A uranyl ion complex of N-methyl-p-tert-butyl­dihomo­ammonio­calix­[4]­arene with di­aqua­di­pyridine­lithium as counter-ion

The title complex, di­aqua­di­pyridine­lithium (N-methyl-p-tert-butyl­dihomo­ammonio­calix­[4]­arene-[kappa]⁴O)­dioxouranium(VI) tri­pyridine solvate monohydrate, [Li(C₅H₅N)₂(H₂O)₂][UO₂(C₄₆H₅₈NO₄)]·3C₅H₅N·H₂O, contains an `internal' tetraphenoxide-coordinated uranyl complex of the macrocycle, in which the protonated N atom is involved in an intramolecular hydrogen bond with the uranyl oxo group located in the cavity. The Li⁺ ion is in a tetrahedral environment and its two water ligands are involved in hydrogen bonds with two phenoxide O atoms, two pyridine mol­ecules and one water mol­ecule. This arrangement is compared with those obtained previously for other homo­aza­calixarenes and also for homo­oxa­calixarenes in the presence of alkali metal hydro­xides.

S1. Comment

Homoazacalixarenes (Takemura, 2002) and homooxacalixarenes (Masci, 2001) are macrocycles that differ from usual calixarenes by the lengthening of at least one methylene bridge, as a result of its replacement by a 2-oxa- or 2-aza-1,3-propylene bridge. Such modifications of the calixarene skeleton provide the molecule with increased flexibility, novel donor atoms and, in the case of homoazacalixarenes, new sites for functionalization. We reported some years ago the synthesis and crystal structures of rare earth (Thuéry et al., 2000a,b; Thuéry, Nierlich, Vicens & Takemura, 2001) and uranyl ion (Thuéry, Nierlich, Vicens, Masci & Takemura, 2001; Thuéry, Nierlich, Harrowfield & Ogden, 2001) complexes of homoazacalixarenes. An interesting peculiarity of these ligands is their ability to complex these metal ions without addition of a base, since the protons can be transferred from the phenol to the amine groups, resulting in the formation of zwitterionic species. In the case of the uranyl ion and the ligands p-chloro-N-benzylhexahomotriazacalix[3]arene and p-methyl-N-benzyltetrahomodiazacalix[4]arene, `external' complexation results, because of the repulsion between the metallic cation and the ammonium groups in the complex. By contrast, in the presence of an extra base (triethylamine), a different `internal' coordination mode is observed in the case of p-methyl-N-benzyltetrahomodiazacalix[4]arene; this mode results from an enlargement of the cavity due to the higher deprotonation degree and removal of intramolecular phenol···phenoxide hydrogen bonds (Thuéry, Nierlich, Vicens & Takemura, 2001). We report here the crystal structure of the uranyl complex, (I), with another ligand comprising only one amine link, obtained in the presence of lithium hydroxide as a base. This result is part of an investigation of mixed uranyl/alkali metal ions complexes, which was first carried out on homooxacalixarenes (Thuéry & Masci, 2003).

The asymmetric unit in (I) contains the uranyl complex itself, which is a monoanion, and the lithium counter-ion bound to two pyridine and two water molecules, as well as one water and three pyridine solvent molecules (Fig. 1 and Table 1). As in the structure of the uranyl complex with p-methyl-N-benzyltetrahomodiazacalix[4]arene obtained in the presence of triethylamine, the cation is complexed in an `internal' mode and is bound to the four phenoxide groups in its equatorial plane, with a mean U—O distance of 2.27 (2) Å, as usual. The four donor atoms are coplanar, the maximum deviation from the plane being 0.008 (3) Å, and the U atom lies 0.106 (3) Å from this plane, on the same side as oxo atom O5. The coordination geometry of U would thus be square-planar-bipyramidal but for the distortion in the plane resulting from the presence of the longer N-containing bridge. The O1—U—O4 angle is about 15° larger than the O1—U—O2 and O3—U—O4 angles, whereas the O2—U—O3 angle is about 6° smaller. The N atom is protonated and involved in a hydrogen bond (Table 2) with the uranyl oxo group located in the macrocycle cavity. Such hydrogen bonds with uranyl oxo groups are extremely common because of the basicity of the O atom, but this case presents the particular feature of an U═O6···N1 angle particularly far from linearity, with a value of 99.2 (2)°. A search of the Cambridge Structural Database (CSD; Version 5.24; Allen, 2002) for hydrogen-bonding contacts between uranyl ions and O– or N-containing donors shows that the largest number of cases correspond to U═O···(O,N) angles of about 110–160° and O···(O,N) distances larger than 2.80 Å (with no straightforward correlation between angle and distance). The N1···O6 and H1···O6 distances in (I) are 3.083 (8) and 2.17 Å, which indicate a weak hydrogen bond; the U═O6···N1 angle is probably small because of the geometric constraints resulting from the macrocyclic nature of the ligand. In the previous `internal' uranyl complex of an homoazacalixarene, the two diametrically located ammonium groups were involved in hydrogen bonds with the closest phenoxide groups and not with the uranyl ion. The two torsion angles defined by the ammonium-containing bridge are both anti angles [C44—N1—C45—C1 = 165.3 (6)° and C45—N1—C44—C36 − 167.2 (6) = °], the resulting conformation bringing the ammonium H atom as close as possible to atom O6. Atom N1 is located 1.895 (9) Å from the mean O₄ plane and 3.808 (6) Å from the U atom. The latter distance is slightly smaller than those observed in other uranyl complexes of homoazacalixarenes (3.93–4.30 Å), which is probably related to the different macrocycle geometry and the presence of the uranyl–ammonium hydrogen bond. In the uranyl-ion complex of the related ligand p-tert-butyldihomooxacalix[4]arene, which differs from (I) by the replacement of the ammonium by an ether group, the U···O_ether distance is shorter [3.534 (8) Å; Harrowfield et al., 1991], and even shorter U···O_ether distances, some of them indicating bonding interactions [2.609 (8)–2.950 (4) Å] have been observed in complexes with other homooxacalixarenes (Masci et al., 2002a,b; Thuéry, Nierlich, Vicens & Masci, 2001). The larger distance with the ammonium N atom in (I) likely arises from a subtle balance between cation···cation repulsion, hydrogen-bonding interaction and macrocycle geometric requirements.

