49—C50	1.374 (11)
O12—C64	1.442 (8)	C49—H49	0.9300
O13—C68	1.417 (8)	C50—C51	1.384 (11)
O13—C69	1.437 (8)	C50—H50	0.9300
O14—C71	1.428 (8)	C51—C52	1.397 (10)
O14—C70	1.433 (8)	C51—H51	0.9300
N1—C61	1.493 (9)	C52—H52	0.9300
N1—C55	1.507 (8)	C53—H53A	0.9700
N1—C67	1.509 (9)	C53—H53B	0.9700
N1—H1	0.92 (8)	C54—H54A	0.9700
N2—C66	1.494 (9)	C54—H54B	0.9700
N2—C60	1.502 (10)	C55—C56	1.507 (10)
N2—C72	1.515 (10)	C55—H55A	0.9700
N2—H2	0.95 (8)	C55—H55B	0.9700
C1—C6	1.380 (10)	C56—H56A	0.9700
C1—C2	1.400 (10)	C56—H56B	0.9700
C1—C54	1.507 (9)	C57—C58	1.496 (11)
C2—C3	1.419 (10)	C57—H57A	0.9700
C3—C4	1.387 (10)	C57—H57B	0.9700
C3—C13	1.519 (9)	C58—H58A	0.9700
C4—C5	1.404 (9)	C58—H58B	0.9700
C4—H4	0.9300	C59—C60	1.511 (10)
C5—C6	1.416 (10)	C59—H59A	0.9700
C5—C7	1.501 (10)	C59—H59B	0.9700
C6—H6	0.9300	C60—H60A	0.9700
C7—C8	1.388 (11)	C60—H60B	0.9700
C7—C12	1.428 (10)	C61—C62	1.513 (10)
C8—C9	1.364 (11)	C61—H61A	0.9700
C8—H8	0.9300	C61—H61B	0.9700
C9—C10	1.371 (12)	C62—H62A	0.9700
C9—H9	0.9300	C62—H62B	0.9700
C10—C11	1.390 (12)	C63—C64	1.496 (10)
C10—H10	0.9300	C63—H63A	0.9700
C11—C12	1.365 (11)	C63—H63B	0.9700
C11—H11	0.9300	C64—H64A	0.9700
C12—H12	0.9300	C64—H64B	0.9700
C13—C14	1.509 (9)	C65—C66	1.519 (11)
C13—H13A	0.9700	C65—H65A	0.9700
C13—H13B	0.9700	C65—H65B	0.9700
C14—C19	1.403 (9)	C66—H66A	0.9700
C14—C15	1.413 (10)	C66—H66B	0.9700
C15—C16	1.427 (9)	C67—C68	1.518 (10)
C16—C17	1.388 (9)	C67—H67A	0.9700
C16—C26	1.472 (9)	C67—H67B	0.9700
C17—C18	1.405 (10)	C68—H68A	0.9700
C17—H17	0.9300	C68—H68B	0.9700
C18—C19	1.378 (9)	C69—C70	1.496 (10)
C18—C20	1.493 (9)	C69—H69A	0.9700
C19—H19	0.9300	C69—H69B	0.9700
C20—C25	1.381 (10)	C70—H70A	0.9700
C20—C21	1.394 (10)	C70—H70B	0.9700
C21—C22	1.404 (10)	C71—C72	1.501 (10)
C21—H21	0.9300	C71—H71A	0.9700
C22—C23	1.388 (11)	C71—H71B	0.9700
C22—H22	0.9300	C72—H72A	0.9700
C23—C24	1.362 (11)	C72—H72B	0.9700
C23—H23	0.9300	S1—O15	1.507 (6)
C24—C25	1.406 (10)	S1—C74	1.760 (12)
C24—H24	0.9300	S1—C73	1.781 (13)
C25—H25	0.9300	S2—O16	1.378 (10)
C26—H26A	0.9700	S2—C76	1.775 (9)
C26—H26B	0.9700	S2—C75	1.791 (10)
C27—C28	1.493 (9)	S3—O17	1.484 (6)
C27—H27A	0.9700	S3—C77	1.752 (11)
C27—H27B	0.9700	S3—C78	1.772 (9)
