The first uranyl complexes with valerate ions

FT–IR spectroscopy and single-crystal X-ray structure analysis were used to characterize the discrete neutral compound di­aqua­dioxidobis(n-valerato-κ²O,O′)uranium(VI), [UO₂(C₄H₉COO)₂(H₂O)₂], (I), and the ionic compound potassium dioxidotris(n-valerato-κ²O,O′)uranium(VI), K[UO₂(C₄H₉COO)₃], (II). The U^VI cation in neutral (I) is at a site of 2/m symmetry. Potassium salt (II) has two U centres and two K⁺ cations residing on twofold axes, while a third independent formula unit is on a general position. The ligands in both compounds were found to suffer severe disorder. The FT–IR spectroscopic results agree with the X-ray data. The composition and structure of the ionic potassium uranyl valerate are similar to those of previously reported potassium uranyl complexes with acetate, propionate and butyrate ligands. Progressive lengthening of the alkyl groups in these otherwise similar compounds was found to have an impact on their structures, including on the number of independent U and K⁺ sites, on the coordination modes of some of the K⁺ centres and on the minimum distances between U atoms. The evolution of the KUO₆ frameworks in the four homologous compounds is analysed in detail, revealing a new example of three-dimensional topological isomerism in coordination com­pounds of U^VI.

S1. Comment

Uranyl carboxylates are used in the nuclear industry for decontamination of uranium (Haas & Northup, 2004). They occur in nature (Lenhart et al., 2000; Rosberg et al., 2000) and affect biological systems (Miller, 2009). In addition, uranyl complexes with organic ions can be used for the construction of uranyl–organic frameworks (Wang & Chen, 2011). To date, the structures of about 70 uranyl complexes with short monocarboxylates (formate, acetate, propionate, isobutyrate and crotonate) have been reported. Uranyl carboxylates with longer hydrocarbon chains are less well studied (Leciejewicz et al., 1995). In particular, the structures of valerate-containing uranyl complexes have not previously been analysed. However, the existence of several uranium(VI) compounds with n-valerate anions (n-C₄H₉COO) has been reported. Courtois (1914) described needle-like crystals formulated as [UO₂(n-C₄H₉COO)₂(H₂O)₂], which can release water molecules in dry air under heating. Rimbach (1904) synthesized K[UO₂(n-C₄H₉COO)₃(H₂O)₂] by the reaction of potassium diuranate and valeric acid in water. Here, we report the structures of two uranyl complexes with n-valerate anions, viz. [UO₂(n-C₄H₉COO)₂(H₂O)₂], (I), and K[UO₂(n-C₄H₉COO)₃], (II).

FT–IR spectroscopy reveals the presence of uranyl, bidentate–chelating carboxylate and alkyl groups in both compounds, as well as terminally coordinated water molecules in (I). The X-ray structure analyses show that (I) and (II) have one and three crystallographically independent U^VI cations, respectively. In both complexes, the U^VI cations adopt hexagonal–bipyramidal geometry, with the O atoms of the uranyl cations situated in the axial positions.

In (I), a number of atoms lie on symmetry elements: atom U1 is on a site of 2/m symmetry, water atom O1 lies on a twofold axis, and uranyl atoms O2 and O3, as well as atoms C1, C2 and C6, are on mirror planes. Most of the atoms in (I) are disordered, as shown in Fig. 1. We interpret the disorder assembly as consisting of two disorder groups, with atom O2 and its centrosymmetrically related congener belonging to one disorder group, and atom O3 and its symmetry relative to the other. The uranyl fragment UO₂ in (I) is symmetrical [U1—O2 = 1.752 (9) Å and U1—O3 = 1.746 (11) Å] and linear. The equatorial plane consists of four O atoms from two chelating valerate anions and two aqua ligands, which are trans to each other. The discrete [UO₂(C₄H₉COO)₂(H₂O)₂] molecules in (I) form two-dimensional hydrogen-bonded motifs. Each of the two disordered congeners forms one hydrogen bond, O1—H1···O4(x + 1/2, y + 1/2, z) (H···O = 1.93 Å and O—H···O = 180°) and O1—H1···O5(-x + 5/2, -y + 1/2, -z + 2) (H···O = 2.20 Å and O—H···O = 129°). According to the criteria of Steiner (2002), these hydrogen bonds are of average strength.

In (II), only two of the three independent uranyl cations, U1O₂²⁺ and U2O₂²⁺ (Figs. 2a and 2b), which lie on twofold axes, are symmetrical [U1—O1 = 1.775 (12) Å, U2—O5 = 1.716 (11) Å, and O—U—O = 179.1 (10) and 180.0 (8)°, respectively]. Atom U3 occupies a general position (Fig. 2c), with a less symmetric U3O₂²⁺ cation [U3—O9 = 1.719 (12) Å, U3—O10 = 1.757 (12) Å and O9—U3—O10 = 179.2 (6)°]. In the equatorial plane of the uranyl cations in (II), there are six O atoms from three chelating valerate anions. The main structural unit of (II) is the anionic mononuclear complex [UO₂(C₄H₉COO)₃]^-, which forms a three-dimensional framework by means of electrostatic interactions with the K⁺ cations (Fig. 3).

The Cambridge Structural Database (CSD, Version?; Allen, 2002) includes three anionic uranyl complexes K[UO₂L₃] which, like (II), possess alkyl monocarboxylate ligands L^-. These are orthorhombic K[UO₂(C₃H₇COO)₃] [(III); Pushkin et al., 2012], cubic K[UO₂(C₂H₅COO)₃] [(IV); Serezhkina et al., 2013] and tetragonal K[UO₂(CH₃COO)₃] [(V); Serezhkina et al., 2010]. Compounds (III)–(V) have bidentate–chelating n-butyrate, propionate and acetate ligands, respectively. The structure of (III) contains four independent U atoms (and K⁺ cations), whereas (IV) and (V) contain one independent U atom (and K⁺ cation) each. All K⁺ cations in (II)–(V) adopt distorted octahedral coordinations, except for one trigonal prismatic K⁺ cation in (III) (Pushkin et al., 2012). The three-dimensional frameworks in (II)–(V), which consist of K, U and O atoms, can be examined in a simple fashion by omitting from consideration the terminal groups (the hydrocarbon chains and the O atoms of the uranyl cations). The four frameworks in (II)–(V), of composition KUO₆, have each U (K) atom connected to three K (U) atoms by double –O– bridges (Fig. 4). The bulky carboxylate anions fill the voids in these frameworks (Fig. 5). The peculiarities of the three-dimensional frameworks are then differentiated only by the steric characteristics and dispositions of the hydrocarbon residues and the manner in which the frameworks accommodate them.

It might be reasonable to expect that the minimum distance between U atoms in one of these structures, d_UU, would become greater as the alkyl side chain progresses from shorter to longer. The minimum d_UU does at first increase, from 6.53 to 7.38 Å, on going from acetate (V) to propionate (IV), but it then decreases to 6.41 Å in the butyrate compound (III) and further to 6.24 Å for valerate (II). We can understand this with reference to the concept of coordination spheres (CS) and coordination sequences. The CS's are successive neighbourhoods of topologically relevant atoms (U and K) around a central atom, here U. For example, in Fig. 4, R⁰ is the central atom, and the atoms labelled R¹ are those of its first CS. The O atoms are bridges and, for the present purposes, are not counted as a CS. The CS's are compared using the further concept of coordination sequences C_P^N (O'Keeffe, 1995), which gives the number of atoms in the Nth CS around the central atom. We take U as the central atom for (II)–(V), so odd CS's consist only of K and even CS's are all U. Thus, C_P shows the number of R atoms (R = K or U) of the Nth coordination shell which are connected to the central U atom through the R—(O—R—)_N chains. If each R atom were connected to three other R atoms through O-atom bridges (Fig. 4), the number of atoms would double in successive CS's. The theoretical population of CS's for (II)–(V) would then be 3, 6, 12, 24, 48, 96, 192 etc. However, this avalanche-like increase of C_P^N is obviated by a steric factor. What actually occurs is that at some point two adjacent R—(O—R—)_N chains share a common R atom (Fig. 6) to form a cyclic pattern. As a result, as linkages appear, the C_P^N values for (II)–(V) become smaller than the theoretically possible values. For acetate (V), this decrease starts from the fourth CS (Fig. 7, curve a) and eight-membered rings are formed; these would be 16-membered rings if O atoms were counted. From a topological point of view, the KUO₆ framework in (V) represents a three-coordinated uninodal net of a rare 3/8/t7 type (Alexandrov et al., 2011). In cubic (IV) (propionate), the linkage of adjacent chains starts only in the fifth CS (Fig. 7, curve b). Accordingly, the cycles in the structure of (IV) contain at least ten atoms. The KUO₆ framework in (IV) also represents a three-coordinated uninodal net, but of one of the most common topological types, srs (Hyde et al., 2008). In contrast with the uninodal nets in (IV) and (V), the KUO₆ frameworks for valerate (II) and butyrate (III) represent more complicated three-coordinated 6-nodal nets. For the U1 atoms in (II) and (III), the linkage of chains starts from the fourth CS (Fig. 7, curve c), as in (V). But for atoms U2, U3 and U4 in (II) and (III), chain linkage begins in the third CS (Fig. 7, curves d and e), so that six-membered rings can also be found in the structures of these complexes. Evidently, the KUO₆ frameworks in (II)–(V) are similar in the first CS, but rearrange and distort in subsequent CS's.

These differences in successive CS's allow the KUO₆ frameworks to accommodate more or less voluminous groups. Since the voids in these structures are continuous and unbounded, it is not possible to determine their volumes. Instead, one can estimate the size of the largest sphere that can fit in the largest cavity in the KUO₆ framework. For (II)–(V), the volumes of these spheres are 1062, 873, 312 and 349 ų, respectively. Thus, the KUO₆ frameworks in (II) and (III) provide more space for the voluminous valerate and butyrate anions through the formation of smaller six-membered rings in earlier CS's.

