Dihydro[2.2.2]cryptand di-[mu]-hydroxo-bis[bis(nitrato-[kappa]²O,O')dioxouranium(VI)] monohydrate

In the title dinuclear uranyl complex, (C₁₈H₃₈N₂O₆)[(UO₂)₂(NO₃)₄(OH)₂]·H₂O, each pair of uranyl ions in the two independent centrosymmetric dianionic dimers is bridged by the two hydroxide ions, with the nitrate ions ensuring equatorial hexagonal coordination. The di­hydro[2.2.2]­cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]­hexa­cosane) dication presents an `in-in' conformation (endo protonation) and it is hydrogen bonded to the hydroxide ions, either directly or via a water mol­ecule, resulting in the formation of linear hydrogen-bonded polymers.

S1. Comment

[2.2.2]Cryptand has recently been used as a basic agent in the synthesis of uranyl ion complexes of hexahomotrioxacalix[3]arenes (Masci et al., 2002). In some of the resulting supramolecular assemblies, dihydro[2.2.2]cryptand (2+) is encapsulated between two complex molecules and held by feeble forces (cation-π and CH-π interactions). Compound (I) was obtained as a by-product during the investigation of a similar reaction with another calixarene. A search of the Cambridge Structural Database (CSD, Version 5.23; Allen & Kennard, 1993) gives few compounds closely related to (I). The di-µ-hydroxo-bis[bis(nitrato-κ²O,O')dioxouranium(VI)] complex has been described previously, in association with choline (Viossat et al., 1983) or 4,4'-bipyridinium (Alcock & Flanders, 1987), as well as the related di-µ-aqua-bis[bis(nitrato-κ²O,O')dioxouranium(VI)] complex (Perry et al., 1980; Hämäläinen et al., 1996). The cis positioning of two nitrate ions bound to a bis(hydroxide) uranyl group was first observed in the related compound di-µ-hydroxo-[bis(nitrato-κ²O,O')dioxouranium(VI)] [tris(aqua)dioxouranium(VI)] monohydrate (Perrin, 1976). \sch

The asymmetric unit in (I) comprises two half complex molecules, a complete dihydro[2.2.2]cryptand (2+) and a water molecule. The two complex molecules have similar geometries. The U atoms are in distorted hexagonal-bipyramidal environments, with a common edge defined by the double hydroxide bridge. The six O atoms from the nitrate and hydroxide ions around each U atom define a plane with r.m.s. deviations of 0.077 (3) and 0.081 (3) Å and distances to U of 0.009 (1) and 0.028 (1) Å in each molecule. The O_axial—U—O_equatorial angles are in the ranges 85.82 (17)–92.94 (18)° in the first molecule and 86.63 (16)–94.33 (17)° in the second, indicating some puckering of the equatorial donor atoms.

The U—O(nitrate) bond lengths are in the range 2.515 (4)–2.561 (4) Å, in agreement with values in the analogous complexes. The U—O(hydroxide) bond lengths are shorter, in the range 2.313 (4)–2.342 (4) Å, and the U—O(hydroxide)-U angles are 112.77 (16) and 113.60 (15)°; all these values are in agreement with those in the previous compounds. The U···U distances are 3.8556 (5) and 3.9156 (5) Å in the two molecules, close to the range of 3.896–3.944 Å in the examples cited above.

The dihydro[2.2.2]cryptand (2+) dication is in the `in-in' conformation, the two H atoms bound to the N atoms being directed inwards, as a result of endo protonation. This is the most common geometry for this cation, although it has been shown that exo protonation, associated with the `out-out' conformation, could be stabilized in the solid state when the H atoms are involved in hydrogen bonding with an external acceptor (MacGillivray & Atwood, 1997a). However, even when such acceptors are available, the `in-in' conformation may be observed, as in the present case or in the assemblies involving uranyl complexes of hexahomotrioxacalix[3]arenes (Masci et al., 2002).

The ammonium H atoms in (I) are involved in loose trifurcated hydrogen bonds with the ether O atoms (MacGillivray & Atwood, 1997b), some of the latter being themselves also hydrogen bonded to external donors. Atom O22 is thus hydrogen bonded to the hydroxide ion of the second complex molecule, whereas atoms O19 and O23, which pertain to different ether chains, are bonded to the two H atoms of the water molecule. This peculiar involvement of three ether O atoms, one in each `arm', in external hydrogen bonds, results in a rather distorted cryptand geometry. All N—C—C—O and O—C—C—O torsion angles are gauche [in the range 50.3 (6)–70.0 (6)°], but two C—O—C—C angles are gauche instead of anti, with values of 77.8 (6) and 75.3 (6)°.