C28—C33	1.382 (10)	C73—H73A	0.9600
C28—C29	1.415 (10)	C73—H73B	0.9600
C29—C30	1.408 (9)	C73—H73C	0.9600
C30—C31	1.374 (10)	C74—H74A	0.9600
C30—C40	1.536 (9)	C74—H74B	0.9600
C31—C32	1.414 (10)	C74—H74C	0.9600
C31—H31	0.9300	C75—H75A	0.9600
C32—C33	1.401 (10)	C75—H75B	0.9600
C32—C34	1.488 (10)	C75—H75C	0.9600
C33—H33	0.9300	C76—H76A	0.9600
C34—C39	1.402 (10)	C76—H76B	0.9600
C34—C35	1.408 (10)	C76—H76C	0.9600
C35—C36	1.389 (11)	C77—H77A	0.9600
C35—H35	0.9300	C77—H77B	0.9600
C36—C37	1.383 (11)	C77—H77C	0.9600
C36—H36	0.9300	C78—H78A	0.9600
C37—C38	1.389 (11)	C78—H78B	0.9600
C37—H37	0.9300	C78—H78C	0.9600
O1—U1—O2	82.39 (16)	C44—C43—C53	121.6 (6)
O2—U1—O4	95.26 (16)	C42—C43—C53	118.9 (6)
O4—U1—O5	87.27 (17)	C45—C44—C43	123.4 (6)
O5—U1—O1	94.96 (17)	C45—C44—H44	118.3
O1—U1—O7	86.57 (19)	C43—C44—H44	118.3
O1—U1—O8	91.88 (18)	C44—C45—C46	116.3 (6)
O2—U1—O7	88.67 (18)	C44—C45—C47	124.0 (6)
O2—U1—O8	91.10 (18)	C46—C45—C47	119.7 (6)
O4—U1—O7	89.09 (19)	C41—C46—C45	122.8 (7)
O4—U1—O8	92.46 (19)	C41—C46—H46	118.6
O5—U1—O7	89.69 (19)	C45—C46—H46	118.6
O5—U1—O8	90.47 (18)	C52—C47—C48	118.5 (7)
O8—U1—O7	178.4 (2)	C52—C47—C45	120.8 (6)
O4—U1—O1	175.10 (16)	C48—C47—C45	120.7 (7)
O5—U1—O2	176.96 (16)	C49—C48—C47	119.4 (7)
O8—U1—O6	64.62 (16)	C49—C48—H48	120.3
O7—U1—O6	114.34 (16)	C47—C48—H48	120.3
O5—U1—O6	52.70 (14)	C50—C49—C48	121.9 (7)
O4—U1—O6	130.92 (14)	C50—C49—H49	119.1
O1—U1—O6	53.34 (14)	C48—C49—H49	119.1
O2—U1—O6	125.93 (14)	C49—C50—C51	119.2 (7)
O8—U1—O3	63.94 (16)	C49—C50—H50	120.4
O7—U1—O3	117.02 (16)	C51—C50—H50	120.4
O5—U1—O3	130.20 (14)	C50—C51—C52	120.0 (7)
O4—U1—O3	54.70 (14)	C50—C51—H51	120.0
O1—U1—O3	125.76 (13)	C52—C51—H51	120.0
O2—U1—O3	52.83 (13)	C51—C52—C47	120.9 (7)
O6—U1—O3	128.47 (10)	C51—C52—H52	119.5
C2—O1—U1	136.9 (4)	C47—C52—H52	119.5
C15—O2—U1	138.9 (4)	O6—C53—C43	110.9 (5)
C26—O3—C27	110.4 (5)	O6—C53—H53A	109.5
C26—O3—U1	101.8 (3)	C43—C53—H53A	109.5
C27—O3—U1	99.2 (4)	O6—C53—H53B	109.5
C29—O4—U1	129.9 (4)	C43—C53—H53B	109.5
C42—O5—U1	135.1 (4)	H53A—C53—H53B	108.1
C53—O6—C54	111.4 (5)	O6—C54—C1	110.3 (5)
C53—O6—U1	102.9 (3)	O6—C54—H54A	109.6
C54—O6—U1	100.7 (3)	C1—C54—H54A	109.6
C56—O9—C57	112.8 (5)	O6—C54—H54B	109.6