The macrocycle in (I) is in the usual cone conformation. With respect to the O₄ reference plane, the four aromatic rings define dihedral angles of 46.5 (2), 64.6 (2), 58.2 (2) and 52.0 (2)°. The bowl shape thus defined accommodates a pyridine molecule, as is often observed. The O1···O2, O2···O3, O3···O4 and O1···O4 distances are 3.157 (7), 2.935 (7), 3.129 (7) and 3.576 (7) Å. A similar geometry is encountered in the uranyl complex of p-tert-butyldihomooxacalix[4]arene, in which, however, the included pyridine molecule is replaced by a triethylammonium counter-ion (Harrowfield et al., 1991).

The lithium ion is surrounded by two water and two pyridine molecules, with mean Li—O and Li—N bond lengths of 1.910 (6) and 2.08 (2) Å, respectively. The angles around Li are in the range 98.6 (7)–113.9 (8)° and the coordination geometry is that of a slightly distorted tetrahedron. The two metal complexes are linked by hydrogen bonds between water atom O7 and phenoxide atom O1, and also between atom O8 and phenoxide atom O3 of a neighbouring molecule at (1 − x, y + 1/2, 1/2 − z). The two water molecules bound to the Li atom are also hydrogen bonded to two pyridine molecules, and the solvent water molecule (containing atom O9) is hydrogen bonded to atom O8 and to a phenoxide O atom of the same neighbouring molecule at (1 − x, y + 1/2, 1/2 − z). Polymeric zigzag chains along the b axis are thus formed, in which successive macrocycles are turned upside down with respect to one another.

The only feeble, but significant, π–π-stacking interaction in (I) is between the two solvent pyridine rings containing atoms N5 and N6 [centroid–centroid distance = 3.800 Å, interplanar spacing = 3.436 Å, centroid offset = 1.622 Å, shortest interatomic contact = N6···C66 = 3.41 (1) Å and dihedral angle between the two rings = 9.6 (5)°].

We have recently reported the synthesis and crystal structure of complexes uniting uranyl and alkali metal ions in the 1:2 ratio with p-tert-butyltetrahomodioxacalix[4]arene (Thuéry & Masci, 2003). This work has evidenced different arrangements depending on the alkali ion, viz. monomeric with Li⁺, dimeric with Na⁺, and polymeric with K⁺ and Cs⁺. The uranyl/lithium stoichiometry in (I) is obviously different because of the cationic nature of the ligand, but the monomeric nature of the complex is once more encountered (considering coordination bonds only, and not hydrogen-bonding interactions). However, the uranyl/alkali metal interactions differ from those found previously. In the series of homooxacalixarene complexes, the presence of U═O—M bonds (M = Li⁺, Na⁺, K⁺ and Cs⁺) is a general trend, whereas the interactions between the two moieties in (I) are indirect and are mediated through hydrogen-bonded lithium-coordinated water molecules and phenoxide groups. The U═O bond lengths in (I) are larger than usual for non-oxo-coordinated ions [mean value 1.76 (4) Å for the structures contained in the CSD] and are comparable to those in the uranyl ions bound to alkali metal ions [1.797 (6)–1.813 (6) = Å].

S2. Experimental

N-methyl-p-tert-butyldihomoammoniocalix[4]arene LH₄ was prepared as reported previously (Takemura, 2002). For the synthesis of complex (I), LH₄ (22 mg, 0.032 mmol) was dissolved in CHCl₃/CH₃OH (2:1, 100 ml) in the presence of a large excess of LiOH·H₂O (15 mg, 0.357 mmol). UO₂(NO₃)₂·6H₂O (20 mg, 0.040 mmol) in pyridine (10 ml) was then added and the resulting orange solution was refluxed for 15 min. Crystals of (I) were obtained from slow evaporation of the solution.

S3. Refinement

The ammonium and hydroxy H atoms were found in difference Fourier maps and were introduced as riding atoms, with isotropic displacement parameters equal to 1.2U_eq of the parent atom. All other H atoms were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH), 0.97 (CH₂) and 0.96 (CH₃) Å and an isotropic displacement parameter equal to 1.2U_eq (CH, CH₂) or 1.5U_eq (CH₃) of the parent atom. After refinement of the pyridine molecule with six C atoms, the N atom was assigned to the position with the lowest displacement factor. However, atom N2 exhibits a high displacement parameter with respect to those of its neighbours, which may indicate some rotational disorder of this pyridine molecule. The minimum and maximum residual electron-density peaks of −1.03 and 0.82 e Å⁻³ are located 0.97 Å from U and 1.16 Å from the solvent pyridine atom C66, respectively, which may indicate an imperfect absorption correction in the first case and some unresolved disorder in the second.

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 PLATON (Spek, 2003).

Figures

Fig. 1. View of complex (I). Ammonium and water H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are shown as dashed lines. The other H atoms have been omitted. Displacement ellipsoids are drawn at the 10% probability level. [Symmetry code: (') 1 − x, y + 1/2, 1/2 − z.]

(I)

Crystal data

[Li(C5H5N)2(H2O)2][UO2(C46H58NO4)]·3C5H5N·H2O	F(000) = 2896
Mr = 1415.45	Dx = 1.384 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 45959 reflections
a = 20.8644 (16) Å	θ = 2.7–25.7°
b = 16.6147 (13) Å	µ = 2.45 mm^−1
c = 19.7150 (14) Å	T = 100 K
β = 96.321 (5)°	Platelet, translucent dark orange
V = 6792.8 (9) Å^3	0.38 × 0.12 × 0.05 mm
Z = 4

Data collection

Nonius Kappa-CCD diffractometer	12756 independent reflections
Radiation source: fine-focus sealed tube	7934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.096
ϕ scans	θmax = 25.7°, θmin = 2.7°
Absorption correction: part of the refinement model (ΔF) (DELABS in PLATON; Spek, 2003)	h = −25→25
Tmin = 0.698, Tmax = 0.872	k = −20→20
45959 measured reflections	l = −23→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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0088P)^2 + 25.0468P] where P = (Fo^2 + 2Fc^2)/3
12756 reflections	(Δ/σ)max = 0.001
806 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −1.03 e Å^−3

