A new adamantane­carboxyl­ate coordination polymer: poly[[(μ₃-adamantane-1,3-dicarboxyl­ato)aqua­di­oxidouranium(VI)] monohydrate]

The title compound, {[U(C₁₂H₁₄O₄)O₂(H₂O)]·H₂O}_n, is the first actinide complex featuring adamantane­carboxyl­ate ligands. The metal ion possesses a penta­gonal–bipyramidal UO₇ coordination involving two axial oxide ligands [U—O = 1.732 (5) and 1.764 (5) Å] and five equatorial O atoms [U—O = 2.259 (5)–2.494 (4) Å] of aqua and carboxyl­ate ligands. The latter display pseudo-chelating and bridging coordination modes of the carboxyl­ate groups that are responsible for the generation of the centrosymmetric discrete uranium–carboxyl­ate [UO₂(μ-RCOO)₂UO₂] dimers [U...U = 5.5130 (5) Å] and their connection into one-dimensional chains. Hydrogen bonding involving two coordinated and two solvent water mol­ecules [O...O = 2.719 (7)–2.872 (7) Å] yields centrosymmetric (H₂O)₄ ensembles and provides noncovalent linkage between the coordination chains to generate a three-dimensional network structure.

S1. Comment

Adamantane carboxylate ligands are receiving growing attention as versatile molecular building blocks for sustaining the structure of coordination solids, in particular focusing upon the construction of framework coordination polymers. This interest is largely predetermined by the geometrically rigid structure of the adamantane skeleton and the ease of its multiple functionalization at the four available bridgehead positions. The defined and proper multiple binding directions, which are supported by such species, were especially relevant for the sophisticated coordination framework architecture involving 1,3-di- (Nielsen et al., 2008; Tang et al., 2009) and 1,3,5,7-adamantanetetracarboxylates in combination with a series of transition metal cations: Cu²⁺ (Chen et al., 2000); Zn²⁺ (Rosi et al., 2005); Ni²⁺ and Cd²⁺ (Kim et al., 2001). The second important feature of such molecular building blocks originates in a relatively high density of donor centres adopted around the adamantane scaffold. That is a prerequisite for a high connection of the framework nodes and it commonly favours the assembly of complex multiple [multiply?] connected `secondary building units', for example binuclear paddle-wheel Cu-carboxylate motifs (Chen et al., 2000). An alternative possibility may be found with the exploitation of rather high coordination numbers, which are typical for the metal ions of the lanthanide and actinide families. However, this particular issue for the coordination chemistry of adamantane carboxylate ligands remains practically unexplored. Ninefold coordination of Eu³⁺ ions was essential for the sustaining three-dimensional framework structure of the thermally stable luminescent 1,3-adamantanedicarboxylate (ADC) complex (Millange et al., 2004) and some mixed-ligand 1,10-phenanthroline–ADC lanthanide coordination polymers which were characterized recently (Li et al., 2009). Herein we report the synthesis and structure of the first actinide adamantane carboxylate complex adopted by dioxouranium(VI) cations and ADC dianions. In addition to the very specific inherent coordination geometries of the UO₂²⁺ ions in the carboxylate coordination frameworks (Borkowski & Cahill, 2006), such species may attract interest for their photoluminescent properties and photocatalytic activity (Chen et al., 2003).

In the title compound, (I), the polymeric array is organized by interconnection of metal ions by bitopic carboxylate ligands. A unique portion of the structure includes the dioxouranium(VI) cation, the carboxylate dianion, one coordinated and one solvate water molecule.

The carboxylate groups of the organic linker display two different coordination modes: bidentate pseudo-chelating (C1O1O2) and bidentate bridging (C2O3O4) (Fig. 1). Thus, the organic ligand is responsible for the connection of three metal ions and generation of the one-dimensional coordination polymer based upon very illustrative dinuclear uranium–carboxylate motifs. The bridging carboxylic groups sustain the centrosymmetric dimers [U1···U1ⁱⁱⁱ = 5.5130 (5) Å; symmetry code (iii): -x, 1 - y, 1 - z], in which the characteristic pentagonal–bipyramidal sevenfold coordination (Katz et al., 1986) around two U ions is completed with equatorial chelate carboxylate [U—O = 2.407 (4) and 2.494 (4) Å] and aqua ligands [2.475 (5) Å] and also includes two typically short axial bonds [U—O = 1.732 (5) and 1.764 (5) Å] within the essentially linear uranyl moiety [O6—U1—O7 178.2 (2)°] (Table 1).