C58—O10—C59	115.6 (6)	C1—C54—H54B	109.6
C62—O11—C63	109.3 (5)	H54A—C54—H54B	108.1
C65—O12—C64	112.7 (6)	N1—C55—C56	110.2 (6)
C68—O13—C69	112.8 (5)	N1—C55—H55A	109.6
C71—O14—C70	111.7 (5)	C56—C55—H55A	109.6
C61—N1—C55	111.4 (6)	N1—C55—H55B	109.6
C61—N1—C67	112.2 (5)	C56—C55—H55B	109.6
C55—N1—C67	111.1 (5)	H55A—C55—H55B	108.1
C61—N1—H1	105 (5)	O9—C56—C55	106.0 (5)
C55—N1—H1	110 (5)	O9—C56—H56A	110.5
C67—N1—H1	107 (5)	C55—C56—H56A	110.5
C66—N2—C60	112.4 (6)	O9—C56—H56B	110.5
C66—N2—C72	110.6 (6)	C55—C56—H56B	110.5
C60—N2—C72	110.6 (6)	H56A—C56—H56B	108.7
C66—N2—H2	108 (5)	O9—C57—C58	107.9 (6)
C60—N2—H2	112 (5)	O9—C57—H57A	110.1
C72—N2—H2	103 (5)	C58—C57—H57A	110.1
C6—C1—C2	120.7 (6)	O9—C57—H57B	110.1
C6—C1—C54	119.9 (6)	C58—C57—H57B	110.1
C2—C1—C54	119.4 (6)	H57A—C57—H57B	108.4
O1—C2—C1	119.7 (6)	O10—C58—C57	110.1 (6)
O1—C2—C3	120.9 (6)	O10—C58—H58A	109.6
C1—C2—C3	119.2 (6)	C57—C58—H58A	109.6
C4—C3—C2	119.1 (6)	O10—C58—H58B	109.6
C4—C3—C13	120.1 (6)	C57—C58—H58B	109.6
C2—C3—C13	120.6 (6)	H58A—C58—H58B	108.2
C3—C4—C5	122.3 (6)	O10—C59—C60	112.0 (6)
C3—C4—H4	118.8	O10—C59—H59A	109.2
C5—C4—H4	118.8	C60—C59—H59A	109.2
C4—C5—C6	117.3 (6)	O10—C59—H59B	109.2
C4—C5—C7	121.6 (6)	C60—C59—H59B	109.2
C6—C5—C7	121.0 (6)	H59A—C59—H59B	107.9
C1—C6—C5	121.2 (6)	N2—C60—C59	113.8 (6)
C1—C6—H6	119.4	N2—C60—H60A	108.8
C5—C6—H6	119.4	C59—C60—H60A	108.8
C8—C7—C12	117.0 (7)	N2—C60—H60B	108.8
C8—C7—C5	121.2 (7)	C59—C60—H60B	108.8
C12—C7—C5	121.8 (7)	H60A—C60—H60B	107.7
C9—C8—C7	121.9 (8)	N1—C61—C62	112.0 (6)
C9—C8—H8	119.1	N1—C61—H61A	109.2
C7—C8—H8	119.1	C62—C61—H61A	109.2
C8—C9—C10	120.9 (8)	N1—C61—H61B	109.2
C8—C9—H9	119.5	C62—C61—H61B	109.2
C10—C9—H9	119.5	H61A—C61—H61B	107.9
C9—C10—C11	118.9 (8)	O11—C62—C61	107.2 (5)
C9—C10—H10	120.6	O11—C62—H62A	110.3
C11—C10—H10	120.6	C61—C62—H62A	110.3
C12—C11—C10	121.1 (8)	O11—C62—H62B	110.3
C12—C11—H11	119.4	C61—C62—H62B	110.3
C10—C11—H11	119.4	H62A—C62—H62B	108.5
C11—C12—C7	120.2 (8)	O11—C63—C64	110.1 (6)
C11—C12—H12	119.9	O11—C63—H63A	109.6
C7—C12—H12	119.9	C64—C63—H63A	109.6
C14—C13—C3	117.3 (5)	O11—C63—H63B	109.6
C14—C13—H13A	108.0	C64—C63—H63B	109.6
C3—C13—H13A	108.0	H63A—C63—H63B	108.2
C14—C13—H13B	108.0	O12—C64—C63	109.8 (6)