The N···N separation is 5.710 (7) Å, much shorter than in the neutral ligand (6.87 Å; Reference?) due to the internal hydrogen bonds and in agreement with those in other diprotonated species (Masci et al., 2002). The O···O separations in each half-molecule are in the range 3.881 (6)–4.303 (6) Å.

The water molecule acts as a hydrogen-bond acceptor towards the hydroxide ion of the first molecule (this bond being seemingly the strongest of all hydrogen bonds in this compound). The cryptand cations are thus held between successive complex molecules, either directly or via the water molecules. Both cryptand and water molecules can be considered as second-sphere ligands with respect to the uranyl ions. This arrangement results in the formation of linear polymers along the (201) direction. A similar arrangement has been decribed in the complex 4,4'-bipyridinium di-µ-hydroxo-bis[bis(nitrato-κ²O,O')dioxouranium(VI)] monohydrate (Alcock & Flanders, 1987), in which chains of alternating uranyl complexes and 4,4'-bipyridinium ions are held together by hydrogen bonds, either directly between ammonium and hydroxide ions or via a water molecule.

S2. Experimental

Reaction of uranyl nitrate hexahydrate with a stoichiometric amount of [2.2.2]cryptand in boiling CH₃CN/CHCl₃ (1:1) in the presence of p-tert-butylcalix[5]arene gave a light-yellow solution, which indicated the absence of complexation of uranyl ions by the calixarene (the characteristic colour of such complexes is dark orange), and yielded crystals of (I) suitable for X-ray crystallography.

S3. Refinement

The H atoms bound to N and O atoms were found in the difference Fourier map and were introduced as riding atoms, with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions as riding atoms, with C—H = 0.97 Å and an isotropic displacement parameter equal to 1.2 times that of the parent atom.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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 and PARST97 (Nardelli, 1995).

Figures

Fig. 1. A view showing the two centrosymmetric complex molecules surrounding the hydrogen-bonded dication and water molecule in (I), with a partial atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms involved in hydrogen bonding are drawn as small spheres of arbitrary radii; other H atoms have been omitted for clarity. Intermolecular hydrogen bonds are shown as dashed lines; intramolecular hydrogen bonds are not represented [symmetry codes: (i) -x, 1 - y, 2 - z; (ii) 2 - x, 1 - y, 1 - z.]

Dihydro[2.2.2]cryptand (2+) di-µ-hydroxo-bis[bis(nitrato-κ²O,O')dioxouranium(VI)] monohydrate

Crystal data

(C18H38N2O6)[U2O4(NO3)4(OH)2]·H2O	Z = 2
Mr = 1218.64	F(000) = 1152
Triclinic, P1	Dx = 2.281 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0595 (5) Å	Cell parameters from 12164 reflections
b = 9.8517 (5) Å	θ = 2.8–25.7°
c = 20.8019 (12) Å	µ = 9.22 mm^−1
α = 86.528 (3)°	T = 100 K
β = 82.042 (3)°	Needle, light yellow
γ = 74.826 (3)°	0.3 × 0.1 × 0.1 mm
V = 1774.04 (17) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	6199 independent reflections
Radiation source: fine-focus sealed tube	5014 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ϕ scans	θmax = 25.7°, θmin = 2.8°
Absorption correction: empirical (using intensity measurements) (DELABS in PLATON; Spek, 2000)	h = −11→11
Tmin = 0.201, Tmax = 0.398	k = −12→12
12164 measured reflections	l = −25→25

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2)]
6199 reflections	(Δ/σ)max = 0.001
460 parameters	Δρmax = 0.92 e Å^−3
0 restraints	Δρmin = −0.90 e Å^−3