Such carboxylate dimers themselves are characteristic for the molecular dioxouranium(VI) species, which commonly accommodate additional single O donors (L), for example L = DMF [DMF = dimethylformamide?] (Navaza et al., 1993; Spitsin et al., 1982) and Ph₃PO (Panattoni et al., 1969). Therefore the dimeric motif may be considered as a special kind of supramolecular synthon for the modular assembly of the uranium–carboxylate frameworks. However, the number of derived polymeric solids as yet is very scarce: it is limited to a one-dimensional polymer with trimesic acid dianion (L = H₂O) (Borkowski & Cahill, 2004) and two-dimensional square grid polymers with camphorate (L = MeOH) (Thuery, 2006) and succinate (L = DMSO) [DMSO = dimethylsulfoxide?] (Shchelokov, et al., 1985) anions. In the latter two, the dimer provides the generation of four-connected nodes of the framework. Rather long aliphatic α,ω-dicarboxylate linkers (C₃ to C₈) typically demonstrate subtle evolution of the pattern. This includes elimination of the neutral O donors and subsequent polymerization of the dimers through a set of additional U–carboxylate bonds (Borkowski & Cahill, 2005, 2006). Therefore, the steric environment of the tertiary carboxylic groups at the adamantane matrix is essential for sustaining the discrete dimers in (I) (compare with the camphorate prototype reported by Thuery, 2006).

The bridging function of the ADC ligands affords one-dimensional double chains running in the c direction (Fig. 2), in which the above dimers [symmetry code: -x, y, 0.5 - z] are linked by a `double adamantane bridge'. Such organization of the polymer and the specific coordination mode of the organic ligand bear close resemblance to one-dimensional structures of [M(phen)(ADC)(HADC)(H₂O)] complexes (M = Sm, Eu) (Li et al., 2009). In particular, the angular orientation of the carboxylic groups installed at the 1,3-positions of the adamantane skeleton is favourable for a double linkage between the coordination dimers and assembly of one-dimensional chains, instead of a four-connected planar network with the single links between the nodes. The same function was observed for the 1,3,5-benzenetricarboxylato dianion, as virtually bifunctional angular linker between the uranium ions (Borkowski & Cahill, 2004).

The interchain interactions occur by means of relatively strong hydrogen bonding, which involves two coordinated (O5 and O5^iv, double donors) and two solvate (O8 and O8^iv, double acceptors) [symmetry code: (iv) 0.5 - x, 1.5 - y, 1 - z] water molecules supporting flat tetramers (H₂O)₄ with very characteristic hydrogen-bonding parameters [cf. O···O 2.753 (7) and 2.772 (6) Å] (Fig. 3, Table 2). An additional hydrogen bond to a coordinated carboxylic group [O8···O2 = 2.719 (7) Å] is also important. These interactions connect the uranium–carboxylate dimers into ribbons along the a direction, while weaker hydrogen bonds with UO₂²⁺ oxo-ligands [O8···O6^v = 2.872 (7) Å; symmetry code: (v) 0.5 - x, 0.5 - y, 1 - z] unite the ribbons to flat hydrogen-bonded layers parallel to the ab plane. Topologically, each layer represents a planar four-connected net in which the above-mentioned coordination dimers and water tetramers constitute the nodes. Successive layers are separated by 9.06 Å and are linked together by adamantane spacers. In this way, the covalent `double adamantane links' between the dimers extend this array in a third direction leading to a hybrid coordination and hydrogen-bonded three-dimensional four- and six-connected framework.

In brief, the title structure is important as a prototype for the construction of actinide and adamantane carboxylate coordination frameworks those could be anticipated especially for the typical MO₂²⁺ dioxocations and a wide range of 1,3-bi-, 1,3,5-tri- and 1,3,5,7-tetrafunctional adamantane tectons and the related functionalized `nanodiamond' molecules.

Related literature

For related literature, see: Borkowski & Cahill (2004, 2005, 2006); Chen et al. (2000, 2003); Katz et al. (1986); Kim et al. (2001); Li et al. (2009); Millange et al. (2004); Navaza et al. (1993); Nielsen et al. (2008); Panattoni et al. (1969); Rosi et al. (2005); Shchelokov et al. (1985); Spitsin et al. (1982); Tang et al. (2009); Thuery (2006).