C3—C13—H13B	108.0	O12—C64—H64A	109.7
H13A—C13—H13B	107.2	C63—C64—H64A	109.7
C19—C14—C15	120.0 (6)	O12—C64—H64B	109.7
C19—C14—C13	120.2 (6)	C63—C64—H64B	109.7
C15—C14—C13	119.6 (6)	H64A—C64—H64B	108.2
O2—C15—C14	121.3 (6)	O12—C65—C66	113.5 (6)
O2—C15—C16	120.6 (6)	O12—C65—H65A	108.9
C14—C15—C16	118.0 (6)	C66—C65—H65A	108.9
C17—C16—C15	119.6 (6)	O12—C65—H65B	108.9
C17—C16—C26	120.7 (6)	C66—C65—H65B	108.9
C15—C16—C26	119.6 (6)	H65A—C65—H65B	107.7
C16—C17—C18	122.8 (6)	N2—C66—C65	112.8 (6)
C16—C17—H17	118.6	N2—C66—H66A	109.0
C18—C17—H17	118.6	C65—C66—H66A	109.0
C19—C18—C17	117.0 (6)	N2—C66—H66B	109.0
C19—C18—C20	122.7 (6)	C65—C66—H66B	109.0
C17—C18—C20	120.1 (6)	H66A—C66—H66B	107.8
C18—C19—C14	122.7 (6)	N1—C67—C68	112.0 (6)
C18—C19—H19	118.7	N1—C67—H67A	109.2
C14—C19—H19	118.7	C68—C67—H67A	109.2
C25—C20—C21	118.9 (7)	N1—C67—H67B	109.2
C25—C20—C18	121.8 (6)	C68—C67—H67B	109.2
C21—C20—C18	119.2 (6)	H67A—C67—H67B	107.9
C20—C21—C22	120.5 (7)	O13—C68—C67	112.3 (6)
C20—C21—H21	119.7	O13—C68—H68A	109.1
C22—C21—H21	119.7	C67—C68—H68A	109.1
C23—C22—C21	119.7 (7)	O13—C68—H68B	109.1
C23—C22—H22	120.2	C67—C68—H68B	109.1
C21—C22—H22	120.2	H68A—C68—H68B	107.9
C24—C23—C22	119.8 (7)	O13—C69—C70	109.1 (6)
C24—C23—H23	120.1	O13—C69—H69A	109.9
C22—C23—H23	120.1	C70—C69—H69A	109.9
C23—C24—C25	120.9 (7)	O13—C69—H69B	109.9
C23—C24—H24	119.6	C70—C69—H69B	109.9
C25—C24—H24	119.6	H69A—C69—H69B	108.3
C20—C25—C24	120.2 (7)	O14—C70—C69	108.3 (6)
C20—C25—H25	119.9	O14—C70—H70A	110.0
C24—C25—H25	119.9	C69—C70—H70A	110.0
O3—C26—C16	110.1 (5)	O14—C70—H70B	110.0
O3—C26—H26A	109.6	C69—C70—H70B	110.0
C16—C26—H26A	109.6	H70A—C70—H70B	108.4
O3—C26—H26B	109.6	O14—C71—C72	106.8 (6)
C16—C26—H26B	109.6	O14—C71—H71A	110.4
H26A—C26—H26B	108.2	C72—C71—H71A	110.4
O3—C27—C28	110.5 (5)	O14—C71—H71B	110.4
O3—C27—H27A	109.6	C72—C71—H71B	110.4
C28—C27—H27A	109.6	H71A—C71—H71B	108.6
O3—C27—H27B	109.6	C71—C72—N2	111.5 (6)
C28—C27—H27B	109.6	C71—C72—H72A	109.3
H27A—C27—H27B	108.1	N2—C72—H72A	109.3
C33—C28—C29	120.4 (6)	C71—C72—H72B	109.3
C33—C28—C27	120.3 (6)	N2—C72—H72B	109.3
C29—C28—C27	119.4 (6)	H72A—C72—H72B	108.0
O4—C29—C30	122.4 (6)	O15—S1—C74	107.0 (5)
O4—C29—C28	119.9 (6)	O15—S1—C73	104.7 (5)