Special details

Experimental. crystal-to-detector distance 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 N and O were found on a Fourier-difference map and all the other ones were introduced at calculated positions. All H atoms were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (NH, OH, CH, CH₂) or 1.5 (CH₃) 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
U	0.651574 (16)	0.672095 (17)	0.227819 (15)	0.02890 (9)
Li	0.5262 (7)	0.9841 (8)	0.1833 (7)	0.042 (3)
N1	0.7243 (3)	0.7300 (3)	0.0658 (3)	0.0298 (15)
H1	0.7237	0.7100	0.1091	0.036*
O1	0.6621 (3)	0.8024 (3)	0.1911 (3)	0.0307 (13)
O2	0.6799 (3)	0.7173 (3)	0.3352 (2)	0.0291 (12)
O3	0.6563 (2)	0.5535 (3)	0.2825 (2)	0.0291 (12)
O4	0.6322 (3)	0.6023 (3)	0.1286 (3)	0.0320 (13)
O5	0.5673 (3)	0.6836 (3)	0.2387 (3)	0.0356 (13)
O6	0.7346 (2)	0.6636 (3)	0.2126 (2)	0.0325 (12)
C1	0.7352 (4)	0.8637 (4)	0.1205 (4)	0.0290 (18)
C2	0.7140 (4)	0.8492 (4)	0.1853 (4)	0.0301 (19)
C3	0.7480 (4)	0.8865 (4)	0.2424 (4)	0.0272 (17)
C4	0.7985 (4)	0.9382 (4)	0.2325 (4)	0.0333 (19)
H4	0.8193	0.9643	0.2705	0.040*
C5	0.8202 (4)	0.9534 (4)	0.1685 (4)	0.0337 (19)
C6	0.7865 (4)	0.9135 (4)	0.1126 (4)	0.034 (2)
H6	0.7992	0.9209	0.0693	0.041*
C7	0.8775 (4)	1.0092 (5)	0.1628 (4)	0.039 (2)
C8	0.9379 (4)	0.9742 (5)	0.2049 (5)	0.049 (2)
H8C	0.9296	0.9680	0.2516	0.074*
H8D	0.9736	1.0101	0.2027	0.074*
H8E	0.9480	0.9227	0.1867	0.074*
C9	0.8935 (5)	1.0153 (6)	0.0891 (4)	0.052 (2)
H9C	0.9068	0.9635	0.0741	0.079*
H9D	0.9278	1.0533	0.0866	0.079*
H9E	0.8560	1.0328	0.0602	0.079*
C10	0.8648 (5)	1.0930 (5)	0.1906 (5)	0.051 (3)
H10A	0.8302	1.1181	0.1620	0.076*
H10B	0.9031	1.1252	0.1910	0.076*
H10C	0.8532	1.0883	0.2362	0.076*
C11	0.7330 (4)	0.8702 (4)	0.3140 (4)	0.0281 (18)
H11A	0.6875	0.8577	0.3129	0.034*
H11B	0.7412	0.9187	0.3409	0.034*
C12	0.7720 (4)	0.8016 (4)	0.3490 (4)	0.0282 (18)
C13	0.7427 (4)	0.7268 (5)	0.3575 (4)	0.0306 (19)
C14	0.7806 (4)	0.6626 (4)	0.3882 (3)	0.0276 (17)
C15	0.8449 (4)	0.6773 (5)	0.4094 (3)	0.0327 (18)
H15	0.8690	0.6357	0.4311	0.039*
C16	0.8762 (4)	0.7502 (4)	0.4006 (4)	0.0324 (19)
C17	0.8378 (4)	0.8110 (4)	0.3706 (4)	0.0313 (19)
H17	0.8567	0.8608	0.3644	0.038*
C18	0.9475 (4)	0.7630 (5)	0.4269 (4)	0.036 (2)
C19	0.9532 (5)	0.7732 (6)	0.5048 (4)	0.054 (3)
H19A	0.9975	0.7818	0.5220	0.081*
H19B	0.9376	0.7256	0.5251	0.081*
H19C	0.9279	0.8187	0.5160	0.081*
C20	0.9884 (4)	0.6906 (5)	0.4092 (5)	0.057 (3)
H20A	0.9825	0.6816	0.3609	0.086*
H20B	0.9753	0.6436	0.4324	0.086*
H20C	1.0331	0.7014	0.4234	0.086*
C21	0.9748 (4)	0.8381 (6)	0.3975 (5)	0.052 (2)
H21A	0.9678	0.8359	0.3486	0.078*
H21B	1.0202	0.8414	0.4119	0.078*
H21C	0.9536	0.8847	0.4133	0.078*
C22	0.7503 (4)	0.5804 (4)	0.3995 (4)	0.0317 (19)
H22A	0.7697	0.5593	0.4429	0.038*
H22B	0.7048	0.5883	0.4033	0.038*
C23	0.7568 (4)	0.5179 (4)	0.3458 (4)	0.0312 (19)
C24	0.7108 (4)	0.5076 (4)	0.2906 (4)	0.0309 (18)
C25	0.7185 (4)	0.4473 (4)	0.2410 (4)	0.0300 (19)
C26	0.7720 (4)	0.3978 (4)	0.2513 (4)	0.0306 (19)
H26	0.7765	0.3571	0.2198	0.037*
C27	0.8197 (4)	0.4055 (4)	0.3063 (4)	0.0305 (18)
C28	0.8096 (4)	0.4675 (4)	0.3527 (4)	0.034 (2)
H28	0.8402	0.4747	0.3902	0.041*
C29	0.8770 (4)	0.3471 (4)	0.3152 (4)	0.0312 (19)
C30	0.9260 (5)	0.3683 (5)	0.3768 (4)	0.049 (2)
H30A	0.9405	0.4227	0.3724	0.073*
H30B	0.9621	0.3324	0.3783	0.073*
H30C	0.9058	0.3632	0.4181	0.073*