Special details

Experimental. A 180° range in ϕ was scanned during both data collections, with 2° ϕ steps. The crystal-to-detector distance was fixed at 28 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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atoms bound to O and N have been found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. 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	−0.05889 (2)	0.69563 (2)	0.973552 (10)	0.02207 (7)
U2	0.87830 (2)	0.66955 (2)	0.545312 (10)	0.02116 (7)
O1	−0.2555 (5)	0.6901 (4)	0.9762 (2)	0.0287 (10)
O2	0.1360 (5)	0.7058 (4)	0.9701 (2)	0.0302 (10)
O3	−0.1093 (5)	0.8079 (4)	1.0834 (2)	0.0327 (10)
O4	−0.1684 (6)	0.9537 (5)	1.0043 (2)	0.0370 (11)
O5	−0.2190 (6)	1.0282 (5)	1.1039 (2)	0.0439 (12)
O6	−0.1018 (5)	0.8883 (4)	0.8868 (2)	0.0363 (11)
O7	−0.0176 (5)	0.6778 (5)	0.8499 (2)	0.0360 (11)
O8	−0.0458 (6)	0.8580 (5)	0.7821 (2)	0.0467 (13)
O9	0.0279 (5)	0.4653 (4)	0.94029 (19)	0.0235 (9)
H9	0.0997	0.4541	0.8962	0.028*
O10	0.7055 (5)	0.6212 (4)	0.53670 (19)	0.0262 (9)
O11	1.0469 (5)	0.7248 (4)	0.55390 (19)	0.0276 (9)
O12	0.8806 (5)	0.5758 (4)	0.6605 (2)	0.0341 (10)
O13	0.7440 (5)	0.7888 (4)	0.6499 (2)	0.0294 (10)
O14	0.7514 (6)	0.6883 (5)	0.7461 (2)	0.0422 (12)
O15	0.7237 (5)	0.9269 (4)	0.5400 (2)	0.0307 (10)
O16	0.8234 (5)	0.8337 (4)	0.4477 (2)	0.0315 (10)
O17	0.6683 (6)	1.0462 (5)	0.4504 (2)	0.0373 (11)
O18	0.9998 (5)	0.4297 (4)	0.55388 (19)	0.0253 (9)
H18	0.9445	0.3837	0.5768	0.030*
N1	−0.1692 (6)	0.9345 (5)	1.0652 (3)	0.0294 (12)
N2	−0.0543 (6)	0.8087 (5)	0.8370 (3)	0.0322 (13)
N3	0.7913 (6)	0.6837 (5)	0.6881 (3)	0.0300 (12)
N4	0.7353 (6)	0.9400 (5)	0.4784 (2)	0.0258 (11)
O19	0.4973 (5)	0.1410 (4)	0.86130 (19)	0.0262 (9)
O20	0.4464 (4)	0.1644 (4)	0.7306 (2)	0.0242 (9)
O21	0.8219 (5)	0.2592 (5)	0.74850 (19)	0.0296 (10)
O22	0.7677 (5)	0.2821 (4)	0.61438 (19)	0.0241 (9)
O23	0.4378 (5)	0.5731 (4)	0.83267 (19)	0.0266 (9)
O24	0.3951 (5)	0.6084 (4)	0.69586 (19)	0.0287 (9)
N5	0.6675 (5)	0.3411 (5)	0.8719 (2)	0.0242 (11)
H5	0.6380	0.3348	0.8342	0.029*
N6	0.4382 (5)	0.3600 (5)	0.6284 (2)	0.0229 (11)
H6	0.5181	0.3430	0.6524	0.027*
C1	0.7112 (7)	0.1988 (6)	0.9044 (3)	0.0269 (13)
H1A	0.7490	0.2069	0.9450	0.032*
H1B	0.7933	0.1369	0.8768	0.032*
C2	0.5711 (7)	0.1354 (6)	0.9177 (3)	0.0255 (13)
H2A	0.6048	0.0382	0.9325	0.031*
H2B	0.4979	0.1867	0.9520	0.031*
C3	0.5765 (7)	0.0344 (6)	0.8156 (3)	0.0276 (14)
H3A	0.6017	−0.0567	0.8377	0.033*
H3B	0.6718	0.0544	0.7952	0.033*
C4	0.4744 (7)	0.0326 (6)	0.7654 (3)	0.0272 (13)
H4A	0.5233	−0.0430	0.7356	0.033*
H4B	0.3775	0.0163	0.7860	0.033*
C5	0.3248 (7)	0.1794 (6)	0.6930 (3)	0.0249 (13)