It is noteworthy that the propionate complex, (IV), which has the largest minimum rings (ten-membered) of all compounds (II)–(V), has the highest possible symmetry, cubic. It could be that, even in the absence of hydrocarbon chains, the KUO₆ framework can not be constructed with larger minimum rings because it reaches the steric hindrance limit. Potassium uranyl propionate, (IV), may be an example of a system in which the hydrocarbon chains (–C₃H₅) fit well in the voids of such a highly symmetric three-dimensional framework. Smaller hydrocarbon chains [–C₂H₃ in (V)] require adjacent R—(O—R—)_N chains to link earlier in order to approach one another. This could cause the lowering of the symmetry to tetragonal. Longer hydrocarbon chains [–C₄H₇ and –C₅H₉ in (III) and (II), respectively] do not fit the voids of such a symmetric framework, and it distorts to accommodate them. The distortion is manifested in the alternating interatomic U···U distances, an increase in the number of independent U atoms and K⁺ cations and even a change in coordination geometry around some of the K⁺ centres. The symmetry of (II) and (III) is lowered to orthorhombic. The variation of the KUO₆ frameworks in these four compounds provides a new example of three-dimensional topological isomerism in coordination compounds of U^VI.

The effect of alkyl group length in the K[UO₂L₃] homologous series on the characteristics of noncovalent interactions was analysed by means of a stereoatomic model of crystal structure (Serezhkin, 2007), based on Voronoi–Dirichlet polyhedra (VDP) descriptors (Blatov et al., 1995). This approach allows one to describe all types of interatomic interactions from a single point of view without using any system of crystal–chemical radii (Serezhkin et al., 2012). The VDP of a point – an atom in the present context – is a convex polyhedron of minimum volume, containing this atom and bounded by planes which are perpendicular bisectors of the line segments connecting this atom to all other atoms. Thus, each face of a VDP in a crystal structure belongs to two atoms A and B, and can be characterized by its `rank of interatomic contact' (RC) (Shevchenko & Serezhkin, 2004), which is the number of chemical bonds in the shortest chain connecting A and B. Thus, RC = 1 for all covalent bonds, and RC = 2 for A and B atoms in the chain A–D–B. If a face of the VDP of atom A is generated with atom B from another molecule (or chain or layer), the rank of the A···B contact is set to zero, because there is no bonding chain connecting A and B. According to this approach, all faces with RC ≥ 2 correspond to different types of non-covalent intramolecular interactions, and the partial contributions of each type can be unambiguously estimated by calculating the relative surface areas of the corresponding faces of the VDP. Our calculations on (II)–(V) showed that the partial contribution of the H···H dispersion interactions increases significantly through the series from the acetate to the valerate derivatives (Fig. 8). Thus, in acetate (V), only 28.5% of noncovalent interactions correspond to H···H contacts, whereas for (IV), (III) and (II) these valuee are 42.6, 57.6 and 60.5%, respectively. On the other hand, the surface areas corresponding to H···O hydrogen bonds and O···O dispersion interactions decrease in this sequence. The respective partial contributions for H···O and O···O contacts are 41.3 and 15.8% in (V), 35.2 and 9.8% in (IV), 22.0 and 9.1% in (III), and 19.6 and 7.7% in (II). The partial contributions of noncovalent H···C interactions in (II)–(V) are almost the same (8.7% on average) and those of the remaining types of contacts (C···C, C···O etc.) do not exceed 4%.

Related literature

For related literature, see: Alexandrov et al. (2011); Allen (2002); Blatov (2012); Blatov et al. (1995); Courtois (1914); Flack (1983); Haas & Northup (2004); Hyde et al. (2008); Leciejewicz et al. (1995); Lenhart et al. (2000); Miller (2009); Moita et al. (1994); O'Keeffe (1995); Pushkin et al. (2012); Rimbach (1904); Rosberg et al. (2000); Serezhkin (2007); Serezhkin et al. (2012); Serezhkina et al. (2010, 2013); Shevchenko & Serezhkin (2004); Steiner (2002); Wang & Chen (2011).

S2. Experimental

UO₂(NO₃)₂.6H₂O (0.2 mmol), valeric acid (0.6 mmol) and NaOH (0.6 mmol) were dissolved in water (6 ml). Yellow prismatic crystals of (I) formed upon isothermal evaporation of the reaction mixture. The same procedure with KOH instead of NaOH afforded plate-like crystals of (II). It is noteworthy that, under the conditions described, Na⁺, in contrast with K⁺, did not enter into the structure. Absorption bands in the FT–IR spectra of (I) and (II) correspond to vibrations of the UO₂²⁺ and C₄H₉COO^- ions, and for (I) to H₂O molecules. Full assignment of absorption bands was made according to Moita et al. (1994) and is provided as Supplementary materials.

S3. Refinement

Refinement of (I) using the space group C2 gave large correlations and an absolute structure parameter of 0.38 (8) (Flack, 1983), and moreover gave the same disordered structural model as was found when the space group C2/m was used. The final refinement used C2/m, which did not produce a correlation problem. The uranyl O atoms and the valerate unit are disordered over two sites across the mirror plane. In (II), three of the seven independent carboxylate anions are disordered, each over two sites with equal occupancies. One of these was refined isotropically (C1–C5A,B). The lengths of 24 C—C bonds and nine 1,3-distances in (II) were restrained. A common set of anisotropic displacement parameters was refined for the last four C atoms of each valerate ligand. In addition, restraints to isotropic behaviour were applied to the anisotropic displacement parameters of two O and four C atoms. H atoms were placed in calculated positions and refined as riding, with C—H = 0.96, 0.98 or 0.99 Å and O—H = 0.85 Å [Please check added text], and with U_iso(H) = 1.5U_eq(C,O) for methyl groups and water molecules or 1.2U_eq(C) for other C atoms. Calculations of coordination sequences and noncovalent interactions were carried out with the program package TOPOS (Blatov, 2012).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The molecule is disordered in such a way that the central UO2(C4H9COO)2 fragment is disordered over two sites (O2/O4/C1–C5 and O3/O5/C6/C2^iv–C5^iv) and each of these fragments has its terminal –C3H7 group symmetrically disordered over two sites. The butyl fragments on atoms C6 and C6^i are depicted without H atoms and without ellipsoids. Second congeners of symmetrically disordered fragments are shown as dashed lines. [Symmetry codes: (i) -x + 2, -y, -z + 2; (ii) x, -y, z; (iii) -x + 2, y, -z + 2; (iv) x + 1, -y, z; (v) x + 1, y, z; (vi) -x + 1, -y, -z + 2; (vii) -x + 1, y, -z + 2.]
	Fig. 2. The structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Three of the seven independent carboxylate groups are equiprobably [equally?] disordered over two sites: (a) molecule 1, atoms C2A–C5A and C2B–C5B, and C6–C10 and C6^i–C10^i; (b) molecule 2, atoms C18–C20 and C18^ii–C20^ii. One of each pair of disordered positions is depicted with dashed lines. (c) A view of molecule 3, shown without disorder. [Symmetry codes: (i) -x, y, -z + 3/2; (ii) x, -y, -z + 2.]
	Fig. 3. The asymmetric unit of (II). Only one disorder group is depicted for each disorder assembly [dashed lines?].
	Fig. 4. The bonding in the first coordination sphere of a central atom R^0 in the KUO6 framework. Each R atom (R = K or U) is connected to three other R atoms by double –O– bridges. Superscripts indicate the number of the coordination sphere.
	Fig. 5. The KUO6 framework in (II) in polyhedral representation. The voids are occupied by carboxylate ligands.
	Fig. 6. Three R—(O—R—)N chains (solid, dashed and dot-and-dashed lines) start from the basic atom R^0. Two of them link in the third coordination sphere through the common atom R^3, forming a six-membered ring. Superscripts indicate the number of the coordination sphere.
	Fig. 7. Coordination sequences (CP^7) from the central U atoms in (a) K[UO2(CH3COO)3], (V); (b) K[UO2(C2H5COO)3], (IV); (c) U1 in K[UO2(C3H7COO)3], (III), and K[UO2(C4H9COO)3], (II); (d,e) U2, U3 and U4 in K[UO2(C3H7COO)3], (III), and K[UO2(C4H9COO)3], (II). The heavy line indicates the largest theoretically possible values. The values of CP are: (a) 3, 6, 12, 21, 34, 52, 71; (b) 3, 6, 12, 24, 35, 48, 69; (c) 3, 6, 12, 20, 30, 44, 63; (d) 3, 6, 10, 17, 30, 45, 60; (e) 3, 6, 10, 16, 29, 44, 59.
	Fig. 8. Partial contributions (Δ) of several types of non-covalent interactions in (a) K[UO2(C4H9COO)3], (II); (b) K[UO2(C3H7COO)3], (III); (c) K[UO2(C2H5COO)3], (IV); (d) K[UO2(CH3COO)3],(V). The values of Δ are: (a) 60, 20, 8, 9; (b) 58, 22, 9, 8; (c) 43, 35, 10, 9; (d) 28, 41, 16, 9.

(I) Diaquadioxidobis(n-valerato-κ²O,O')uranium(VI)

Crystal data

[U(C5H9O2)2O2(H2O)2]	F(000) = 476
Mr = 508.31	Dx = 2.185 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 125 reflections
a = 7.782 (4) Å	θ = 2.5–26.8°
b = 10.802 (5) Å	µ = 10.53 mm^−1
c = 9.512 (5) Å	T = 100 K
β = 104.885 (9)°	Prism, yellow
V = 772.7 (7) Å^3	0.21 × 0.11 × 0.08 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	1187 independent reflections
Radiation source: fine-focus sealed tube	1187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→10
Tmin = 0.261, Tmax = 0.430	k = −15→15
4876 measured reflections	l = −13→13

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
1187 reflections	(Δ/σ)max < 0.001
85 parameters	Δρmax = 2.06 e Å^−3
0 restraints	Δρmin = −2.05 e Å^−3

Special details

Experimental. FT–IR spectra were measured using a Perkin–Elmer Spectrum 100 FT–IR spectrometer, using pressed KBr pellets.