C31	0.9126 (4)	0.3478 (5)	0.2515 (4)	0.046 (2)
H31A	0.8836	0.3320	0.2126	0.069*
H31B	0.9482	0.3108	0.2575	0.069*
H31C	0.9285	0.4011	0.2445	0.069*
C32	0.8512 (4)	0.2622 (4)	0.3252 (5)	0.048 (2)
H32A	0.8658	0.2268	0.2917	0.071*
H32B	0.8047	0.2634	0.3199	0.071*
H32C	0.8662	0.2433	0.3700	0.071*
C33	0.6687 (4)	0.4398 (4)	0.1785 (4)	0.0313 (19)
H33A	0.6289	0.4655	0.1880	0.038*
H33B	0.6597	0.3833	0.1694	0.038*
C34	0.6923 (4)	0.4788 (4)	0.1150 (4)	0.0309 (18)
C35	0.6714 (4)	0.5581 (4)	0.0950 (4)	0.0296 (18)
C36	0.6956 (4)	0.5905 (4)	0.0366 (4)	0.033 (2)
C37	0.7373 (4)	0.5462 (4)	0.0018 (4)	0.035 (2)
H37	0.7517	0.5687	−0.0370	0.042*
C38	0.7591 (4)	0.4692 (4)	0.0218 (4)	0.0314 (19)
C39	0.7347 (4)	0.4368 (4)	0.0785 (4)	0.0320 (19)
H39	0.7472	0.3852	0.0925	0.038*
C40	0.8077 (4)	0.4243 (5)	−0.0176 (4)	0.038 (2)
C41	0.8670 (5)	0.4772 (5)	−0.0244 (5)	0.059 (3)
H41A	0.8546	0.5229	−0.0526	0.089*
H41B	0.8989	0.4465	−0.0448	0.089*
H41C	0.8848	0.4953	0.0200	0.089*
C42	0.7754 (5)	0.4053 (5)	−0.0894 (4)	0.054 (3)
H42A	0.7414	0.3670	−0.0864	0.081*
H42B	0.8068	0.3831	−0.1163	0.081*
H42C	0.7579	0.4538	−0.1104	0.081*
C43	0.8308 (4)	0.3454 (5)	0.0174 (4)	0.044 (2)
H43A	0.8542	0.3571	0.0609	0.066*
H43B	0.8585	0.3175	−0.0106	0.066*
H43C	0.7943	0.3123	0.0237	0.066*
C44	0.6810 (4)	0.6752 (4)	0.0183 (3)	0.0321 (18)
H44A	0.6361	0.6867	0.0227	0.038*
H44B	0.6885	0.6849	−0.0287	0.038*
C45	0.7025 (4)	0.8173 (4)	0.0610 (4)	0.0314 (18)
H45A	0.7134	0.8406	0.0187	0.038*
H45B	0.6561	0.8202	0.0613	0.038*
C46	0.7948 (4)	0.7223 (4)	0.0568 (4)	0.037 (2)
H46A	0.8011	0.7336	0.0102	0.055*
H46B	0.8091	0.6686	0.0681	0.055*
H46C	0.8192	0.7599	0.0862	0.055*
O7	0.5620 (3)	0.9007 (3)	0.1323 (3)	0.0415 (15)
H7A	0.5906	0.8682	0.1560	0.050*
H7B	0.5381	0.8645	0.1053	0.050*
O8	0.4437 (3)	1.0196 (3)	0.1433 (3)	0.0402 (14)
H8A	0.4249	0.9821	0.1104	0.048*
H8B	0.4070	1.0335	0.1615	0.048*
O9	0.4084 (3)	1.1714 (4)	0.0743 (3)	0.0512 (15)
H9A	0.4316	1.1325	0.0935	0.061*
H9B	0.3751	1.1769	0.0984	0.061*
N2	0.8809 (5)	0.6649 (6)	0.2273 (4)	0.078 (3)
C47	0.8727 (5)	0.5856 (6)	0.2050 (5)	0.049 (2)
H47	0.8377	0.5549	0.2152	0.058*
C48	0.9187 (6)	0.5547 (7)	0.1673 (5)	0.070 (3)
H48	0.9151	0.5023	0.1507	0.083*
C49	0.9708 (6)	0.6027 (9)	0.1542 (5)	0.072 (4)
H49	1.0016	0.5805	0.1291	0.087*
C50	0.9788 (4)	0.6756 (8)	0.1745 (5)	0.055 (3)
H50	1.0142	0.7055	0.1645	0.066*
C51	0.9357 (6)	0.7062 (7)	0.2097 (6)	0.066 (3)
H51	0.9415	0.7592	0.2244	0.079*
N3	0.5238 (3)	0.9488 (4)	0.2834 (3)	0.0379 (17)
C52	0.5436 (5)	0.8765 (5)	0.3084 (5)	0.044 (2)
H52	0.5571	0.8387	0.2782	0.053*
C53	0.5449 (5)	0.8555 (5)	0.3754 (5)	0.053 (3)
H53	0.5588	0.8045	0.3900	0.063*
C54	0.5256 (5)	0.9102 (5)	0.4207 (4)	0.049 (2)
H54	0.5262	0.8973	0.4667	0.058*
C55	0.5052 (5)	0.9850 (6)	0.3970 (5)	0.051 (3)
H55	0.4916	1.0236	0.4264	0.062*
C56	0.5055 (5)	1.0008 (5)	0.3286 (5)	0.046 (2)
H56	0.4919	1.0515	0.3129	0.055*
N4	0.5858 (4)	1.0847 (4)	0.2006 (4)	0.0435 (19)
C57	0.6470 (5)	1.0749 (5)	0.2272 (5)	0.049 (2)
H57	0.6629	1.0227	0.2319	0.059*
C58	0.6877 (5)	1.1369 (6)	0.2478 (4)	0.044 (2)
H58	0.7303	1.1270	0.2647	0.053*
C59	0.6636 (5)	1.2149 (5)	0.2430 (5)	0.049 (3)
H59	0.6897	1.2584	0.2573	0.059*
C60	0.6003 (5)	1.2266 (5)	0.2164 (5)	0.049 (2)
H60	0.5827	1.2781	0.2131	0.059*
C61	0.5638 (4)	1.1606 (5)	0.1950 (4)	0.040 (2)
H61	0.5216	1.1689	0.1757	0.048*
N5	0.4803 (4)	0.7864 (5)	0.0644 (4)	0.050 (2)