S2. Experimental

The 1,3-adamantanedicarboxylic acid (H₂ADC) was synthesized by Koch–Haaf carboxylation of 1,3-dihydroxyadamantane. For the preparation of the title compound, the mixture of H₂ADC (11.5 mg, 0.051 mmol), UO₂(OAc)₂.2H₂O (24.5 mg, 0.058 mmol) and NH₄OAc (5.5 mg, 0.071 mmol) in 2 ml of water was sealed in a 15 ml Pyrex tube, heated at 453 K for 48 h and then cooled to room temperature at a rate of 3 K h^-1. Yellow–orange crystals of the product, (I), were collected by filtration, yielding 17.5 mg (65%, based on the ligand).

S3. Refinement

The structure was solved by direct methods. All H atoms were located from difference maps and then refined as riding, with O—H distances constrained to 0.85 Å, C—H (CH₂) distances constrained to 0.97 Å and C—H (CH) distances constrained to 0.98 Å, and with U_iso(H) = 1.2U_eq (parent C atom) and U_iso(H) = 1.5U_eq (parent O atom).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed lines indicate OH···O interactions. Symmetry codes: (i) -x, y, 0.5 - z; (ii) x, 1 - y, 1/2 + z; (iii) –x, 1 - y, 1 - z.
	Fig. 2. Projection of the structure of (I) on an ac plane showing a set of coordination chains along the c direction. The hydrogen bonds are omitted for clarity. Symmetry codes: (i) -x, y, 0.5 - z; (iii) -x, 1 - y, 1 - z.
	Fig. 3. The hydrogen-bonded layer constituted by aquauranium–carboxylate dimers (indicated with open bonds) and solvate water molecules. The adamantanediyl groups are omitted for clarity (they connect the layers in the direction, which is nearly orthogonal to the drawing plane). Symmetry codes: (iii) –x, 1 - y, 1 - z; (iv) 0.5 - x, 1.5 - y, 1 - z; (v) 0.5 - x, 0.5 - y, 1 - z.

poly[[(µ₃-adamantane-1,3-dicarboxylato)aquadioxidouranium(VI)] monohydrate]

Crystal data

[U(C12H14O4)O2(H2O)]·H2O	F(000) = 1968
Mr = 528.29	Dx = 2.353 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 24.254 (2) Å	Cell parameters from 9431 reflections
b = 6.7855 (6) Å	θ = 1.9–26.9°
c = 20.2586 (16) Å	µ = 10.92 mm^−1
β = 116.549 (4)°	T = 296 K
V = 2982.5 (4) Å^3	Prism, yellow
Z = 8	0.19 × 0.09 × 0.08 mm

Data collection

Bruker APEX2 area-detector diffractometer	3151 independent reflections
Radiation source: fine-focus sealed tube	2525 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 26.9°, θmin = 1.9°
Absorption correction: numerical face indexed (SADABS; Bruker, 2008)	h = −24→30
Tmin = 0.264, Tmax = 0.464	k = −8→8
9437 measured reflections	l = −25→24

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 2.1114P] where P = (Fo^2 + 2Fc^2)/3
3151 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 1.87 e Å^−3
0 restraints	Δρmin = −1.30 e Å^−3