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	Occ. (<1)
U1	1.0000	0.0000	1.0000	0.00883 (9)
O1	1.0000	0.2248 (5)	1.0000	0.0481 (18)
H1	1.0628	0.2782	0.9704	0.072*
O2	1.0290 (12)	0.0000	0.8233 (10)	0.026 (2)	0.5
O3	1.1439 (13)	0.0000	1.1743 (11)	0.042 (3)	0.5
O4	0.7057 (7)	−0.1000 (6)	0.9038 (7)	0.0189 (12)	0.5
O5	1.2305 (8)	0.0995 (6)	0.8998 (8)	0.0209 (13)	0.5
C1	0.6208 (15)	0.0000	0.8634 (12)	0.013 (2)	0.5
C2	0.4305 (8)	0.0000	0.7720 (7)	0.0239 (13)
H2	0.3507	0.0095	0.8333	0.029*	0.5
H3	0.4048	−0.0775	0.7215	0.029*	0.5
C3	0.4012 (14)	0.1116 (9)	0.6565 (10)	0.0246 (19)	0.5
H4	0.4099	0.1916	0.7087	0.029*	0.5
H5	0.4960	0.1095	0.6043	0.029*	0.5
C4	0.2191 (14)	0.1023 (10)	0.5463 (11)	0.028 (2)	0.5
H6	0.2084	0.0203	0.4985	0.033*	0.5
H7	0.1247	0.1086	0.5986	0.033*	0.5
C5	0.1909 (16)	0.2019 (11)	0.4314 (12)	0.033 (2)	0.5
H8	0.0756	0.1920	0.3654	0.050*	0.5
H9	0.1985	0.2817	0.4769	0.050*	0.5
H10	0.2806	0.1952	0.3788	0.050*	0.5
C6	1.2869 (14)	0.0000	0.8611 (13)	0.014 (2)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.00675 (13)	0.00607 (13)	0.01403 (15)	0.000	0.00333 (10)	0.000
O1	0.033 (3)	0.009 (2)	0.115 (6)	0.000	0.043 (3)	0.000
O2	0.020 (4)	0.043 (6)	0.016 (4)	0.000	0.009 (4)	0.000
O3	0.016 (5)	0.097 (11)	0.018 (5)	0.000	0.010 (4)	0.000
O4	0.009 (3)	0.011 (3)	0.035 (4)	−0.001 (2)	0.003 (2)	−0.001 (2)
O5	0.017 (3)	0.009 (3)	0.039 (4)	0.003 (2)	0.013 (3)	0.004 (2)
C1	0.017 (5)	0.011 (5)	0.014 (5)	0.000	0.011 (4)	0.000
C2	0.014 (3)	0.034 (4)	0.023 (3)	0.000	0.002 (2)	0.000
C3	0.032 (5)	0.022 (4)	0.020 (4)	−0.006 (4)	0.006 (4)	0.002 (4)
C4	0.027 (5)	0.030 (5)	0.024 (5)	0.004 (4)	0.003 (4)	0.006 (4)
C5	0.040 (6)	0.031 (6)	0.030 (5)	0.005 (4)	0.011 (5)	0.009 (4)
C6	0.007 (4)	0.021 (6)	0.015 (5)	0.000	0.005 (4)	0.000

Geometric parameters (Å, º)

U1—O3	1.746 (11)	C1—O4^ii	1.273 (9)
U1—O3^i	1.746 (11)	C1—C2	1.512 (13)
U1—O2^i	1.752 (9)	C2—C6^iv	1.567 (12)
U1—O2	1.752 (9)	C2—C3^ii	1.608 (10)
U1—O1^i	2.428 (5)	C2—C3	1.608 (10)
U1—O1	2.428 (5)	C2—H2	0.9599
U1—O5^i	2.482 (6)	C2—H3	0.9600
U1—O5^ii	2.482 (6)	C3—C4	1.534 (14)
U1—O5^iii	2.482 (6)	C3—H4	0.9900
U1—O5	2.482 (6)	C3—H5	0.9900
U1—O4	2.485 (6)	C4—C5	1.508 (14)
U1—O4^i	2.485 (6)	C4—H6	0.9900
O1—H1	0.8500	C4—H7	0.9900
O2—O3^i	1.351 (13)	C5—H8	0.9600
O3—O2^i	1.351 (13)	C5—H9	0.9599
O4—C1	1.273 (9)	C5—H10	0.9601
O4—O5^i	1.806 (10)	C6—O5^ii	1.251 (8)
O5—C6	1.251 (8)	C6—C2^v	1.567 (12)
O5—O4^i	1.806 (10)
O3—U1—O3^i	180	O5^i—U1—O4^i	137.4 (2)
O3—U1—O2^i	45.4 (4)	O5^ii—U1—O4^i	68.9 (2)
O3^i—U1—O2^i	134.6 (4)	O5^iii—U1—O4^i	111.1 (2)
O3—U1—O2	134.5 (4)	O5—U1—O4^i	42.6 (2)
O3^i—U1—O2	45.4 (4)	O4—U1—O4^i	180
O2^i—U1—O2	180	U1—O1—H1	132.8
O3—U1—O1^i	90	O3^i—O2—U1	67.0 (6)
O3^i—U1—O1^i	90	O2^i—O3—U1	67.5 (6)
O2^i—U1—O1^i	90	C1—O4—O5^i	107.1 (7)
O2—U1—O1^i	90	C1—O4—U1	95.8 (5)
O3—U1—O1	90	O5^i—O4—U1	68.6 (3)
O3^i—U1—O1	90	C6—O5—O4^i	106.4 (7)
O2^i—U1—O1	90	C6—O5—U1	94.8 (5)
O2—U1—O1	90	O4^i—O5—U1	68.8 (3)
O1^i—U1—O1	180	O4^ii—C1—O4	116.1 (11)
O3—U1—O5^i	89.2 (3)	O4^ii—C1—C2	122.0 (5)
O3^i—U1—O5^i	90.8 (3)	O4—C1—C2	122.0 (5)
O2^i—U1—O5^i	49.3 (3)	O4^ii—C1—U1	58.4 (5)
O2—U1—O5^i	130.7 (3)	O4—C1—U1	58.4 (5)
O1^i—U1—O5^i	64.34 (14)	C2—C1—U1	171.9 (7)
O1—U1—O5^i	115.66 (14)	C1—C2—C6^iv	114.8 (7)
O3—U1—O5^ii	90.8 (3)	C1—C2—C3^ii	109.8 (5)
O3^i—U1—O5^ii	89.2 (3)	C6^iv—C2—C3^ii	111.9 (5)
O2^i—U1—O5^ii	130.7 (3)	C1—C2—C3	109.8 (5)
O2—U1—O5^ii	49.3 (3)	C6^iv—C2—C3	111.9 (5)
O1^i—U1—O5^ii	64.34 (14)	C3^ii—C2—C3	97.2 (8)
O1—U1—O5^ii	115.66 (14)	C1—C2—H2	110.0
O5^i—U1—O5^ii	128.7 (3)	C3^ii—C2—H2	119.6
O3—U1—O5^iii	89.2 (3)	C3—C2—H2	109.5
O3^i—U1—O5^iii	90.8 (3)	C1—C2—H3	109.6
O2^i—U1—O5^iii	49.3 (3)	C6^iv—C2—H3	100.6
O2—U1—O5^iii	130.7 (3)	C3—C2—H3	109.7
O1^i—U1—O5^iii	115.66 (14)	H2—C2—H3	108.2
O1—U1—O5^iii	64.34 (14)	C4—C3—C2	111.2 (7)
O5^i—U1—O5^iii	51.3 (3)	C4—C3—H4	109.4
O5^ii—U1—O5^iii	180	C2—C3—H4	109.4
O3—U1—O5	90.8 (3)	C4—C3—H5	109.4
O3^i—U1—O5	89.2 (3)	C2—C3—H5	109.4
O2^i—U1—O5	130.7 (3)	H4—C3—H5	108.0
O2—U1—O5	49.3 (3)	C5—C4—C3	112.7 (9)
O1^i—U1—O5	115.66 (14)	C5—C4—H6	109.1
O1—U1—O5	64.34 (14)	C3—C4—H6	109.1
O5^i—U1—O5	180	C5—C4—H7	109.1
O5^ii—U1—O5	51.3 (3)	C3—C4—H7	109.1
O5^iii—U1—O5	128.7 (3)	H6—C4—H7	107.8
O3—U1—O4	131.0 (3)	C4—C5—C5^vi	86.1 (9)
O3^i—U1—O4	49.0 (3)	C4—C5—H8	109.5
O2^i—U1—O4	91.1 (3)	C5^vi—C5—H8	141.6
O2—U1—O4	88.9 (3)	C4—C5—H9	109.5
O1^i—U1—O4	64.24 (14)	H8—C5—H9	109.5
O1—U1—O4	115.76 (14)	C4—C5—H10	109.5
O5^i—U1—O4	42.6 (2)	C5^vi—C5—H10	96.9
O5^ii—U1—O4	111.1 (2)	H8—C5—H10	109.5
O5^iii—U1—O4	68.9 (2)	H9—C5—H10	109.5
O5—U1—O4	137.3 (2)	O5—C6—O5^ii	118.4 (10)
O3—U1—O4^i	49.0 (3)	O5—C6—C2^v	120.8 (5)
O3^i—U1—O4^i	131.0 (3)	O5^ii—C6—C2^v	120.8 (5)
O2^i—U1—O4^i	88.9 (3)	O5—C6—U1	59.5 (5)
O2—U1—O4^i	91.1 (3)	O5^ii—C6—U1	59.5 (5)
O1^i—U1—O4^i	115.76 (14)	C2^v—C6—U1	174.9 (7)
O1—U1—O4^i	64.24 (14)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^vii	0.85	1.93	2.781 (7)	180
O1—H1···O5^viii	0.85	2.20	2.808 (8)	128

Symmetry codes: (vii) x+1/2, y+1/2, z; (viii) −x+5/2, −y+1/2, −z+2.