C62	0.4587 (5)	0.7354 (6)	0.1109 (5)	0.054 (3)
H62	0.4739	0.7426	0.1566	0.065*
C63	0.4161 (5)	0.6742 (6)	0.0945 (5)	0.066 (3)
H63	0.4035	0.6400	0.1279	0.079*
C64	0.3922 (5)	0.6648 (7)	0.0264 (6)	0.067 (3)
H64	0.3634	0.6237	0.0127	0.081*
C65	0.4126 (5)	0.7180 (7)	−0.0199 (5)	0.063 (3)
H65	0.3971	0.7139	−0.0658	0.075*
C66	0.4564 (5)	0.7781 (6)	0.0019 (5)	0.056 (3)
H66	0.4689	0.8141	−0.0302	0.067*
N6	0.3667 (4)	0.9377 (4)	0.0455 (4)	0.052 (2)
C67	0.3322 (5)	0.8818 (6)	0.0741 (5)	0.054 (3)
H67	0.3421	0.8708	0.1204	0.065*
C68	0.2824 (5)	0.8398 (6)	0.0381 (5)	0.052 (2)
H68	0.2603	0.8004	0.0597	0.062*
C69	0.2660 (6)	0.8565 (6)	−0.0287 (6)	0.071 (3)
H69	0.2318	0.8298	−0.0535	0.085*
C70	0.3009 (6)	0.9135 (6)	−0.0592 (5)	0.061 (3)
H70	0.2912	0.9257	−0.1053	0.074*
C71	0.3501 (5)	0.9522 (6)	−0.0207 (5)	0.055 (3)
H71	0.3734	0.9908	−0.0418	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U	0.03129 (16)	0.02766 (14)	0.02778 (14)	−0.00008 (17)	0.00346 (10)	0.00015 (16)
Li	0.035 (9)	0.039 (7)	0.051 (9)	0.004 (6)	0.005 (7)	0.010 (7)
N1	0.040 (5)	0.023 (3)	0.027 (3)	0.000 (3)	0.007 (3)	−0.001 (3)
O1	0.032 (3)	0.028 (3)	0.033 (3)	−0.001 (2)	0.005 (2)	0.000 (2)
O2	0.027 (3)	0.031 (3)	0.029 (3)	0.000 (2)	0.003 (2)	−0.002 (2)
O3	0.027 (3)	0.032 (3)	0.028 (3)	0.000 (2)	0.002 (2)	0.006 (2)
O4	0.033 (3)	0.027 (3)	0.035 (3)	0.000 (2)	−0.001 (3)	0.004 (2)
O5	0.033 (3)	0.034 (3)	0.040 (3)	−0.002 (3)	0.006 (3)	−0.006 (3)
O6	0.027 (3)	0.033 (3)	0.037 (3)	0.000 (3)	0.002 (2)	0.000 (3)
C1	0.033 (5)	0.026 (4)	0.029 (4)	0.004 (4)	0.003 (4)	0.002 (3)
C2	0.031 (5)	0.029 (4)	0.030 (4)	0.004 (3)	0.003 (4)	0.004 (3)
C3	0.028 (5)	0.025 (4)	0.029 (4)	0.000 (3)	0.002 (3)	0.001 (3)
C4	0.035 (5)	0.032 (4)	0.033 (4)	0.006 (4)	0.002 (4)	−0.003 (4)
C5	0.037 (5)	0.024 (4)	0.040 (5)	−0.003 (4)	0.005 (4)	0.004 (4)
C6	0.048 (6)	0.027 (4)	0.028 (4)	−0.003 (4)	0.003 (4)	0.002 (3)
C7	0.039 (6)	0.035 (4)	0.044 (5)	−0.006 (4)	0.011 (4)	−0.002 (4)
C8	0.034 (6)	0.055 (6)	0.059 (6)	−0.003 (4)	0.006 (5)	0.008 (5)
C9	0.045 (6)	0.057 (6)	0.057 (6)	−0.014 (5)	0.015 (5)	−0.001 (5)
C10	0.053 (7)	0.045 (5)	0.054 (6)	−0.023 (5)	0.009 (5)	0.001 (5)
C11	0.026 (5)	0.028 (4)	0.031 (4)	0.000 (3)	0.007 (4)	−0.004 (3)
C12	0.035 (5)	0.030 (4)	0.021 (4)	0.001 (3)	0.008 (3)	−0.004 (3)
C13	0.030 (5)	0.037 (4)	0.026 (4)	0.002 (4)	0.007 (4)	−0.012 (4)
C14	0.029 (5)	0.028 (4)	0.025 (4)	0.001 (4)	−0.001 (3)	−0.003 (3)
C15	0.048 (5)	0.026 (4)	0.023 (4)	0.013 (4)	0.001 (3)	−0.001 (4)
C16	0.040 (5)	0.034 (4)	0.024 (4)	0.003 (4)	0.002 (4)	−0.003 (3)
C17	0.035 (5)	0.028 (4)	0.032 (4)	−0.001 (3)	0.010 (4)	0.004 (3)
C18	0.034 (5)	0.033 (4)	0.039 (5)	0.001 (4)	−0.002 (4)	−0.005 (4)
C19	0.046 (7)	0.080 (7)	0.034 (5)	0.004 (5)	−0.005 (4)	−0.005 (5)
C20	0.030 (6)	0.063 (7)	0.079 (7)	0.002 (5)	0.006 (5)	−0.014 (5)
C21	0.036 (6)	0.064 (6)	0.055 (6)	0.001 (5)	−0.006 (4)	0.003 (5)
C22	0.036 (5)	0.032 (4)	0.027 (4)	0.000 (4)	0.005 (4)	0.003 (4)
C23	0.044 (6)	0.023 (4)	0.026 (4)	0.004 (4)	0.001 (4)	0.003 (3)
C24	0.035 (5)	0.028 (4)	0.029 (4)	−0.002 (4)	0.001 (4)	0.007 (4)
C25	0.039 (5)	0.021 (4)	0.031 (4)	−0.001 (4)	0.008 (4)	0.002 (3)
C26	0.040 (6)	0.021 (4)	0.033 (4)	−0.007 (4)	0.011 (4)	0.002 (3)
C27	0.030 (5)	0.030 (4)	0.032 (4)	−0.002 (4)	0.006 (4)	0.005 (4)
C28	0.045 (6)	0.030 (4)	0.028 (4)	−0.003 (4)	0.005 (4)	0.009 (4)