C30—C29—C28	117.6 (6)	C74—S1—C73	96.9 (6)
C31—C30—C29	120.4 (6)	O16—S2—C76	110.3 (6)
C31—C30—C40	119.9 (6)	O16—S2—C75	113.0 (6)
C29—C30—C40	119.7 (6)	C76—S2—C75	95.8 (4)
C30—C31—C32	123.1 (6)	O17—S3—C77	107.8 (4)
C30—C31—H31	118.5	O17—S3—C78	109.4 (4)
C32—C31—H31	118.5	C77—S3—C78	97.7 (5)
C33—C32—C31	115.4 (6)	S1—C73—H73A	109.5
C33—C32—C34	121.5 (6)	S1—C73—H73B	109.5
C31—C32—C34	123.0 (6)	H73A—C73—H73B	109.5
C28—C33—C32	122.9 (6)	S1—C73—H73C	109.5
C28—C33—H33	118.6	H73A—C73—H73C	109.5
C32—C33—H33	118.6	H73B—C73—H73C	109.5
C39—C34—C35	117.2 (7)	S1—C74—H74A	109.5
C39—C34—C32	121.9 (6)	S1—C74—H74B	109.5
C35—C34—C32	120.7 (6)	H74A—C74—H74B	109.5
C36—C35—C34	120.9 (7)	S1—C74—H74C	109.5
C36—C35—H35	119.5	H74A—C74—H74C	109.5
C34—C35—H35	119.5	H74B—C74—H74C	109.5
C37—C36—C35	121.0 (7)	S2—C75—H75A	109.5
C37—C36—H36	119.5	S2—C75—H75B	109.5
C35—C36—H36	119.5	H75A—C75—H75B	109.5
C36—C37—C38	118.7 (7)	S2—C75—H75C	109.5
C36—C37—H37	120.6	H75A—C75—H75C	109.5
C38—C37—H37	120.6	H75B—C75—H75C	109.5
C39—C38—C37	120.8 (7)	S2—C76—H76A	109.5
C39—C38—H38	119.6	S2—C76—H76B	109.5
C37—C38—H38	119.6	H76A—C76—H76B	109.5
C38—C39—C34	121.3 (7)	S2—C76—H76C	109.5
C38—C39—H39	119.3	H76A—C76—H76C	109.5
C34—C39—H39	119.3	H76B—C76—H76C	109.5
C41—C40—C30	113.8 (6)	S3—C77—H77A	109.5
C41—C40—H40A	108.8	S3—C77—H77B	109.5
C30—C40—H40A	108.8	H77A—C77—H77B	109.5
C41—C40—H40B	108.8	S3—C77—H77C	109.5
C30—C40—H40B	108.8	H77A—C77—H77C	109.5
H40A—C40—H40B	107.7	H77B—C77—H77C	109.5
C46—C41—C42	119.2 (6)	S3—C78—H78A	109.5
C46—C41—C40	119.6 (6)	S3—C78—H78B	109.5
C42—C41—C40	121.1 (6)	H78A—C78—H78B	109.5
O5—C42—C43	121.0 (6)	S3—C78—H78C	109.5
O5—C42—C41	120.1 (6)	H78A—C78—H78C	109.5
C43—C42—C41	118.8 (6)	H78B—C78—H78C	109.5
C44—C43—C42	119.4 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9	0.92 (8)	2.24 (7)	2.647 (7)	106 (6)
N1—H1···O11	0.92 (8)	2.28 (8)	2.756 (8)	112 (6)
N1—H1···O13	0.92 (8)	2.50 (8)	2.901 (8)	107 (5)
N2—H2···O10	0.95 (8)	2.53 (8)	2.892 (8)	103 (5)
N2—H2···O12	0.95 (8)	2.55 (8)	2.895 (8)	101 (5)
N2—H2···O14	0.95 (8)	2.20 (8)	2.718 (8)	113 (6)
C61—H61B···Cg1	0.97	2.97	3.77	141
C69—H69B···Cg2	0.97	2.64	3.56	159
C71—H71A···Cg3	0.97	2.66	3.52	148