Special details

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	0.091295 (10)	0.44436 (4)	0.456080 (12)	0.02661 (9)
O1	0.0659 (2)	0.2247 (8)	0.3533 (2)	0.0482 (14)
O2	0.1569 (2)	0.3541 (7)	0.3948 (2)	0.0377 (11)
O3	0.0878 (2)	0.3742 (8)	0.0510 (3)	0.0474 (13)
O4	0.0042 (2)	0.3483 (9)	0.0646 (3)	0.0561 (15)
O5	0.1937 (2)	0.6033 (7)	0.5193 (3)	0.0476 (13)
H1W	0.2242	0.5708	0.5118	0.071*
H2W	0.1989	0.7211	0.5352	0.071*
O6	0.1239 (2)	0.2431 (7)	0.5162 (2)	0.0420 (12)
O7	0.0615 (2)	0.6434 (8)	0.3972 (3)	0.0564 (14)
O8	0.2729 (2)	0.5055 (7)	0.4596 (3)	0.0516 (14)
H3W	0.2426	0.4561	0.4226	0.077*
H4W	0.3054	0.4444	0.4656	0.077*
C1	0.1156 (3)	0.2427 (10)	0.3485 (3)	0.0300 (15)
C2	0.0599 (3)	0.3091 (9)	0.0843 (3)	0.0271 (14)
C3	0.1230 (3)	0.1392 (9)	0.2865 (3)	0.0234 (13)
C4	0.0902 (3)	0.2727 (8)	0.2181 (3)	0.0221 (12)
H4A	0.1099	0.4010	0.2276	0.027*
H4B	0.0475	0.2907	0.2079	0.027*
C5	0.0935 (3)	0.1767 (8)	0.1507 (3)	0.0216 (12)
C6	0.0611 (3)	−0.0247 (9)	0.1370 (3)	0.0269 (14)
H6A	0.0185	−0.0069	0.1274	0.032*
H6B	0.0616	−0.0870	0.0942	0.032*
C7	0.0941 (3)	−0.1554 (9)	0.2046 (3)	0.0300 (14)
H7	0.0737	−0.2842	0.1950	0.036*
C8	0.0908 (3)	−0.0616 (8)	0.2708 (3)	0.0265 (14)
H8A	0.1107	−0.1465	0.3136	0.032*
H8B	0.0480	−0.0450	0.2609	0.032*
C9	0.1904 (3)	0.1136 (10)	0.3022 (3)	0.0290 (14)
H9A	0.2106	0.2410	0.3114	0.035*
H9B	0.2117	0.0323	0.3457	0.035*
C10	0.1928 (3)	0.0160 (9)	0.2356 (3)	0.0271 (14)
H10	0.2360	−0.0024	0.2457	0.033*
C11	0.1605 (3)	0.1463 (9)	0.1672 (3)	0.0248 (13)
H11A	0.1811	0.2728	0.1757	0.030*
H11B	0.1626	0.0844	0.1253	0.030*
C12	0.1610 (3)	−0.1837 (9)	0.2211 (4)	0.0346 (15)
H12A	0.1634	−0.2470	0.1796	0.042*
H12B	0.1813	−0.2676	0.2641	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.02513 (14)	0.03552 (16)	0.02354 (13)	−0.00016 (12)	0.01477 (10)	−0.00556 (11)
O1	0.032 (3)	0.079 (4)	0.044 (3)	−0.016 (3)	0.027 (2)	−0.034 (3)
O2	0.032 (3)	0.054 (3)	0.031 (2)	−0.007 (2)	0.018 (2)	−0.017 (2)
O3	0.038 (3)	0.067 (3)	0.047 (3)	0.011 (3)	0.028 (3)	0.037 (3)
O4	0.033 (3)	0.089 (4)	0.055 (3)	0.024 (3)	0.027 (3)	0.049 (3)
O5	0.035 (3)	0.054 (3)	0.063 (3)	−0.013 (2)	0.031 (3)	−0.026 (3)
O6	0.055 (3)	0.039 (3)	0.043 (3)	0.002 (2)	0.032 (3)	0.005 (2)
O7	0.055 (3)	0.066 (4)	0.055 (3)	0.027 (3)	0.030 (3)	0.019 (3)
O8	0.033 (3)	0.047 (3)	0.082 (4)	−0.006 (2)	0.032 (3)	−0.015 (3)
C1	0.032 (4)	0.037 (4)	0.023 (3)	0.005 (3)	0.015 (3)	−0.003 (3)
C2	0.031 (4)	0.030 (3)	0.023 (3)	0.001 (3)	0.014 (3)	0.006 (3)
C3	0.027 (3)	0.026 (3)	0.020 (3)	0.006 (3)	0.013 (3)	0.000 (3)
C4	0.027 (3)	0.015 (3)	0.030 (3)	−0.002 (3)	0.017 (3)	−0.002 (3)
C5	0.023 (3)	0.018 (3)	0.027 (3)	0.002 (3)	0.014 (3)	0.002 (3)
C6	0.029 (4)	0.026 (3)	0.025 (3)	0.004 (3)	0.012 (3)	−0.003 (3)
C7	0.038 (4)	0.012 (3)	0.045 (4)	−0.002 (3)	0.024 (3)	0.000 (3)
C8	0.031 (4)	0.018 (3)	0.037 (3)	0.004 (3)	0.021 (3)	0.010 (3)
C9	0.021 (3)	0.041 (4)	0.026 (3)	0.002 (3)	0.012 (3)	−0.003 (3)
C10	0.024 (3)	0.032 (3)	0.029 (3)	0.009 (3)	0.015 (3)	0.002 (3)
C11	0.028 (3)	0.027 (3)	0.026 (3)	−0.004 (3)	0.018 (3)	−0.003 (3)
C12	0.041 (4)	0.024 (3)	0.041 (4)	0.014 (3)	0.021 (3)	0.001 (3)