C29	0.033 (5)	0.026 (4)	0.035 (4)	0.007 (3)	0.005 (4)	0.008 (3)
C30	0.046 (6)	0.055 (5)	0.044 (5)	0.016 (5)	−0.005 (5)	0.004 (5)
C31	0.042 (6)	0.053 (6)	0.043 (5)	0.013 (4)	0.006 (4)	0.003 (4)
C32	0.054 (7)	0.027 (4)	0.063 (6)	0.006 (4)	0.012 (5)	0.009 (4)
C33	0.040 (5)	0.028 (4)	0.026 (4)	−0.007 (4)	0.001 (4)	0.002 (3)
C34	0.029 (5)	0.028 (4)	0.034 (4)	−0.003 (3)	−0.005 (4)	−0.002 (4)
C35	0.029 (5)	0.035 (4)	0.024 (4)	0.001 (4)	−0.003 (3)	−0.004 (4)
C36	0.038 (6)	0.031 (4)	0.029 (4)	−0.003 (4)	−0.003 (4)	−0.008 (4)
C37	0.050 (6)	0.036 (4)	0.019 (4)	−0.003 (4)	0.008 (4)	−0.002 (4)
C38	0.038 (5)	0.027 (4)	0.028 (4)	−0.006 (4)	0.001 (4)	−0.004 (3)
C39	0.035 (5)	0.029 (4)	0.031 (4)	0.004 (4)	0.004 (4)	−0.002 (4)
C40	0.045 (6)	0.038 (5)	0.030 (4)	0.000 (4)	0.005 (4)	−0.003 (4)
C41	0.064 (8)	0.045 (5)	0.073 (7)	0.002 (5)	0.029 (6)	0.001 (5)
C42	0.077 (8)	0.045 (5)	0.039 (5)	0.012 (5)	0.003 (5)	−0.005 (4)
C43	0.040 (6)	0.050 (6)	0.042 (5)	0.005 (4)	0.003 (4)	0.000 (4)
C44	0.044 (5)	0.030 (4)	0.020 (3)	−0.006 (4)	−0.002 (3)	−0.007 (4)
C45	0.041 (5)	0.028 (4)	0.025 (4)	0.000 (4)	0.003 (3)	0.004 (4)
C46	0.035 (5)	0.044 (5)	0.034 (4)	0.006 (4)	0.013 (4)	−0.001 (4)
O7	0.043 (4)	0.038 (3)	0.041 (3)	0.004 (3)	−0.004 (3)	−0.001 (3)
O8	0.029 (4)	0.048 (3)	0.044 (3)	0.007 (3)	0.005 (3)	−0.006 (3)
O9	0.048 (4)	0.056 (3)	0.049 (3)	−0.001 (4)	0.005 (3)	−0.001 (3)
N2	0.078 (7)	0.098 (7)	0.056 (5)	−0.020 (6)	−0.007 (5)	0.011 (6)
C47	0.048 (7)	0.047 (5)	0.050 (6)	−0.001 (5)	0.002 (5)	0.008 (5)
C48	0.096 (10)	0.065 (7)	0.049 (6)	0.028 (7)	0.016 (7)	0.019 (6)
C49	0.055 (8)	0.124 (11)	0.043 (6)	0.028 (8)	0.026 (6)	0.031 (7)
C50	0.031 (6)	0.088 (8)	0.046 (6)	−0.025 (6)	0.005 (4)	0.007 (6)
C51	0.063 (9)	0.070 (7)	0.060 (7)	−0.035 (6)	−0.010 (6)	0.008 (6)
N3	0.032 (4)	0.037 (4)	0.043 (4)	−0.002 (3)	0.001 (3)	−0.001 (3)
C52	0.051 (6)	0.033 (5)	0.048 (6)	0.001 (4)	0.004 (5)	0.001 (4)
C53	0.053 (7)	0.044 (5)	0.061 (6)	−0.002 (5)	0.004 (5)	−0.003 (5)
C54	0.060 (7)	0.050 (5)	0.035 (5)	0.003 (5)	0.000 (5)	0.008 (4)
C55	0.059 (7)	0.056 (6)	0.039 (5)	0.002 (5)	0.003 (5)	−0.003 (5)
C56	0.051 (6)	0.028 (4)	0.056 (6)	0.007 (4)	−0.003 (5)	−0.004 (4)
N4	0.049 (5)	0.035 (4)	0.047 (4)	0.000 (4)	0.008 (4)	−0.003 (3)
C57	0.038 (6)	0.048 (5)	0.062 (6)	0.008 (5)	0.005 (5)	0.006 (5)
C58	0.032 (6)	0.058 (6)	0.043 (5)	−0.001 (5)	0.001 (4)	0.008 (5)
C59	0.062 (8)	0.037 (5)	0.049 (6)	−0.016 (5)	0.003 (5)	0.004 (4)
C60	0.057 (7)	0.035 (5)	0.056 (6)	−0.002 (5)	0.006 (5)	0.011 (4)
C61	0.037 (5)	0.042 (5)	0.043 (5)	0.003 (4)	0.010 (4)	0.008 (4)
N5	0.041 (5)	0.059 (5)	0.051 (5)	0.003 (4)	0.005 (4)	−0.012 (4)
C62	0.054 (7)	0.064 (6)	0.044 (6)	0.005 (5)	0.002 (5)	−0.003 (5)
C63	0.074 (8)	0.058 (6)	0.063 (7)	−0.009 (7)	−0.003 (6)	0.001 (6)
C64	0.055 (7)	0.071 (7)	0.076 (7)	−0.004 (6)	0.009 (6)	−0.020 (7)
C65	0.057 (8)	0.090 (8)	0.040 (5)	−0.001 (6)	0.005 (5)	−0.024 (6)
C66	0.033 (6)	0.090 (8)	0.044 (6)	−0.007 (5)	0.001 (5)	0.009 (5)
N6	0.055 (6)	0.051 (5)	0.050 (5)	0.010 (4)	0.006 (4)	−0.008 (4)
C67	0.067 (8)	0.053 (6)	0.043 (5)	0.011 (5)	0.008 (5)	−0.007 (5)
C68	0.046 (6)	0.056 (6)	0.054 (6)	0.006 (5)	0.009 (5)	0.011 (5)
C69	0.083 (9)	0.054 (6)	0.071 (8)	−0.009 (6)	−0.017 (7)	0.010 (6)
C70	0.076 (9)	0.053 (6)	0.052 (6)	−0.005 (6)	−0.009 (6)	0.001 (5)
C71	0.062 (8)	0.055 (6)	0.049 (6)	0.011 (5)	0.013 (5)	−0.003 (5)