H5A	0.2331	0.1669	0.7201	0.030*
H5B	0.3533	0.1093	0.6596	0.030*
C6	0.2937 (6)	0.3272 (6)	0.6620 (3)	0.0246 (13)
H6A	0.2214	0.3353	0.6308	0.030*
H6B	0.2467	0.3956	0.6953	0.030*
C7	0.8056 (7)	0.3940 (7)	0.8416 (3)	0.0292 (14)
H7A	0.7693	0.4843	0.8200	0.035*
H7B	0.8631	0.4078	0.8756	0.035*
C8	0.9112 (7)	0.2933 (7)	0.7932 (3)	0.0307 (15)
H8A	0.9890	0.3362	0.7703	0.037*
H8B	0.9630	0.2085	0.8156	0.037*
C9	0.9186 (7)	0.1770 (7)	0.6967 (3)	0.0279 (14)
H9A	0.9747	0.0878	0.7141	0.034*
H9B	0.9931	0.2262	0.6761	0.034*
C10	0.8246 (7)	0.1509 (7)	0.6475 (3)	0.0292 (14)
H10A	0.8875	0.0819	0.6169	0.035*
H10B	0.7393	0.1153	0.6686	0.035*
C11	0.6919 (7)	0.2700 (7)	0.5600 (3)	0.0266 (13)
H11A	0.7536	0.1912	0.5342	0.032*
H11B	0.6831	0.3547	0.5329	0.032*
C12	0.5320 (7)	0.2480 (6)	0.5812 (3)	0.0282 (14)
H12A	0.4790	0.2519	0.5435	0.034*
H12B	0.5414	0.1557	0.6019	0.034*
C13	0.5640 (7)	0.4490 (6)	0.9185 (3)	0.0278 (14)
H13A	0.4762	0.4144	0.9372	0.033*
H13B	0.6205	0.4583	0.9536	0.033*
C14	0.5067 (8)	0.5902 (7)	0.8883 (3)	0.0303 (14)
H14A	0.4313	0.6504	0.9191	0.036*
H14B	0.5914	0.6333	0.8756	0.036*
C15	0.3891 (8)	0.7066 (7)	0.7995 (3)	0.0313 (14)
H15A	0.4788	0.7398	0.7821	0.038*
H15B	0.3248	0.7750	0.8301	0.038*
C16	0.3009 (7)	0.6942 (6)	0.7456 (3)	0.0312 (14)
H16A	0.2157	0.6544	0.7626	0.037*
H16B	0.2585	0.7871	0.7275	0.037*
C17	0.3132 (8)	0.6170 (7)	0.6410 (3)	0.0308 (14)
H17A	0.3032	0.7084	0.6193	0.037*
H17B	0.2108	0.6046	0.6548	0.037*
C18	0.4034 (7)	0.5025 (6)	0.5955 (3)	0.0275 (14)
H18A	0.3451	0.5006	0.5600	0.033*
H18B	0.4996	0.5238	0.5773	0.033*
O25	0.2383 (5)	0.3929 (4)	0.8317 (2)	0.0311 (10)
H25A	0.3124	0.4464	0.8191	0.037*
H25B	0.2970	0.3029	0.8310	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.02178 (12)	0.02027 (12)	0.02378 (13)	−0.00479 (9)	−0.00285 (9)	−0.00035 (9)
U2	0.02052 (12)	0.02157 (13)	0.02093 (12)	−0.00477 (9)	−0.00186 (9)	−0.00142 (9)
O1	0.027 (2)	0.033 (2)	0.028 (2)	−0.0096 (19)	−0.0025 (19)	−0.0047 (19)
O2	0.028 (2)	0.029 (2)	0.034 (2)	−0.0110 (19)	−0.0016 (19)	0.003 (2)
O3	0.046 (3)	0.022 (2)	0.032 (2)	−0.009 (2)	−0.010 (2)	0.0009 (19)
O4	0.047 (3)	0.025 (2)	0.038 (3)	−0.007 (2)	−0.006 (2)	−0.002 (2)
O5	0.062 (3)	0.027 (2)	0.040 (3)	−0.015 (2)	0.015 (2)	−0.009 (2)
O6	0.042 (3)	0.023 (2)	0.037 (3)	0.001 (2)	−0.005 (2)	0.003 (2)
O7	0.043 (3)	0.028 (2)	0.028 (2)	0.003 (2)	0.002 (2)	0.004 (2)
O8	0.040 (3)	0.050 (3)	0.038 (3)	0.001 (2)	0.006 (2)	0.020 (2)
O9	0.027 (2)	0.023 (2)	0.022 (2)	−0.0112 (17)	0.0020 (17)	−0.0021 (17)
O10	0.026 (2)	0.024 (2)	0.029 (2)	−0.0083 (18)	−0.0047 (18)	0.0006 (18)
O11	0.027 (2)	0.031 (2)	0.026 (2)	−0.0091 (19)	−0.0025 (18)	−0.0007 (19)