Geometric parameters (Å, º)

U1—O1	2.407 (4)	C4—H4B	0.9700
U1—O2	2.494 (4)	C5—C11	1.518 (8)
U1—O3^i	2.317 (4)	C5—C6	1.539 (8)
U1—O4^ii	2.259 (5)	C6—C7	1.523 (8)
U1—O5	2.475 (5)	C6—H6A	0.9700
U1—O6	1.764 (5)	C6—H6B	0.9700
U1—O7	1.732 (5)	C7—C12	1.515 (9)
O1—C1	1.258 (7)	C7—C8	1.519 (8)
O2—C1	1.271 (7)	C7—H7	0.9800
O3—C2	1.232 (7)	C8—H8A	0.9700
O4—C2	1.252 (7)	C8—H8B	0.9700
O5—H1W	0.8500	C9—C10	1.528 (8)
O5—H2W	0.8500	C9—H9A	0.9700
O8—H3W	0.8500	C9—H9B	0.9700
O8—H4W	0.8500	C10—C12	1.522 (9)
C1—C3	1.520 (7)	C10—C11	1.532 (8)
C2—C5	1.516 (8)	C10—H10	0.9800
C3—C9	1.529 (8)	C11—H11A	0.9700
C3—C8	1.532 (8)	C11—H11B	0.9700
C3—C4	1.545 (8)	C12—H12A	0.9700
C4—C5	1.547 (7)	C12—H12B	0.9700
C4—H4A	0.9700
O1—U1—O2	52.46 (14)	C2—C5—C6	109.7 (5)
O1—U1—O3^i	163.17 (16)	C11—C5—C6	109.2 (5)
O1—U1—O4^ii	79.39 (15)	C2—C5—C4	108.3 (4)
O1—U1—O5	121.85 (14)	C11—C5—C4	109.6 (5)
O1—U1—O6	88.9 (2)	C6—C5—C4	108.0 (4)
O1—U1—O7	91.2 (2)	C7—C6—C5	109.5 (5)
O2—U1—O3^i	144.32 (16)	C7—C6—H6A	109.8
O2—U1—O4^ii	131.85 (15)	C5—C6—H6A	109.8
O2—U1—O5	69.44 (14)	C7—C6—H6B	109.8
O2—U1—O6	87.95 (17)	C5—C6—H6B	109.8
O2—U1—O7	90.66 (19)	H6A—C6—H6B	108.2
O3^i—U1—O4^ii	83.80 (16)	C12—C7—C8	109.4 (5)
O3^i—U1—O5	74.89 (15)	C12—C7—C6	110.7 (5)
O3^i—U1—O6	90.58 (19)	C8—C7—C6	109.6 (5)
O3^i—U1—O7	89.9 (2)	C12—C7—H7	109.0
O4^ii—U1—O5	158.49 (15)	C8—C7—H7	109.0
O4^ii—U1—O6	90.6 (2)	C6—C7—H7	109.0
O4^ii—U1—O7	91.1 (2)	C7—C8—C3	109.4 (4)
O5—U1—O6	86.7 (2)	C7—C8—H8A	109.8
O5—U1—O7	91.7 (2)	C3—C8—H8A	109.8
O6—U1—O7	178.2 (2)	C7—C8—H8B	109.8
C1—O1—U1	97.0 (4)	C3—C8—H8B	109.8
C1—O2—U1	92.5 (3)	H8A—C8—H8B	108.2
C2—O3—U1^iii	151.5 (4)	C10—C9—C3	108.9 (5)
C2—O4—U1^ii	171.8 (5)	C10—C9—H9A	109.9
U1—O5—H1W	123.2	C3—C9—H9A	109.9
U1—O5—H2W	123.5	C10—C9—H9B	109.9
H1W—O5—H2W	108.4	C3—C9—H9B	109.9
H3W—O8—H4W	108.4	H9A—C9—H9B	108.3
O1—C1—O2	118.0 (5)	C12—C10—C9	109.9 (5)
O1—C1—C3	119.4 (6)	C12—C10—C11	109.2 (5)
O2—C1—C3	122.5 (5)	C9—C10—C11	110.0 (5)
O3—C2—O4	121.7 (6)	C12—C10—H10	109.3
O3—C2—C5	119.2 (5)	C9—C10—H10	109.3
O4—C2—C5	119.0 (5)	C11—C10—H10	109.3