Geometric parameters (Å, º)

U—O1	2.301 (5)	C32—H32B	0.9600
U—O2	2.262 (5)	C32—H32C	0.9600
U—O3	2.243 (5)	C33—C34	1.538 (10)
U—O4	2.272 (5)	C33—H33A	0.9700
U—O5	1.805 (5)	C33—H33B	0.9700
U—O6	1.796 (5)	C34—C39	1.388 (11)
U—N1	3.808 (6)	C34—C35	1.430 (10)
Li—O7	1.914 (15)	C35—C36	1.414 (11)
Li—O8	1.906 (15)	C36—C37	1.379 (11)
Li—N3	2.064 (16)	C36—C44	1.477 (10)
Li—N4	2.089 (16)	C37—C38	1.400 (10)
N1—C46	1.507 (10)	C37—H37	0.9300
N1—C45	1.519 (9)	C38—C39	1.387 (10)
N1—C44	1.528 (9)	C38—C40	1.537 (11)
N1—O1	3.153 (8)	C39—H39	0.9300
N1—O4	3.202 (8)	C40—C42	1.532 (11)
N1—H1	0.9177	C40—C43	1.534 (11)
O1—C2	1.349 (9)	C40—C41	1.537 (12)
O1—O2	3.157 (7)	C41—H41A	0.9600
O1—O4	3.576 (7)	C41—H41B	0.9600
O2—C13	1.347 (9)	C41—H41C	0.9600
O2—O3	2.935 (7)	C42—H42A	0.9600
O3—C24	1.364 (9)	C42—H42B	0.9600
O3—O4	3.129 (7)	C42—H42C	0.9600
O4—C35	1.329 (9)	C43—H43A	0.9600
C1—C6	1.375 (11)	C43—H43B	0.9600
C1—C2	1.418 (10)	C43—H43C	0.9600
C1—C45	1.503 (10)	C44—H44A	0.9700
C2—C3	1.405 (10)	C44—H44B	0.9700
C3—C4	1.390 (11)	C45—H45A	0.9700
C3—C11	1.504 (10)	C45—H45B	0.9700
C4—C5	1.410 (11)	C46—H46A	0.9600
C4—H4	0.9300	C46—H46B	0.9600
C5—C6	1.406 (11)	C46—H46C	0.9600
C5—C7	1.528 (11)	O7—H7A	0.8974
C6—H6	0.9300	O7—H7B	0.9138
C7—C10	1.530 (11)	O8—H8A	0.9525
C7—C9	1.530 (11)	O8—H8B	0.9108
C7—C8	1.544 (12)	O9—H9A	0.8688
C8—H8C	0.9600	O9—H9B	0.8897
C8—H8D	0.9600	N2—C47	1.394 (12)
C8—H8E	0.9600	N2—C51	1.410 (14)
C9—H9C	0.9600	C47—C48	1.376 (14)
C9—H9D	0.9600	C47—H47	0.9300
C9—H9E	0.9600	C48—C49	1.396 (16)
C10—H10A	0.9600	C48—H48	0.9300
C10—H10B	0.9600	C49—C50	1.281 (15)
C10—H10C	0.9600	C49—H49	0.9300
C11—C12	1.521 (10)	C50—C51	1.297 (14)
C11—H11A	0.9700	C50—H50	0.9300
C11—H11B	0.9700	C51—H51	0.9300
C12—C17	1.402 (11)	N3—C56	1.327 (10)
C12—C13	1.402 (10)	N3—C52	1.346 (10)
C13—C14	1.422 (10)	C52—C53	1.363 (12)
C14—C15	1.382 (11)	C52—H52	0.9300
C14—C22	1.532 (10)	C53—C54	1.366 (12)
C15—C16	1.396 (11)	C53—H53	0.9300
C15—H15	0.9300	C54—C55	1.379 (12)
C16—C17	1.381 (10)	C54—H54	0.9300
C16—C18	1.536 (11)	C55—C56	1.374 (12)
C17—H17	0.9300	C55—H55	0.9300
C18—C21	1.513 (11)	C56—H56	0.9300
C18—C20	1.537 (11)	N4—C57	1.335 (12)
C18—C19	1.536 (11)	N4—C61	1.342 (10)
C19—H19A	0.9600	C57—C58	1.367 (12)
C19—H19B	0.9600	C57—H57	0.9300
C19—H19C	0.9600	C58—C59	1.390 (12)
C20—H20A	0.9600	C58—H58	0.9300
C20—H20B	0.9600	C59—C60	1.380 (13)
C20—H20C	0.9600	C59—H59	0.9300
C21—H21A	0.9600	C60—C61	1.375 (11)
C21—H21B	0.9600	C60—H60	0.9300
C21—H21C	0.9600	C61—H61	0.9300
C22—C23	1.501 (10)	N5—C66	1.285 (11)
C22—H22A	0.9700	N5—C62	1.361 (11)
C22—H22B	0.9700	C62—C63	1.365 (13)
C23—C24	1.380 (10)	C62—H62	0.9300
C23—C28	1.378 (11)	C63—C64	1.388 (14)
C24—C25	1.422 (10)	C63—H63	0.9300
C25—C26	1.384 (11)	C64—C65	1.372 (14)
C25—C33	1.526 (10)	C64—H64	0.9300
C26—C27	1.395 (11)	C65—C66	1.389 (13)
C26—H26	0.9300	C65—H65	0.9300
C27—C28	1.408 (10)	C66—H66	0.9300
C27—C29	1.535 (10)	N6—C71	1.334 (11)
C28—H28	0.9300	N6—C67	1.338 (12)
C29—C32	1.530 (10)	C67—C68	1.381 (13)
C29—C31	1.528 (11)	C67—H67	0.9300
C29—C30	1.539 (11)	C68—C69	1.354 (13)
C30—H30A	0.9600	C68—H68	0.9300
C30—H30B	0.9600	C69—C70	1.374 (14)
C30—H30C	0.9600	C69—H69	0.9300
C31—H31A	0.9600	C70—C71	1.369 (13)
C31—H31B	0.9600	C70—H70	0.9300
C31—H31C	0.9600	C71—H71	0.9300
C32—H32A	0.9600
O1—U—O2	87.56 (17)	H31A—C31—H31B	109.5
O2—U—O3	81.30 (17)	C29—C31—H31C	109.5
O3—U—O4	87.73 (17)	H31A—C31—H31C	109.5
O4—U—O1	102.91 (17)	H31B—C31—H31C	109.5
O1—U—N1	55.79 (15)	C29—C32—H32A	109.3
O4—U—N1	57.05 (15)	C29—C32—H32B	109.9
O5—U—O6	176.8 (2)	H32A—C32—H32B	109.4
O6—U—O3	91.1 (2)	C29—C32—H32C	109.3
O5—U—O3	91.6 (2)	H32A—C32—H32C	109.4