O12	0.043 (3)	0.026 (2)	0.028 (2)	−0.001 (2)	0.002 (2)	−0.005 (2)
O13	0.033 (2)	0.027 (2)	0.025 (2)	−0.0047 (19)	0.0013 (19)	−0.0004 (19)
O14	0.059 (3)	0.043 (3)	0.020 (2)	−0.010 (3)	0.006 (2)	−0.002 (2)
O15	0.035 (2)	0.027 (2)	0.027 (2)	−0.0028 (19)	−0.003 (2)	−0.0040 (19)
O16	0.035 (2)	0.028 (2)	0.027 (2)	−0.001 (2)	−0.002 (2)	−0.0032 (19)
O17	0.049 (3)	0.024 (2)	0.033 (3)	0.002 (2)	−0.010 (2)	0.003 (2)
O18	0.030 (2)	0.023 (2)	0.022 (2)	−0.0073 (18)	−0.0014 (18)	0.0045 (17)
N1	0.039 (3)	0.021 (3)	0.028 (3)	−0.010 (2)	0.001 (2)	−0.001 (2)
N2	0.028 (3)	0.028 (3)	0.031 (3)	0.004 (2)	0.006 (2)	0.008 (3)
N3	0.035 (3)	0.029 (3)	0.027 (3)	−0.013 (3)	0.002 (2)	−0.001 (3)
N4	0.031 (3)	0.021 (3)	0.026 (3)	−0.004 (2)	−0.008 (2)	−0.001 (2)
O19	0.025 (2)	0.025 (2)	0.026 (2)	−0.0040 (18)	−0.0008 (18)	−0.0039 (18)
O20	0.022 (2)	0.022 (2)	0.028 (2)	−0.0066 (17)	−0.0033 (17)	0.0018 (18)
O21	0.028 (2)	0.039 (3)	0.023 (2)	−0.011 (2)	−0.0042 (19)	−0.0006 (19)
O22	0.027 (2)	0.022 (2)	0.024 (2)	−0.0068 (18)	−0.0052 (18)	−0.0017 (17)
O23	0.033 (2)	0.023 (2)	0.022 (2)	−0.0050 (19)	−0.0016 (18)	−0.0028 (18)
O24	0.030 (2)	0.031 (2)	0.024 (2)	−0.0045 (19)	−0.0064 (19)	−0.0029 (19)
N5	0.024 (3)	0.027 (3)	0.020 (2)	−0.003 (2)	−0.002 (2)	−0.004 (2)
N6	0.022 (2)	0.021 (3)	0.027 (3)	−0.008 (2)	−0.003 (2)	0.001 (2)
C1	0.030 (3)	0.021 (3)	0.029 (3)	−0.005 (3)	−0.005 (3)	0.004 (3)
C2	0.032 (3)	0.021 (3)	0.023 (3)	−0.005 (3)	−0.005 (3)	0.001 (3)
C3	0.028 (3)	0.024 (3)	0.029 (3)	−0.005 (3)	−0.004 (3)	0.005 (3)
C4	0.026 (3)	0.021 (3)	0.033 (3)	−0.005 (3)	−0.002 (3)	0.008 (3)
C5	0.022 (3)	0.032 (3)	0.022 (3)	−0.010 (3)	−0.005 (2)	0.003 (3)
C6	0.017 (3)	0.032 (3)	0.026 (3)	−0.009 (3)	−0.003 (2)	0.000 (3)
C7	0.029 (3)	0.032 (3)	0.031 (3)	−0.015 (3)	−0.008 (3)	0.004 (3)
C8	0.029 (3)	0.043 (4)	0.026 (3)	−0.019 (3)	−0.010 (3)	0.004 (3)
C9	0.028 (3)	0.032 (3)	0.022 (3)	−0.006 (3)	−0.002 (3)	0.002 (3)
C10	0.028 (3)	0.029 (3)	0.033 (3)	−0.011 (3)	−0.010 (3)	0.003 (3)
C11	0.024 (3)	0.033 (3)	0.023 (3)	−0.008 (3)	0.000 (3)	−0.001 (3)
C12	0.032 (3)	0.026 (3)	0.028 (3)	−0.008 (3)	−0.004 (3)	−0.004 (3)
C13	0.028 (3)	0.027 (3)	0.027 (3)	−0.004 (3)	−0.002 (3)	−0.004 (3)
C14	0.036 (4)	0.029 (3)	0.023 (3)	−0.003 (3)	−0.001 (3)	−0.011 (3)
C15	0.043 (4)	0.027 (3)	0.025 (3)	−0.008 (3)	−0.007 (3)	−0.002 (3)
C16	0.034 (3)	0.022 (3)	0.031 (3)	0.002 (3)	−0.002 (3)	0.004 (3)
C17	0.034 (4)	0.027 (3)	0.030 (3)	−0.005 (3)	−0.009 (3)	0.005 (3)
C18	0.031 (3)	0.026 (3)	0.026 (3)	−0.011 (3)	−0.004 (3)	0.007 (3)
O25	0.031 (2)	0.023 (2)	0.035 (2)	−0.0043 (19)	0.002 (2)	0.0016 (19)