C1—C3—C9	113.0 (5)	C5—C11—C10	110.1 (4)
C1—C3—C8	110.1 (5)	C5—C11—H11A	109.6
C9—C3—C8	110.0 (5)	C10—C11—H11A	109.6
C1—C3—C4	105.5 (5)	C5—C11—H11B	109.6
C9—C3—C4	109.2 (4)	C10—C11—H11B	109.6
C8—C3—C4	109.0 (5)	H11A—C11—H11B	108.2
C3—C4—C5	109.6 (4)	C7—C12—C10	109.3 (5)
C3—C4—H4A	109.8	C7—C12—H12A	109.8
C5—C4—H4A	109.8	C10—C12—H12A	109.8
C3—C4—H4B	109.8	C7—C12—H12B	109.8
C5—C4—H4B	109.8	C10—C12—H12B	109.8
H4A—C4—H4B	108.2	H12A—C12—H12B	108.3
C2—C5—C11	112.0 (4)
O7—U1—O1—C1	89.4 (4)	O4—C2—C5—C6	59.0 (7)
O6—U1—O1—C1	−88.9 (4)	O3—C2—C5—C4	121.9 (6)
O4^ii—U1—O1—C1	−179.7 (4)	O4—C2—C5—C4	−58.6 (7)
O3^i—U1—O1—C1	−177.1 (6)	C3—C4—C5—C2	178.9 (4)
O5—U1—O1—C1	−3.4 (5)	C3—C4—C5—C11	−58.7 (6)
O2—U1—O1—C1	−0.6 (4)	C3—C4—C5—C6	60.2 (6)
O7—U1—O2—C1	−90.4 (4)	C2—C5—C6—C7	−178.6 (4)
O6—U1—O2—C1	90.7 (4)	C11—C5—C6—C7	58.3 (6)
O4^ii—U1—O2—C1	1.7 (5)	C4—C5—C6—C7	−60.8 (6)
O3^i—U1—O2—C1	178.8 (4)	C5—C6—C7—C12	−58.9 (6)
O1—U1—O2—C1	0.6 (4)	C5—C6—C7—C8	61.9 (6)
O5—U1—O2—C1	178.0 (4)	C12—C7—C8—C3	60.4 (6)
U1—O1—C1—O2	1.0 (6)	C6—C7—C8—C3	−61.2 (7)
U1—O1—C1—C3	−176.3 (5)	C1—C3—C8—C7	175.3 (5)
U1—O2—C1—O1	−1.0 (6)	C9—C3—C8—C7	−59.5 (6)
U1—O2—C1—C3	176.2 (5)	C4—C3—C8—C7	60.1 (6)
U1^iii—O3—C2—O4	−1.3 (14)	C1—C3—C9—C10	−177.8 (5)
U1^iii—O3—C2—C5	178.2 (7)	C8—C3—C9—C10	58.7 (6)
O1—C1—C3—C9	−159.9 (6)	C4—C3—C9—C10	−60.8 (6)
O2—C1—C3—C9	22.9 (8)	C3—C9—C10—C12	−59.4 (7)
O1—C1—C3—C8	−36.5 (8)	C3—C9—C10—C11	60.8 (6)
O2—C1—C3—C8	146.3 (6)	C2—C5—C11—C10	178.6 (5)
O1—C1—C3—C4	80.9 (7)	C6—C5—C11—C10	−59.6 (6)
O2—C1—C3—C4	−96.3 (7)	C4—C5—C11—C10	58.5 (6)
C1—C3—C4—C5	−178.4 (5)	C12—C10—C11—C5	60.6 (6)
C9—C3—C4—C5	59.9 (6)	C9—C10—C11—C5	−60.0 (6)
C8—C3—C4—C5	−60.2 (6)	C8—C7—C12—C10	−61.1 (6)
O3—C2—C5—C11	1.0 (8)	C6—C7—C12—C10	59.8 (6)
O4—C2—C5—C11	−179.5 (6)	C9—C10—C12—C7	60.9 (7)
O3—C2—C5—C6	−120.5 (6)	C11—C10—C12—C7	−59.8 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1W···O8	0.85	1.96	2.772 (6)	160
O5—H2W···O8^iv	0.85	1.96	2.753 (7)	154
O8—H3W···O2	0.85	2.02	2.719 (7)	139
O8—H4W···O6^v	0.85	2.03	2.872 (7)	170

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