(II) Potassium dioxidotris(n-valerato-κ²O,O')uranium(VI)

Crystal data

K[U(C5H9O2)3O2]	F(000) = 4672
Mr = 612.50	Dx = 1.927 Mg m^−3
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 1355 reflections
a = 17.294 (3) Å	θ = 2.6–22.2°
b = 23.405 (4) Å	µ = 7.92 mm^−1
c = 20.862 (3) Å	T = 100 K
V = 8444 (2) Å^3	Plate, yellow
Z = 16	0.24 × 0.15 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	10209 independent reflections
Radiation source: fine-focus sealed tube	8322 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
ω scans	θmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −18→22
Tmin = 0.252, Tmax = 0.797	k = −30→30
37788 measured reflections	l = −27→27

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)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.193	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.25	(Δ/σ)max = 0.008
10209 reflections	Δρmax = 2.77 e Å^−3
366 parameters	Δρmin = −1.85 e Å^−3
63 restraints	Absolute structure: Flack (1983), with 4677 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.061 (16)

Special details

Experimental. FT–IR spectra were measured using a Perkin–Elmer Spectrum 100 FT–IR spectrometer, using pressed KBr pellets.

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	Occ. (<1)
U1	0.0000	0.10330 (3)	0.7500	0.03262 (18)
U2	0.32439 (4)	0.0000	1.0000	0.0370 (2)
U3	0.34413 (3)	−0.08589 (3)	0.67491 (3)	0.03730 (16)
K1	0.4201 (3)	0.0000	0.5000	0.0403 (10)
K2	0.0000	0.29034 (19)	0.7500	0.0474 (12)
K3	0.20505 (19)	0.01060 (15)	0.81415 (15)	0.0379 (7)
O1	−0.0331 (9)	0.1027 (7)	0.8305 (6)	0.069 (4)
O2	0.0726 (9)	0.1921 (7)	0.7716 (8)	0.072 (4)
O3	0.1384 (8)	0.1109 (6)	0.7845 (7)	0.060 (3)
O4	0.0563 (8)	0.0102 (5)	0.7711 (9)	0.075 (5)
O5	0.3244 (7)	0.0717 (5)	1.0172 (5)	0.046 (3)
O6	0.4421 (6)	0.0165 (6)	0.9372 (5)	0.052 (3)
O7	0.3337 (7)	0.0246 (6)	0.8848 (5)	0.053 (3)
O8	0.1958 (6)	0.0060 (7)	0.9489 (6)	0.054 (3)
O9	0.2687 (7)	−0.1247 (6)	0.6436 (6)	0.053 (3)
O10	0.4212 (7)	−0.0468 (5)	0.7079 (6)	0.048 (3)
O11	0.4406 (10)	−0.1623 (6)	0.6445 (6)	0.070 (4)
O12	0.4146 (6)	−0.0952 (5)	0.5728 (5)	0.042 (2)
O13	0.3180 (7)	−0.0077 (5)	0.5969 (6)	0.050 (3)
O14	0.2630 (7)	−0.0011 (6)	0.6940 (5)	0.054 (3)
O15	0.2761 (7)	−0.0914 (5)	0.7815 (5)	0.044 (3)
O16	0.3585 (7)	−0.1560 (5)	0.7607 (5)	0.046 (3)
C1	0.1340 (17)	0.1637 (14)	0.7807 (15)	0.103 (9)*
C2A	0.170 (3)	0.2166 (18)	0.809 (3)	0.152 (12)*	0.50
H2AA	0.1439	0.2258	0.8498	0.183*	0.50
H2AB	0.1616	0.2490	0.7792	0.183*	0.50
C3A	0.255 (3)	0.210 (3)	0.821 (3)	0.152 (12)*	0.50
H3AA	0.2808	0.2470	0.8156	0.183*	0.50
H3AB	0.2767	0.1832	0.7882	0.183*	0.50
C4A	0.272 (5)	0.186 (3)	0.887 (3)	0.152 (12)*	0.50
H4AA	0.2477	0.1482	0.8909	0.183*	0.50
H4AB	0.3283	0.1818	0.8916	0.183*	0.50
C5A	0.242 (6)	0.225 (3)	0.939 (3)	0.152 (12)*	0.50
H5AA	0.2482	0.2060	0.9802	0.228*	0.50
H5AB	0.1868	0.2326	0.9312	0.228*	0.50
H5AC	0.2707	0.2608	0.9383	0.228*	0.50
C2B	0.207 (3)	0.195 (3)	0.762 (3)	0.152 (12)*	0.50
H2BA	0.2171	0.2009	0.7174	0.228*	0.50
H2BC	0.1870	0.2298	0.7804	0.228*	0.50
C3B	0.2763 (18)	0.173 (3)	0.797 (3)	0.152 (12)*	0.50
H3BA	0.3212	0.1977	0.7879	0.183*	0.50
H3BB	0.2885	0.1340	0.7813	0.183*	0.50
C4B	0.264 (3)	0.170 (4)	0.869 (3)	0.152 (12)*	0.50
H4BA	0.2134	0.1872	0.8791	0.183*	0.50
H4BB	0.2636	0.1299	0.8824	0.183*	0.50
C5B	0.326 (5)	0.202 (4)	0.905 (3)	0.152 (12)*	0.50
H5BA	0.3193	0.1957	0.9507	0.228*	0.50
H5BB	0.3230	0.2426	0.8950	0.228*	0.50
H5BC	0.3772	0.1873	0.8916	0.228*	0.50
C6	0.000 (4)	−0.0145 (13)	0.7371 (17)	0.062 (10)	0.50
C7	0.010 (7)	−0.0762 (17)	0.755 (4)	0.141 (14)	0.50
H7A	0.0625	−0.0896	0.7536	0.170*	0.50
H7B	−0.0155	−0.0896	0.7169	0.170*	0.50
C8	−0.035 (5)	−0.093 (2)	0.813 (3)	0.141 (14)	0.50
H8A	−0.0293	−0.1330	0.8052	0.170*	0.50
H8B	−0.0886	−0.0853	0.8033	0.170*	0.50
C9	−0.034 (5)	−0.097 (2)	0.885 (2)	0.141 (14)	0.50
H9A	−0.0716	−0.0692	0.9029	0.170*	0.50
H9B	0.0180	−0.0857	0.9005	0.170*	0.50
C10	−0.053 (5)	−0.155 (3)	0.910 (3)	0.141 (14)	0.50
H10A	−0.0545	−0.1546	0.9566	0.170*	0.50
H10B	−0.0130	−0.1823	0.8955	0.170*	0.50
H10C	−0.1032	−0.1673	0.8930	0.170*	0.50
C11	0.4070 (11)	0.0303 (11)	0.8873 (8)	0.061 (6)
C12	0.4497 (19)	0.0480 (13)	0.8273 (15)	0.104 (5)
H12A	0.4132	0.0674	0.7980	0.125*
H12B	0.4689	0.0133	0.8053	0.125*
C13	0.5187 (19)	0.0882 (10)	0.8408 (14)	0.104 (5)
H13A	0.5514	0.0889	0.8019	0.125*
H13B	0.5499	0.0707	0.8754	0.125*
C14	0.5028 (16)	0.1494 (10)	0.8598 (14)	0.104 (5)
H14A	0.4727	0.1684	0.8255	0.125*
H14B	0.4715	0.1501	0.8995	0.125*
C15	0.5772 (16)	0.1816 (13)	0.8707 (15)	0.104 (5)
H15A	0.5657	0.2221	0.8782	0.125*
H15B	0.6103	0.1779	0.8328	0.125*
H15C	0.6039	0.1658	0.9081	0.125*
C16	0.1622 (10)	0.0000	1.0000	0.048 (5)
C17	0.0757 (10)	0.0000	1.0000	0.069 (5)
H17A	0.0598	−0.0350	0.9895	0.082*	0.50
H17B	0.0598	0.0264	0.9632	0.082*	0.50
C18	0.0330 (16)	0.0213 (19)	1.057 (3)	0.069 (5)	0.50
H18A	0.0539	0.0573	1.0700	0.082*	0.50
H18B	0.0429	−0.0054	1.0906	0.082*	0.50
C19	−0.0542 (16)	0.0226 (18)	1.053 (2)	0.069 (5)	0.50
H19A	−0.0692	0.0431	1.0136	0.082*	0.50
H19B	−0.0729	−0.0172	1.0490	0.082*	0.50
C20	−0.096 (2)	0.0498 (17)	1.108 (2)	0.069 (5)	0.50
H20A	−0.1510	0.0519	1.0990	0.082*	0.50
H20B	−0.0753	0.0884	1.1153	0.082*	0.50