Geometric parameters (Å, º)

U1—O1	1.789 (4)	N6—C18	1.500 (7)
U1—O2	1.786 (4)	N6—C12	1.520 (8)
U1—O3	2.531 (4)	N6—H6	0.9096
U1—O4	2.561 (4)	C1—C2	1.540 (8)
U1—O6	2.529 (4)	C1—H1A	0.9700
U1—O7	2.559 (4)	C1—H1B	0.9700
U1—O9	2.313 (4)	C2—H2A	0.9700
U1—O9^i	2.317 (4)	C2—H2B	0.9700
U1—U1^i	3.8556 (5)	C3—C4	1.492 (8)
U2—O10	1.785 (4)	C3—H3A	0.9700
U2—O11	1.784 (4)	C3—H3B	0.9700
U2—O12	2.515 (4)	C4—H4A	0.9700
U2—O13	2.534 (4)	C4—H4B	0.9700
U2—O15	2.560 (4)	C5—C6	1.529 (8)
U2—O16	2.539 (4)	C5—H5A	0.9700
U2—O18	2.338 (4)	C5—H5B	0.9700
U2—O18^ii	2.341 (4)	C6—H6A	0.9700
U2—U2^ii	3.9156 (5)	C6—H6B	0.9700
O3—N1	1.281 (6)	C7—C8	1.506 (9)
O4—N1	1.268 (7)	C7—H7A	0.9700
O5—N1	1.215 (7)	C7—H7B	0.9700
O6—N2	1.293 (7)	C8—H8A	0.9700
O7—N2	1.266 (6)	C8—H8B	0.9700
O8—N2	1.214 (7)	C9—C10	1.493 (8)
O9—U1^i	2.317 (4)	C9—H9A	0.9700
O9—H9	1.0420	C9—H9B	0.9700
O12—N3	1.269 (7)	C10—H10A	0.9700
O13—N3	1.284 (6)	C10—H10B	0.9700
O14—N3	1.210 (7)	C11—C12	1.522 (8)
O15—N4	1.273 (6)	C11—H11A	0.9700
O16—N4	1.282 (6)	C11—H11B	0.9700
O17—N4	1.222 (6)	C12—H12A	0.9700
O18—U2^ii	2.341 (4)	C12—H12B	0.9700
O18—H18	0.8426	C13—C14	1.486 (9)
O19—C2	1.420 (7)	C13—H13A	0.9700
O19—C3	1.436 (7)	C13—H13B	0.9700
O20—C5	1.410 (7)	C14—H14A	0.9700
O20—C4	1.427 (7)	C14—H14B	0.9700
O21—C8	1.421 (7)	C15—C16	1.494 (9)
O21—C9	1.434 (7)	C15—H15A	0.9700
O22—C11	1.428 (7)	C15—H15B	0.9700
O22—C10	1.433 (7)	C16—H16A	0.9700
O23—C14	1.427 (7)	C16—H16B	0.9700
O23—C15	1.439 (7)	C17—C18	1.506 (9)
O24—C16	1.412 (7)	C17—H17A	0.9700
O24—C17	1.433 (7)	C17—H17B	0.9700
N5—C1	1.499 (7)	C18—H18A	0.9700
N5—C13	1.516 (7)	C18—H18B	0.9700
N5—C7	1.523 (8)	O25—H25A	0.9566
N5—H5	0.8733	O25—H25B	0.9069
N6—C6	1.499 (7)
O1—U1—O2	178.51 (18)	C2—C1—H1B	109.6
O3—U1—O4	49.89 (14)	H1A—C1—H1B	108.1
O4—U1—O6	59.24 (14)	O19—C2—C1	111.6 (5)
O6—U1—O7	50.29 (14)	O19—C2—H2A	109.3
O7—U1—O9	67.56 (14)	C1—C2—H2A	109.2
O9—U1—O9^i	67.23 (16)	O19—C2—H2B	109.4
O9^i—U1—O3	66.26 (13)	C1—C2—H2B	109.3
U1—O9—U1^i	112.77 (16)	H2A—C2—H2B	107.9
O2—U1—O9	89.83 (17)	O19—C3—C4	108.6 (5)
O1—U1—O9	91.35 (17)	O19—C3—H3A	110.0