H20C	−0.0874	0.0269	1.1472	0.082*	0.50
C21	0.4524 (12)	−0.1406 (10)	0.5877 (10)	0.066 (6)
C22	0.5108 (19)	−0.1678 (11)	0.5443 (15)	0.122 (6)
H22A	0.5630	−0.1540	0.5563	0.146*
H22B	0.5006	−0.1554	0.4997	0.146*
C23	0.510 (2)	−0.2323 (12)	0.5468 (18)	0.122 (6)
H23A	0.5313	−0.2441	0.5889	0.146*
H23B	0.5463	−0.2465	0.5137	0.146*
C24	0.4340 (19)	−0.2626 (15)	0.5376 (18)	0.122 (6)
H24A	0.4077	−0.2500	0.4979	0.146*
H24B	0.3991	−0.2567	0.5746	0.146*
C25	0.460 (2)	−0.3233 (15)	0.5330 (16)	0.122 (6)
H25A	0.4149	−0.3481	0.5262	0.146*
H25B	0.4860	−0.3343	0.5728	0.146*
H25C	0.4957	−0.3275	0.4969	0.146*
C26	0.2732 (13)	0.0181 (8)	0.6360 (10)	0.061 (6)
C27	0.231 (3)	0.0714 (13)	0.6171 (16)	0.137 (7)
H27A	0.1756	0.0661	0.6286	0.164*
H27B	0.2507	0.1032	0.6436	0.164*
C28	0.234 (3)	0.0898 (9)	0.5486 (14)	0.137 (7)
H28A	0.2126	0.0584	0.5221	0.164*
H28B	0.2889	0.0943	0.5367	0.164*
C29	0.192 (2)	0.1441 (10)	0.5305 (13)	0.137 (7)
H29A	0.2049	0.1540	0.4856	0.164*
H29B	0.1357	0.1375	0.5330	0.164*
C30	0.213 (3)	0.1931 (8)	0.5730 (15)	0.137 (7)
H30A	0.1797	0.2258	0.5633	0.164*
H30B	0.2672	0.2037	0.5657	0.164*
H30C	0.2061	0.1820	0.6179	0.164*
C31	0.3111 (11)	−0.1346 (6)	0.7976 (8)	0.041 (4)
C32	0.2879 (17)	−0.1604 (15)	0.8567 (15)	0.102 (5)
H32A	0.3194	−0.1430	0.8912	0.122*
H32B	0.3024	−0.2013	0.8546	0.122*
C33	0.2067 (16)	−0.1577 (13)	0.8771 (13)	0.102 (5)
H33A	0.1900	−0.1173	0.8804	0.122*
H33B	0.2008	−0.1757	0.9198	0.122*
C34	0.1576 (13)	−0.1884 (12)	0.8291 (12)	0.102 (5)
H34A	0.1546	−0.2300	0.8372	0.122*
H34B	0.1741	−0.1812	0.7843	0.122*
C35	0.0841 (15)	−0.1576 (13)	0.8462 (14)	0.102 (5)
H35A	0.0419	−0.1715	0.8190	0.122*
H35B	0.0910	−0.1165	0.8395	0.122*
H35C	0.0715	−0.1648	0.8913	0.122*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.0222 (4)	0.0287 (3)	0.0469 (4)	0.000	−0.0068 (3)	0.000
U2	0.0215 (4)	0.0604 (5)	0.0291 (3)	0.000	0.000	−0.0013 (3)
U3	0.0305 (3)	0.0432 (3)	0.0382 (3)	0.0000 (2)	−0.0049 (2)	0.0012 (2)
K1	0.031 (2)	0.063 (3)	0.0266 (19)	0.000	0.000	0.000 (2)
K2	0.050 (3)	0.025 (2)	0.067 (3)	0.000	−0.010 (3)	0.000
K3	0.0304 (16)	0.0468 (19)	0.0364 (15)	0.0076 (14)	−0.0041 (12)	0.0042 (13)
O1	0.081 (10)	0.091 (10)	0.034 (6)	−0.009 (8)	0.008 (6)	−0.018 (6)
O2	0.065 (6)	0.066 (5)	0.085 (6)	−0.005 (4)	−0.003 (4)	0.002 (4)
O3	0.048 (5)	0.059 (5)	0.072 (5)	0.002 (4)	−0.008 (4)	0.003 (4)
O4	0.044 (8)	0.033 (6)	0.147 (15)	0.004 (6)	−0.040 (9)	0.009 (7)
O5	0.043 (7)	0.046 (6)	0.048 (6)	−0.006 (5)	0.000 (5)	−0.005 (5)
O6	0.017 (5)	0.107 (11)	0.033 (5)	−0.007 (6)	−0.001 (4)	−0.001 (6)
O7	0.032 (7)	0.095 (10)	0.032 (5)	0.003 (6)	0.001 (5)	0.011 (5)
O8	0.022 (5)	0.092 (10)	0.050 (6)	0.013 (6)	−0.006 (5)	0.020 (6)
O9	0.037 (7)	0.067 (8)	0.055 (7)	−0.012 (6)	0.000 (5)	−0.013 (6)
O10	0.035 (7)	0.057 (8)	0.050 (6)	−0.010 (5)	−0.003 (5)	−0.009 (5)
O11	0.109 (13)	0.053 (8)	0.047 (7)	0.041 (8)	−0.014 (7)	−0.011 (6)
O12	0.034 (6)	0.048 (7)	0.044 (5)	0.003 (5)	−0.002 (4)	−0.001 (5)
O13	0.049 (7)	0.046 (7)	0.055 (7)	0.017 (6)	0.014 (5)	0.023 (5)
O14	0.034 (6)	0.073 (8)	0.054 (7)	0.027 (6)	0.017 (5)	0.034 (6)
O15	0.045 (7)	0.048 (7)	0.040 (5)	0.002 (5)	0.007 (5)	0.004 (5)
O16	0.053 (8)	0.046 (6)	0.039 (6)	0.006 (5)	−0.005 (5)	0.001 (5)
C6	0.061 (11)	0.062 (11)	0.062 (12)	0.002 (5)	0.000 (5)	−0.003 (5)
C7	0.139 (15)	0.140 (15)	0.145 (15)	−0.001 (5)	−0.001 (5)	0.002 (5)
C8	0.139 (15)	0.140 (15)	0.145 (15)	−0.001 (5)	−0.001 (5)	0.002 (5)
C9	0.139 (15)	0.140 (15)	0.145 (15)	−0.001 (5)	−0.001 (5)	0.002 (5)
C10	0.139 (15)	0.140 (15)	0.145 (15)	−0.001 (5)	−0.001 (5)	0.002 (5)
C11	0.041 (11)	0.110 (17)	0.034 (8)	0.021 (11)	0.008 (7)	0.005 (9)
C12	0.112 (13)	0.098 (11)	0.103 (10)	0.014 (9)	0.045 (10)	−0.003 (8)
C13	0.112 (13)	0.098 (11)	0.103 (10)	0.014 (9)	0.045 (10)	−0.003 (8)
C14	0.112 (13)	0.098 (11)	0.103 (10)	0.014 (9)	0.045 (10)	−0.003 (8)
C15	0.112 (13)	0.098 (11)	0.103 (10)	0.014 (9)	0.045 (10)	−0.003 (8)
C16	0.026 (11)	0.070 (15)	0.048 (12)	0.000	0.000	0.011 (11)
C17	0.024 (9)	0.057 (11)	0.125 (17)	0.000	0.000	0.016 (10)
C18	0.024 (9)	0.057 (11)	0.125 (17)	0.000	0.000	0.016 (10)
C19	0.024 (9)	0.057 (11)	0.125 (17)	0.000	0.000	0.016 (10)
C20	0.024 (9)	0.057 (11)	0.125 (17)	0.000	0.000	0.016 (10)
C21	0.051 (12)	0.078 (14)	0.069 (13)	0.028 (11)	−0.017 (10)	−0.024 (11)
C22	0.128 (7)	0.119 (7)	0.118 (7)	0.009 (5)	0.001 (5)	−0.002 (5)
C23	0.128 (7)	0.119 (7)	0.118 (7)	0.009 (5)	0.001 (5)	−0.002 (5)
C24	0.128 (7)	0.119 (7)	0.118 (7)	0.009 (5)	0.001 (5)	−0.002 (5)
C25	0.128 (7)	0.119 (7)	0.118 (7)	0.009 (5)	0.001 (5)	−0.002 (5)
C26	0.073 (14)	0.041 (10)	0.070 (12)	0.026 (9)	0.031 (10)	0.014 (8)
C27	0.23 (2)	0.064 (9)	0.116 (12)	0.035 (12)	0.027 (14)	0.027 (8)
C28	0.23 (2)	0.064 (9)	0.116 (12)	0.035 (12)	0.027 (14)	0.027 (8)
C29	0.23 (2)	0.064 (9)	0.116 (12)	0.035 (12)	0.027 (14)	0.027 (8)
C30	0.23 (2)	0.064 (9)	0.116 (12)	0.035 (12)	0.027 (14)	0.027 (8)
C31	0.055 (11)	0.024 (7)	0.044 (8)	−0.007 (7)	−0.020 (8)	0.005 (6)
C32	0.077 (10)	0.123 (12)	0.104 (10)	0.034 (9)	0.013 (7)	0.035 (9)
C33	0.077 (10)	0.123 (12)	0.104 (10)	0.034 (9)	0.013 (7)	0.035 (9)
C34	0.077 (10)	0.123 (12)	0.104 (10)	0.034 (9)	0.013 (7)	0.035 (9)
C35	0.077 (10)	0.123 (12)	0.104 (10)	0.034 (9)	0.013 (7)	0.035 (9)

Geometric parameters (Å, º)