O2—U1—O9^i	90.88 (16)	C4—C3—H3A	110.0
O1—U1—O9^i	90.41 (17)	O19—C3—H3B	110.0
O2—U1—O6	89.46 (17)	C4—C3—H3B	110.0
O1—U1—O6	89.19 (17)	H3A—C3—H3B	108.3
O9—U1—O6	117.84 (14)	O20—C4—C3	109.2 (5)
O9^i—U1—O6	174.92 (14)	O20—C4—H4A	109.9
O2—U1—O3	87.30 (18)	C3—C4—H4A	109.9
O1—U1—O3	92.53 (17)	O20—C4—H4B	109.8
O9—U1—O3	133.33 (13)	C3—C4—H4B	109.8
O6—U1—O3	108.70 (14)	H4A—C4—H4B	108.3
O2—U1—O7	88.64 (18)	O20—C5—C6	107.6 (5)
O1—U1—O7	90.98 (17)	O20—C5—H5A	110.2
O9^i—U1—O7	134.78 (14)	C6—C5—H5A	110.2
O3—U1—O7	158.66 (14)	O20—C5—H5B	110.2
O2—U1—O4	92.95 (18)	C6—C5—H5B	110.2
O1—U1—O4	85.82 (17)	H5A—C5—H5B	108.5
O9—U1—O4	175.91 (14)	N6—C6—C5	112.1 (5)
O9^i—U1—O4	115.69 (14)	N6—C6—H6A	109.2
O7—U1—O4	109.49 (14)	C5—C6—H6A	109.2
O10—U2—O11	177.80 (17)	N6—C6—H6B	109.1
O12—U2—O13	50.52 (13)	C5—C6—H6B	109.2
O13—U2—O15	61.18 (13)	H6A—C6—H6B	107.9
O15—U2—O16	50.02 (13)	C8—C7—N5	112.3 (5)
O12—U2—O18	66.28 (13)	C8—C7—H7A	109.2
O18—U2—O18^ii	66.40 (15)	N5—C7—H7A	109.2
O18^ii—U2—O16	66.15 (13)	C8—C7—H7B	109.1
U2—O18—U2^ii	113.60 (15)	N5—C7—H7B	109.1
O11—U2—O18	94.33 (17)	H7A—C7—H7B	107.9
O10—U2—O18	87.87 (16)	O21—C8—C7	108.8 (5)
O11—U2—O18^ii	89.10 (17)	O21—C8—H8A	109.9
O10—U2—O18^ii	91.93 (16)	C7—C8—H8A	110.0
O11—U2—O12	87.87 (17)	O21—C8—H8B	109.9
O10—U2—O12	92.87 (17)	C7—C8—H8B	109.9
O18^ii—U2—O12	132.18 (13)	H8A—C8—H8B	108.3
O11—U2—O13	90.25 (16)	O21—C9—C10	110.7 (5)
O10—U2—O13	88.62 (16)	O21—C9—H9A	109.5
O18—U2—O13	116.38 (13)	C10—C9—H9A	109.5
O18^ii—U2—O13	177.19 (13)	O21—C9—H9B	109.5
O11—U2—O16	92.02 (17)	C10—C9—H9B	109.5
O10—U2—O16	86.63 (16)	H9A—C9—H9B	108.1
O18—U2—O16	131.96 (13)	O22—C10—C9	107.5 (5)
O18^ii—U2—O16	66.15 (13)	O22—C10—H10A	110.2
O12—U2—O16	161.65 (14)	C9—C10—H10A	110.2
O13—U2—O16	111.15 (13)	O22—C10—H10B	110.2
O11—U2—O15	89.99 (16)	C9—C10—H10B	110.2
O10—U2—O15	87.81 (16)	H10A—C10—H10B	108.5
O18—U2—O15	175.09 (14)	O22—C11—C12	111.6 (5)
O18^ii—U2—O15	116.08 (13)	O22—C11—H11A	109.3
O12—U2—O15	111.63 (13)	C12—C11—H11A	109.3
N1—O3—U1	98.0 (3)	O22—C11—H11B	109.3
N1—O4—U1	97.0 (3)	C12—C11—H11B	109.3
N2—O6—U1	97.4 (3)	H11A—C11—H11B	107.9