U1—O1	1.775 (12)	C5B—H5BC	0.9800
U1—O1^i	1.775 (12)	C6—O4^i	1.14 (6)
U1—O4^i	2.426 (12)	C6—C7	1.502 (11)
U1—O4	2.426 (12)	C7—C8	1.502 (10)
U1—O2	2.470 (15)	C7—H7A	0.9601
U1—O2^i	2.470 (15)	C7—H7B	0.9600
U1—O3	2.505 (13)	C8—C9	1.500 (11)
U1—O3^i	2.505 (13)	C8—H8A	0.9600
U2—O5	1.716 (11)	C8—H8B	0.9700
U2—O5^ii	1.716 (11)	C9—C10	1.498 (10)
U2—O6^ii	2.451 (10)	C9—H9A	0.9900
U2—O6	2.451 (10)	C9—H9B	0.9900
U2—O8	2.470 (10)	C10—H10A	0.9800
U2—O8^ii	2.470 (10)	C10—H10B	0.9800
U2—O7	2.476 (10)	C10—H10C	0.9800
U2—O7^ii	2.476 (10)	C11—C12	1.51 (3)
U3—O9	1.719 (12)	C12—C13	1.55 (4)
U3—O10	1.757 (12)	C12—H12A	0.9900
U3—O16	2.441 (11)	C12—H12B	0.9900
U3—O14	2.462 (12)	C13—C14	1.512 (10)
U3—O12	2.464 (11)	C13—H13A	0.9900
U3—O13	2.491 (10)	C13—H13B	0.9900
U3—O15	2.520 (10)	C14—C15	1.508 (10)
U3—O11	2.526 (13)	C14—H14A	0.9900
K1—O13^iii	2.690 (11)	C14—H14B	0.9900
K1—O13	2.690 (11)	C15—H15A	0.9800
K1—O12	2.698 (11)	C15—H15B	0.9800
K1—O12^iii	2.698 (11)	C15—H15C	0.9800
K1—O6^iv	2.747 (11)	C16—O8^ii	1.223 (15)
K1—O6^v	2.747 (11)	C16—C17	1.496 (10)
K2—O2^i	2.657 (17)	C17—C18	1.48 (5)
K2—O2	2.657 (16)	C17—C18^ii	1.48 (5)
K2—O11^vi	2.670 (13)	C17—H17A	0.8924
K2—O11^vii	2.670 (13)	C17—H17B	1.0234
K2—O16^vi	2.759 (13)	C18—C19	1.510 (10)
K2—O16^vii	2.759 (13)	C18—H18A	0.9603
K3—O3	2.688 (14)	C18—H18B	0.9599
K3—O7	2.688 (12)	C19—C20	1.498 (10)
K3—O14	2.713 (11)	C19—H19A	0.9900
K3—O4	2.724 (13)	C19—H19B	0.9900
K3—O15	2.769 (12)	C20—H20A	0.9800
K3—O8	2.817 (12)	C20—H20B	0.9800
O2—C1	1.27 (3)	C20—H20C	0.9800
O3—C1	1.24 (3)	C21—C22	1.498 (10)
O4—C6^i	1.14 (6)	C22—C23	1.511 (10)
O4—C6	1.34 (5)	C22—H22A	0.9900
O6—C11	1.25 (2)	C22—H22B	0.9900
O6—K1^viii	2.747 (11)	C23—C24	1.509 (10)
O7—C11	1.28 (2)	C23—H23A	0.9900
O8—C16	1.223 (15)	C23—H23B	0.9900
O11—C21	1.31 (3)	C24—C25	1.49 (4)
O11—K2^ix	2.670 (13)	C24—H24A	0.9900
O12—C21	1.29 (2)	C24—H24B	0.9900
O13—C26	1.28 (2)	C25—H25A	0.9800
O14—C26	1.30 (2)	C25—H25B	0.9800
O15—C31	1.227 (19)	C25—H25C	0.9800
O16—C31	1.23 (2)	C26—C27	1.50 (4)
O16—K2^ix	2.759 (12)	C27—C28	1.49 (4)
C1—C2A	1.504 (10)	C27—H27A	0.9900
C2A—C3A	1.501 (10)	C27—H27B	0.9900
C2A—H2AA	0.9900	C28—C29	1.509 (10)
C2A—H2AB	0.9900	C28—H28A	0.9900
C2A—H2BC	0.7316	C28—H28B	0.9900
C3A—C4A	1.505 (10)	C29—C30	1.495 (10)
C3A—H3AA	0.9900	C29—H29A	0.9900
C3A—H3AB	0.9900	C29—H29B	0.9900
C4A—C5A	1.502 (10)	C30—H30A	0.9800
C4A—H4AA	0.9900	C30—H30B	0.9800
C4A—H4AB	0.9900	C30—H30C	0.9800
C5A—H5AA	0.9800	C31—C32	1.43 (3)
C5A—H5AB	0.9800	C32—C33	1.47 (4)
C5A—H5AC	0.9800	C32—H32A	0.9900
C2B—C3B	1.500 (10)	C32—H32B	0.9900
C2B—H2BA	0.9600	C33—C34	1.497 (10)
C2B—H2BC	0.9600	C33—H33A	0.9900
C3B—C4B	1.502 (10)	C33—H33B	0.9900
C3B—H3BA	0.9900	C34—C35	1.504 (10)
C3B—H3BB	0.9900	C34—H34A	0.9900
C4B—C5B	1.503 (10)	C34—H34B	0.9900
C4B—H4BA	0.9900	C35—H35A	0.9800
C4B—H4BB	0.9900	C35—H35B	0.9800
C5B—H5BA	0.9800	C35—H35C	0.9800
C5B—H5BB	0.9800
O1—U1—O1^i	179.1 (10)	O3—K3—U3	122.1 (3)
O1—U1—O4^i	92.0 (7)	O7—K3—U3	88.4 (3)
O1^i—U1—O4^i	87.1 (7)	O14—K3—U3	30.2 (2)
O1—U1—O4	87.1 (7)	O4—K3—U3	107.3 (4)
O1^i—U1—O4	92.0 (7)	O15—K3—U3	32.0 (2)
O4^i—U1—O4	52.3 (6)	O8—K3—U3	132.1 (3)
O1—U1—O2	89.9 (6)	U1—K3—U3	119.80 (7)
O1^i—U1—O2	90.9 (6)	O3—K3—U2	117.0 (3)
O4^i—U1—O2	173.1 (5)	O7—K3—U2	30.2 (2)
O4—U1—O2	121.2 (5)	O14—K3—U2	129.4 (3)
O1—U1—O2^i	90.9 (6)	O4—K3—U2	137.1 (4)
O1^i—U1—O2^i	89.9 (6)	O15—K3—U2	87.7 (2)
O4^i—U1—O2^i	121.2 (5)	O8—K3—U2	31.3 (2)
O4—U1—O2^i	173.1 (5)	U1—K3—U2	132.77 (8)
O2—U1—O2^i	65.4 (8)	U3—K3—U2	107.26 (7)
O1—U1—O3	92.1 (6)	C1—O2—U1	90.6 (16)
O1^i—U1—O3	87.9 (6)	C1—O2—K2	151.1 (18)
O4^i—U1—O3	120.0 (4)	U1—O2—K2	117.2 (6)
O4—U1—O3	68.2 (4)	C1—O3—U1	89.7 (16)
O2—U1—O3	53.3 (5)	C1—O3—K3	155.6 (17)
O2^i—U1—O3	118.6 (5)	U1—O3—K3	114.4 (5)
O1—U1—O3^i	87.9 (6)	C6^i—O4—U1	95 (2)
O1^i—U1—O3^i	92.1 (6)	C6—O4—U1	89.9 (18)
O4^i—U1—O3^i	68.2 (4)	C6^i—O4—K3	149 (2)
O4—U1—O3^i	120.0 (4)	C6—O4—K3	150 (2)
O2—U1—O3^i	118.6 (5)	U1—O4—K3	115.9 (5)
O2^i—U1—O3^i	53.3 (5)	C11—O6—U2	94.8 (10)
O3—U1—O3^i	171.8 (6)	C11—O6—K1^viii	148.9 (11)
O1—U1—C6	94.8 (9)	U2—O6—K1^viii	116.3 (4)
O1^i—U1—C6	84.3 (9)	C11—O7—U2	92.9 (10)
O4^i—U1—C6	24.3 (13)	C11—O7—K3	149.0 (10)
O4—U1—C6	28.9 (12)	U2—O7—K3	116.8 (5)
O2—U1—C6	148.8 (13)	C16—O8—U2	92.6 (9)
O2^i—U1—C6	145.1 (13)	C16—O8—K3	154.3 (11)
O3—U1—C6	95.7 (13)	U2—O8—K3	112.5 (4)
O3^i—U1—C6	92.4 (13)	C21—O11—U3	93.2 (10)
O1—U1—C6^i	84.3 (9)	C21—O11—K2^ix	148.1 (14)
O1^i—U1—C6^i	94.8 (9)	U3—O11—K2^ix	110.0 (5)
O4^i—U1—C6^i	28.9 (12)	C21—O12—U3	96.6 (12)
O4—U1—C6^i	24.3 (13)	C21—O12—K1	143.2 (13)
O2—U1—C6^i	145.1 (13)	U3—O12—K1	115.5 (4)
O2^i—U1—C6^i	148.8 (13)	C26—O13—U3	92.3 (10)
O3—U1—C6^i	92.4 (13)	C26—O13—K1	147.8 (11)
O3^i—U1—C6^i	95.7 (13)	U3—O13—K1	114.9 (4)
C6—U1—C6^i	11.1 (15)	C26—O14—U3	93.0 (10)
O1—U1—C1	93.2 (8)	C26—O14—K3	150.7 (11)
O1^i—U1—C1	87.3 (9)	U3—O14—K3	116.2 (4)
O4^i—U1—C1	146.1 (8)	C31—O15—U3	93.0 (10)
O4—U1—C1	94.6 (8)	C31—O15—K3	149.7 (10)
O2—U1—C1	27.0 (7)	U3—O15—K3	112.4 (4)
O2^i—U1—C1	92.2 (9)	C31—O16—U3	96.7 (9)
O3—U1—C1	26.4 (7)	C31—O16—K2^ix	145.7 (10)
O3^i—U1—C1	145.5 (8)	U3—O16—K2^ix	109.7 (4)
C6—U1—C1	121.8 (15)	O3—C1—O2	126 (3)
C6^i—U1—C1	118.8 (14)	O3—C1—C2A	140 (3)
O1—U1—C1^i	87.3 (9)	O2—C1—C2A	88 (3)
O1^i—U1—C1^i	93.2 (8)	O3—C1—U1	63.9 (14)
O4^i—U1—C1^i	94.6 (8)	O2—C1—U1	62.3 (14)
O4—U1—C1^i	146.1 (8)	C2A—C1—U1	148 (3)
O2—U1—C1^i	92.2 (9)	C1—C2A—C3A	112.2 (11)
O2^i—U1—C1^i	27.0 (7)	C1—C2A—H2AA	108.8
O3—U1—C1^i	145.5 (8)	C3A—C2A—H2AA	109.1
O3^i—U1—C1^i	26.4 (7)	C1—C2A—H2AB	109.6
C6—U1—C1^i	118.8 (14)	C3A—C2A—H2AB	109.1
C6^i—U1—C1^i	121.8 (15)	H2AA—C2A—H2AB	107.9
C1—U1—C1^i	119.1 (14)	C1—C2A—H2BC	101.4
O5—U2—O5^ii	180.0 (8)	C3A—C2A—H2BC	77.5
O5—U2—O6^ii	92.4 (5)	H2AA—C2A—H2BC	142.9
O5^ii—U2—O6^ii	87.6 (5)	C2A—C3A—C4A	112.2 (11)
O5—U2—O6	87.6 (5)	C2A—C3A—H3AA	109.1
O5^ii—U2—O6	92.4 (5)	C4A—C3A—H3AA	109.4
O6^ii—U2—O6	67.7 (5)	C2A—C3A—H3AB	109.1
O5—U2—O8	92.0 (5)	C4A—C3A—H3AB	109.0
O5^ii—U2—O8	88.0 (5)	H3AA—C3A—H3AB	107.9
O6^ii—U2—O8	170.9 (4)	C5A—C4A—C3A	112.3 (11)
O6—U2—O8	120.5 (4)	C5A—C4A—H4AA	109.4
O5—U2—O8^ii	88.0 (5)	C3A—C4A—H4AA	109.4
O5^ii—U2—O8^ii	92.0 (5)	C5A—C4A—H4AB	108.8
O6^ii—U2—O8^ii	120.5 (4)	C3A—C4A—H4AB	109.0
O6—U2—O8^ii	170.9 (4)	H4AA—C4A—H4AB	109.0
O8—U2—O8^ii	51.6 (5)	C4A—C5A—H5AA	109.5
O5—U2—O7	88.6 (5)	C4A—C5A—H5AB	109.1
O5^ii—U2—O7	91.4 (5)	H5AA—C5A—H5AB	109.5
O6^ii—U2—O7	120.1 (4)	C4A—C5A—H5AC	109.8
O6—U2—O7	52.5 (4)	H5AA—C5A—H5AC	109.5
O8—U2—O7	68.0 (4)	H5AB—C5A—H5AC	109.5
O8^ii—U2—O7	119.4 (4)	C3B—C2B—H2BA	112.0
O5—U2—O7^ii	91.4 (5)	C3B—C2B—H2BC	112.8
O5^ii—U2—O7^ii	88.6 (5)	H2BA—C2B—H2BC	109.5
O6^ii—U2—O7^ii	52.5 (4)	C2B—C3B—C4B	112.6 (11)
O6—U2—O7^ii	120.1 (4)	C2B—C3B—H3BA	110.0
O8—U2—O7^ii	119.4 (4)	C4B—C3B—H3BA	108.7
O8^ii—U2—O7^ii	68.0 (4)	C2B—C3B—H3BB	109.2
O7—U2—O7^ii	172.6 (6)	C4B—C3B—H3BB	108.0
O5—U2—C16	90.0 (4)	H3BA—C3B—H3BB	107.8
O5^ii—U2—C16	90.0 (4)	C5B—C4B—C3B	112.2 (11)
O6^ii—U2—C16	146.2 (2)	C5B—C4B—H4BA	109.5
O6—U2—C16	146.2 (2)	C3B—C4B—H4BA	108.0
O8—U2—C16	25.8 (3)	C5B—C4B—H4BB	109.2
O8^ii—U2—C16	25.8 (3)	C3B—C4B—H4BB	108.7
O7—U2—C16	93.7 (3)	H4BA—C4B—H4BB	109.0
O7^ii—U2—C16	93.7 (3)	C4B—C5B—H5BA	109.1
O5—U2—C11^ii	94.1 (6)	C4B—C5B—H5BB	109.5
O5^ii—U2—C11^ii	85.9 (6)	H5BA—C5B—H5BB	111.0
O6^ii—U2—C11^ii	26.0 (5)	C4B—C5B—H5BC	109.8
O6—U2—C11^ii	93.7 (5)	H5BA—C5B—H5BC	109.5
O8—U2—C11^ii	145.5 (5)	H5BB—C5B—H5BC	109.5
O8^ii—U2—C11^ii	94.6 (5)	O4^i—C6—O4	119 (3)
O7—U2—C11^ii	146.0 (5)	O4^i—C6—C7	128 (6)
O7^ii—U2—C11^ii	26.6 (5)	O4—C6—C7	102 (6)
C16—U2—C11^ii	120.2 (4)	O4^i—C6—U1	60.8 (15)
O5—U2—C11	85.9 (6)	O4—C6—U1	61.2 (13)
O5^ii—U2—C11	94.1 (6)	C7—C6—U1	159 (5)
O6^ii—U2—C11	93.7 (5)	C6—C7—C8	112.9 (11)
O6—U2—C11	26.0 (5)	C6—C7—H7A	114.6
O8—U2—C11	94.6 (5)	C8—C7—H7A	115.7
O8^ii—U2—C11	145.5 (5)	C6—C7—H7B	93.2
O7—U2—C11	26.6 (5)	C8—C7—H7B	110.1
O7^ii—U2—C11	146.0 (5)	H7A—C7—H7B	107.8
C16—U2—C11	120.2 (4)	C9—C8—C7	145 (9)
C11^ii—U2—C11	119.6 (8)	C9—C8—H8A	96.6
O5—U2—K3	97.4 (4)	C7—C8—H8A	93.0
O5^ii—U2—K3	82.6 (4)	C9—C8—H8B	103.0
O6^ii—U2—K3	150.4 (2)	C7—C8—H8B	106.1
O6—U2—K3	84.8 (2)	H8A—C8—H8B	104.4
O8—U2—K3	36.3 (3)	C8—C9—C10	113.2 (11)
O8^ii—U2—K3	87.8 (3)	C8—C9—H9A	108.0
O7—U2—K3	33.1 (3)	C10—C9—H9A	108.1
O7^ii—U2—K3	154.0 (3)	C8—C9—H9B	109.9
C16—U2—K3	62.02 (4)	C10—C9—H9B	109.7
C11^ii—U2—K3	168.3 (5)	H9A—C9—H9B	107.7
C11—U2—K3	59.5 (4)	C9—C10—H10A	109.6
O9—U3—O10	179.2 (6)	C9—C10—H10B	108.6
O9—U3—O16	90.0 (5)	H10A—C10—H10B	109.5
O10—U3—O16	89.2 (5)	C9—C10—H10C	110.3
O9—U3—O14	93.2 (6)	H10A—C10—H10C	109.5
O10—U3—O14	87.1 (5)	H10B—C10—H10C	109.5
O16—U3—O14	118.8 (4)	O6—C11—O7	119.3 (16)
O9—U3—O12	90.0 (5)	O6—C11—C12	122 (2)
O10—U3—O12	90.5 (5)	O7—C11—C12	119 (2)
O16—U3—O12	121.6 (4)	O6—C11—U2	59.3 (9)
O14—U3—O12	119.5 (4)	O7—C11—U2	60.5 (8)
O9—U3—O13	90.2 (6)	C12—C11—U2	178.4 (18)
O10—U3—O13	90.6 (5)	C11—C12—C13	113 (3)
O16—U3—O13	172.6 (4)	C11—C12—H12A	109.0
O14—U3—O13	53.9 (4)	C13—C12—H12A	109.2
O12—U3—O13	65.8 (4)	C11—C12—H12B	109.0
O9—U3—O15	87.4 (5)	C13—C12—H12B	108.7
O10—U3—O15	92.0 (5)	H12A—C12—H12B	107.7
O16—U3—O15	50.7 (4)	C12—C13—C14	119 (2)
O14—U3—O15	68.4 (4)	C12—C13—H13A	107.5
O12—U3—O15	171.8 (4)	C14—C13—H13A	107.7
O13—U3—O15	122.0 (4)	C12—C13—H13B	107.8
O9—U3—O11	91.8 (6)	C14—C13—H13B	107.2
O10—U3—O11	88.0 (6)	H13A—C13—H13B	107.0
O16—U3—O11	68.9 (4)	C15—C14—C13	111 (2)
O14—U3—O11	170.8 (5)	C15—C14—H14A	109.6
O12—U3—O11	52.7 (4)	C13—C14—H14A	109.2
O13—U3—O11	118.4 (4)	C15—C14—H14B	109.3
O15—U3—O11	119.6 (4)	C13—C14—H14B	109.7
O9—U3—C26	91.0 (7)	H14A—C14—H14B	108.1
O10—U3—C26	89.6 (7)	C14—C15—H15A	109.6
O16—U3—C26	146.0 (5)	C14—C15—H15B	109.2
O14—U3—C26	27.2 (4)	H15A—C15—H15B	109.5
O12—U3—C26	92.4 (5)	C14—C15—H15C	109.6
O13—U3—C26	26.6 (5)	H15A—C15—H15C	109.5
O15—U3—C26	95.4 (5)	H15B—C15—H15C	109.5
O11—U3—C26	145.0 (5)	O8^ii—C16—O8	123.2 (18)
O9—U3—C31	88.7 (5)	O8^ii—C16—C17	118.4 (9)
O10—U3—C31	90.5 (5)	O8—C16—C17	118.4 (9)
O16—U3—C31	25.3 (4)	O8^ii—C16—U2	61.6 (9)
O14—U3—C31	93.6 (4)	O8—C16—U2	61.6 (9)
O12—U3—C31	146.9 (4)	C17—C16—U2	180.000 (3)
O13—U3—C31	147.3 (4)	C18—C17—C18^ii	120 (3)
O15—U3—C31	25.4 (4)	C18—C17—C16	120.0 (15)