N2—O7—U1	96.8 (3)	N6—C12—C11	110.9 (5)
U1—O9—H9	113.4	N6—C12—H12A	109.5
U1^i—O9—H9	124.4	C11—C12—H12A	109.4
N3—O12—U2	97.8 (3)	N6—C12—H12B	109.5
N3—O13—U2	96.5 (3)	C11—C12—H12B	109.5
N4—O15—U2	96.9 (3)	H12A—C12—H12B	108.1
N4—O16—U2	97.6 (3)	C14—C13—N5	114.2 (5)
U2—O18—H18	113.1	C14—C13—H13A	108.7
U2^ii—O18—H18	115.5	N5—C13—H13A	108.7
O5—N1—O4	123.5 (5)	C14—C13—H13B	108.7
O5—N1—O3	121.6 (5)	N5—C13—H13B	108.7
O4—N1—O3	114.9 (5)	H13A—C13—H13B	107.6
O8—N2—O7	123.2 (6)	O23—C14—C13	108.1 (5)
O8—N2—O6	121.5 (5)	O23—C14—H14A	110.0
O7—N2—O6	115.3 (5)	C13—C14—H14A	110.1
O14—N3—O12	123.1 (6)	O23—C14—H14B	110.1
O14—N3—O13	121.8 (5)	C13—C14—H14B	110.1
O12—N3—O13	115.1 (5)	H14A—C14—H14B	108.4
O17—N4—O15	122.6 (5)	O23—C15—C16	110.9 (5)
O17—N4—O16	122.3 (5)	O23—C15—H15A	109.5
O15—N4—O16	115.1 (5)	C16—C15—H15A	109.4
C2—O19—C3	113.6 (4)	O23—C15—H15B	109.4
C5—O20—C4	111.0 (4)	C16—C15—H15B	109.5
C8—O21—C9	111.2 (5)	H15A—C15—H15B	108.1
C11—O22—C10	113.7 (4)	O24—C16—C15	111.6 (5)
C14—O23—C15	110.0 (4)	O24—C16—H16A	109.3
C16—O24—C17	109.7 (4)	C15—C16—H16A	109.3
C1—N5—C13	111.3 (5)	O24—C16—H16B	109.3
C1—N5—C7	113.5 (4)	C15—C16—H16B	109.3
C13—N5—C7	109.5 (5)	H16A—C16—H16B	108.0
C1—N5—H5	110.6	O24—C17—C18	107.7 (5)
C13—N5—H5	118.1	O24—C17—H17A	110.2
C7—N5—H5	92.7	C18—C17—H17A	110.1
C6—N6—C18	111.0 (4)	O24—C17—H17B	110.2
C6—N6—C12	113.3 (4)	C18—C17—H17B	110.1
C18—N6—C12	111.0 (5)	H17A—C17—H17B	108.5
C6—N6—H6	115.4	N6—C18—C17	112.7 (5)
C18—N6—H6	114.5	N6—C18—H18A	109.1
C12—N6—H6	90.0	C17—C18—H18A	109.1
N5—C1—C2	110.5 (5)	N6—C18—H18B	109.0
N5—C1—H1A	109.5	C17—C18—H18B	109.0
C2—C1—H1A	109.5	H18A—C18—H18B	107.8
N5—C1—H1B	109.5	H25A—O25—H25B	103.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O19	0.87	2.56	2.837 (6)	100
N5—H5···O21	0.87	2.28	2.805 (6)	119
N5—H5···O23	0.87	2.57	2.824 (6)	98
N6—H6···O20	0.91	2.47	2.777 (6)	100
N6—H6···O22	0.91	2.23	2.858 (6)	126
N6—H6···O24	0.91	2.72	2.806 (6)	86
O9—H9···O25	1.04	1.73	2.746 (6)	165
O18—H18···O22	0.84	2.14	2.961 (6)	165
O25—H25B···O19	0.91	2.22	3.035 (6)	150
O25—H25A···O23	0.96	1.95	2.849 (6)	155