O11—U3—C31	94.2 (5)	C18^ii—C17—C16	120.0 (15)
C26—U3—C31	120.7 (5)	C18—C17—H17A	110.5
O9—U3—C21	91.0 (6)	C18^ii—C17—H17A	48.7
O10—U3—C21	89.2 (6)	C16—C17—H17A	108.0
O16—U3—C21	95.5 (6)	C18—C17—H17B	105.1
O14—U3—C21	145.4 (5)	C18^ii—C17—H17B	58.0
O12—U3—C21	26.1 (5)	C16—C17—H17B	105.7
O13—U3—C21	91.8 (5)	H17A—C17—H17B	106.8
O15—U3—C21	146.2 (5)	C17—C18—C19	118 (4)
O11—U3—C21	26.6 (6)	C17—C18—H18A	109.9
C26—U3—C21	118.4 (6)	C19—C18—H18A	111.8
C31—U3—C21	120.8 (6)	C17—C18—H18B	106.4
O9—U3—K2^ix	105.1 (5)	C19—C18—H18B	103.0
O10—U3—K2^ix	74.3 (4)	C20—C19—C18	117 (3)
O16—U3—K2^ix	37.6 (3)	C20—C19—H19A	108.1
O14—U3—K2^ix	148.2 (3)	C18—C19—H19A	108.1
O12—U3—K2^ix	86.8 (3)	C20—C19—H19B	108.1
O13—U3—K2^ix	148.8 (3)	C18—C19—H19B	108.3
O15—U3—K2^ix	86.3 (3)	H19A—C19—H19B	107.3
O11—U3—K2^ix	36.1 (3)	C19—C20—H20A	109.6
C26—U3—K2^ix	163.9 (5)	C19—C20—H20B	109.4
C31—U3—K2^ix	61.7 (4)	H20A—C20—H20B	109.5
C21—U3—K2^ix	61.5 (4)	C19—C20—H20C	109.4
O13^iii—K1—O13	98.0 (6)	H20A—C20—H20C	109.5
O13^iii—K1—O12	117.1 (3)	H20B—C20—H20C	108.0
O13—K1—O12	59.9 (3)	O11—C21—O12	117.5 (16)
O13^iii—K1—O12^iii	59.9 (3)	O11—C21—C22	119 (2)
O13—K1—O12^iii	117.1 (3)	O12—C21—C22	123 (2)
O12—K1—O12^iii	176.0 (5)	O11—C21—U3	60.1 (9)
O13^iii—K1—O6^iv	156.7 (4)	O12—C21—U3	57.3 (9)
O13—K1—O6^iv	102.7 (4)	C22—C21—U3	177.7 (19)
O12—K1—O6^iv	83.0 (4)	C21—C22—C23	113 (3)
O12^iii—K1—O6^iv	100.5 (4)	C21—C22—H22A	108.7
O13^iii—K1—O6^v	102.7 (4)	C23—C22—H22A	108.9
O13—K1—O6^v	156.7 (4)	C21—C22—H22B	109.0
O12—K1—O6^v	100.5 (4)	C23—C22—H22B	108.9
O12^iii—K1—O6^v	83.0 (4)	H22A—C22—H22B	107.7
O6^iv—K1—O6^v	59.6 (4)	C22—C23—C24	118 (3)
O13^iii—K1—U3	117.5 (3)	C22—C23—H23A	107.7
O13—K1—U3	31.1 (2)	C24—C23—H23A	108.1
O12—K1—U3	30.6 (2)	C22—C23—H23B	107.7
O12^iii—K1—U3	147.1 (2)	C24—C23—H23B	107.6
O6^iv—K1—U3	85.8 (2)	H23A—C23—H23B	107.1
O6^v—K1—U3	126.5 (3)	C23—C24—C25	101 (3)
O13^iii—K1—U3^iii	31.1 (2)	C23—C24—H24A	111.9
O13—K1—U3^iii	117.5 (3)	C25—C24—H24A	111.6
O12—K1—U3^iii	147.1 (2)	C23—C24—H24B	111.3
O12^iii—K1—U3^iii	30.6 (2)	C25—C24—H24B	111.5
O6^iv—K1—U3^iii	126.5 (3)	H24A—C24—H24B	109.3
O6^v—K1—U3^iii	85.8 (2)	C24—C25—H25A	109.4
U3—K1—U3^iii	145.01 (12)	C24—C25—H25B	109.6
O13^iii—K1—U2^v	131.0 (3)	H25A—C25—H25B	109.5
O13—K1—U2^v	131.0 (3)	C24—C25—H25C	109.4
O12—K1—U2^v	92.0 (3)	H25A—C25—H25C	109.5
O12^iii—K1—U2^v	92.0 (3)	H25B—C25—H25C	109.5
O6^iv—K1—U2^v	29.8 (2)	O13—C26—O14	120.7 (16)
O6^v—K1—U2^v	29.8 (2)	O13—C26—C27	122 (2)
U3—K1—U2^v	107.49 (6)	O14—C26—C27	117.8 (19)
U3^iii—K1—U2^v	107.49 (6)	O13—C26—U3	61.0 (8)
O2^i—K2—O2	60.3 (7)	O14—C26—U3	59.8 (9)
O2^i—K2—O11^vi	132.9 (4)	C27—C26—U3	176 (2)
O2—K2—O11^vi	92.2 (5)	C28—C27—C26	118 (3)
O2^i—K2—O11^vii	92.2 (5)	C28—C27—H27A	108.0
O2—K2—O11^vii	132.9 (4)	C26—C27—H27A	108.0
O11^vi—K2—O11^vii	130.9 (6)	C28—C27—H27B	107.5
O2^i—K2—O16^vi	143.0 (4)	C26—C27—H27B	107.5
O2—K2—O16^vi	89.3 (4)	H27A—C27—H27B	107.2
O11^vi—K2—O16^vi	62.4 (4)	C27—C28—C29	118 (3)
O11^vii—K2—O16^vi	94.9 (5)	C27—C28—H28A	107.6
O2^i—K2—O16^vii	89.3 (4)	C29—C28—H28A	108.1
O2—K2—O16^vii	143.0 (4)	C27—C28—H28B	108.1
O11^vi—K2—O16^vii	94.9 (5)	C29—C28—H28B	107.8
O11^vii—K2—O16^vii	62.4 (4)	H28A—C28—H28B	107.2
O16^vi—K2—O16^vii	125.9 (5)	C30—C29—C28	112.5 (10)
O2^i—K2—U3^vi	161.9 (3)	C30—C29—H29A	109.5
O2—K2—U3^vi	103.1 (3)	C28—C29—H29A	109.1
O11^vi—K2—U3^vi	33.9 (3)	C30—C29—H29B	108.9
O11^vii—K2—U3^vi	105.3 (4)	C28—C29—H29B	108.9
O16^vi—K2—U3^vi	32.7 (2)	H29A—C29—H29B	107.8
O16^vii—K2—U3^vi	102.8 (3)	C29—C30—H30A	109.3
O2^i—K2—U3^vii	103.1 (3)	C29—C30—H30B	109.2
O2—K2—U3^vii	161.9 (3)	H30A—C30—H30B	109.5
O11^vi—K2—U3^vii	105.3 (4)	C29—C30—H30C	109.9
O11^vii—K2—U3^vii	33.9 (3)	H30A—C30—H30C	109.5
O16^vi—K2—U3^vii	102.8 (3)	H30B—C30—H30C	109.5
O16^vii—K2—U3^vii	32.7 (2)	O15—C31—O16	119.6 (15)
U3^vi—K2—U3^vii	94.21 (9)	O15—C31—C32	116 (2)
O2^i—K2—U1	30.1 (3)	O16—C31—C32	123.7 (18)
O2—K2—U1	30.1 (3)	O15—C31—U3	61.6 (8)
O11^vi—K2—U1	114.5 (3)	O16—C31—U3	57.9 (8)
O11^vii—K2—U1	114.5 (3)	C32—C31—U3	174.8 (17)
O16^vi—K2—U1	117.1 (3)	C31—C32—C33	120 (2)
O16^vii—K2—U1	117.1 (3)	C31—C32—H32A	107.5
U3^vi—K2—U1	132.90 (4)	C33—C32—H32A	107.6
U3^vii—K2—U1	132.90 (4)	C31—C32—H32B	107.3
O3—K3—O7	112.0 (4)	C33—C32—H32B	107.0
O3—K3—O14	92.0 (4)	H32A—C32—H32B	106.9
O7—K3—O14	102.3 (4)	C32—C33—C34	109 (3)
O3—K3—O4	61.4 (4)	C32—C33—H33A	109.4
O7—K3—O4	164.2 (5)	C34—C33—H33A	109.7
O14—K3—O4	92.5 (5)	C32—C33—H33B	109.9
O3—K3—O15	152.4 (4)	C34—C33—H33B	110.4
O7—K3—O15	82.7 (4)	H33A—C33—H33B	108.3
O14—K3—O15	61.4 (3)	C33—C34—C35	95 (2)
O4—K3—O15	109.6 (4)	C33—C34—H34A	112.1
O3—K3—O8	103.8 (4)	C35—C34—H34A	113.4
O7—K3—O8	60.3 (3)	C33—C34—H34B	113.1
O14—K3—O8	159.8 (3)	C35—C34—H34B	112.3
O4—K3—O8	106.0 (5)	H34A—C34—H34B	110.0
O15—K3—O8	103.7 (4)	C34—C35—H35A	108.8
O3—K3—U1	31.5 (3)	C34—C35—H35B	110.3
O7—K3—U1	141.2 (3)	H35A—C35—H35B	109.5
O14—K3—U1	93.9 (2)	C34—C35—H35C	109.3
O4—K3—U1	30.0 (3)	H35A—C35—H35C	109.5
O15—K3—U1	135.5 (3)	H35B—C35—H35C	109.5
O8—K3—U1	106.2 (2)

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