O6—U—O2	91.5 (2)	H32B—C32—H32C	109.5
O5—U—O2	90.6 (2)	C25—C33—C34	111.8 (6)
O6—U—O4	84.2 (2)	C25—C33—H33A	109.2
O5—U—O4	94.2 (2)	C34—C33—H33A	109.2
O2—U—O4	168.15 (17)	C25—C33—H33B	109.2
O6—U—O1	84.0 (2)	C34—C33—H33B	109.2
O5—U—O1	93.7 (2)	H33A—C33—H33B	107.9
O3—U—O1	167.69 (18)	C39—C34—C35	120.9 (7)
O6—U—N1	53.05 (18)	C39—C34—C33	119.3 (7)
O5—U—N1	123.79 (19)	C35—C34—C33	119.8 (7)
O3—U—N1	128.68 (15)	O4—C35—C36	119.3 (7)
O2—U—N1	127.88 (16)	O4—C35—C34	124.0 (7)
O7—Li—O8	113.2 (8)	C36—C35—C34	116.7 (7)
O7—Li—N3	110.4 (7)	C37—C36—C35	120.3 (7)
O7—Li—N4	113.9 (8)	C37—C36—C44	120.7 (7)
O8—Li—N3	111.6 (8)	C35—C36—C44	118.6 (7)
O8—Li—N4	108.4 (7)	C36—C37—C38	123.3 (7)
N3—Li—N4	98.6 (7)	C36—C37—H37	118.3
C46—N1—C45	111.3 (5)	C38—C37—H37	118.3
C46—N1—C44	113.3 (5)	C39—C38—C37	116.5 (7)
C45—N1—C44	112.3 (6)	C39—C38—C40	122.7 (7)
C46—N1—U	124.2 (4)	C37—C38—C40	120.8 (7)
C45—N1—U	98.6 (4)	C38—C39—C34	122.3 (7)
C44—N1—U	95.7 (4)	C38—C39—H39	118.9
C46—N1—H1	101.0	C34—C39—H39	118.9
C45—N1—H1	111.6	C42—C40—C43	108.9 (7)
C44—N1—H1	106.7	C42—C40—C41	108.3 (7)
C2—O1—U	132.4 (4)	C43—C40—C41	108.1 (8)
C13—O2—U	119.3 (4)	C42—C40—C38	108.7 (7)
C35—O4—U	130.5 (5)	C43—C40—C38	112.3 (6)
C6—C1—C2	121.9 (7)	C41—C40—C38	110.4 (7)
C6—C1—C45	120.8 (7)	C40—C41—H41A	109.5
C2—C1—C45	117.1 (7)	C40—C41—H41B	109.5
O1—C2—C3	121.7 (7)	H41A—C41—H41B	109.5
O1—C2—C1	120.5 (7)	C40—C41—H41C	109.5
C3—C2—C1	117.8 (7)	H41A—C41—H41C	109.5
C4—C3—C2	118.9 (7)	H41B—C41—H41C	109.5
C4—C3—C11	118.8 (7)	C40—C42—H42A	109.5
C2—C3—C11	122.2 (7)	C40—C42—H42B	109.5
C3—C4—C5	124.0 (7)	H42A—C42—H42B	109.5
C3—C4—H4	118.0	C40—C42—H42C	109.5
C5—C4—H4	118.0	H42A—C42—H42C	109.5
C6—C5—C4	115.8 (7)	H42B—C42—H42C	109.5
C6—C5—C7	123.8 (7)	C40—C43—H43A	109.5
C4—C5—C7	120.4 (7)	C40—C43—H43B	109.5
C1—C6—C5	121.5 (7)	H43A—C43—H43B	109.5
C1—C6—H6	119.2	C40—C43—H43C	109.5
C5—C6—H6	119.2	H43A—C43—H43C	109.5
C10—C7—C5	110.9 (7)	H43B—C43—H43C	109.5
C10—C7—C9	110.2 (7)	C36—C44—N1	109.1 (6)
C5—C7—C9	111.4 (7)	C36—C44—H44A	109.9
C10—C7—C8	108.3 (7)	N1—C44—H44A	109.9
C5—C7—C8	109.3 (7)	C36—C44—H44B	109.9
C9—C7—C8	106.6 (7)	N1—C44—H44B	109.9
C7—C8—H8C	109.5	H44A—C44—H44B	108.3
C7—C8—H8D	109.5	C1—C45—N1	109.6 (6)
H8C—C8—H8D	109.5	C1—C45—H45A	109.8
C7—C8—H8E	109.5	N1—C45—H45A	109.8
H8C—C8—H8E	109.5	C1—C45—H45B	109.8
H8D—C8—H8E	109.5	N1—C45—H45B	109.8
C7—C9—H9C	109.5	H45A—C45—H45B	108.2
C7—C9—H9D	109.5	N1—C46—H46A	109.5
H9C—C9—H9D	109.5	N1—C46—H46B	109.5
C7—C9—H9E	109.5	H46A—C46—H46B	109.5
H9C—C9—H9E	109.5	N1—C46—H46C	109.5
H9D—C9—H9E	109.5	H46A—C46—H46C	109.5
C7—C10—H10A	109.5	H46B—C46—H46C	109.5
C7—C10—H10B	109.5	Li—O7—H7A	115.9
H10A—C10—H10B	109.5	Li—O7—H7B	124.3
C7—C10—H10C	109.5	H7A—O7—H7B	101.4
H10A—C10—H10C	109.5	Li—O8—H8A	111.4
H10B—C10—H10C	109.5	Li—O8—H8B	132.5
C3—C11—C12	113.9 (6)	H8A—O8—H8B	97.8
C3—C11—H11A	108.8	H9A—O9—H9B	105.8
C12—C11—H11A	108.8	C47—N2—C51	117.2 (10)
C3—C11—H11B	108.8	C48—C47—N2	117.1 (10)
C12—C11—H11B	108.8	C48—C47—H47	121.5
H11A—C11—H11B	107.7	N2—C47—H47	121.5
C17—C12—C13	119.1 (7)	C47—C48—C49	119.3 (11)
C17—C12—C11	120.8 (6)	C47—C48—H48	120.3
C13—C12—C11	120.1 (7)	C49—C48—H48	120.3
O2—C13—C12	119.0 (7)	C50—C49—C48	124.0 (10)
O2—C13—C14	121.8 (7)	C50—C49—H49	118.1
C12—C13—C14	119.1 (7)	C48—C49—H49	117.9
C15—C14—C13	118.1 (7)	C49—C50—C51	117.7 (9)
C15—C14—C22	121.0 (7)	C49—C50—H50	121.1
C13—C14—C22	120.8 (7)	C51—C50—H50	121.2
C14—C15—C16	124.6 (7)	C50—C51—N2	124.7 (10)
C14—C15—H15	117.7	C50—C51—H51	117.7
C16—C15—H15	117.7	N2—C51—H51	117.6
C17—C16—C15	115.5 (8)	C56—N3—C52	115.8 (7)
C17—C16—C18	122.5 (7)	C56—N3—Li	119.7 (7)
C15—C16—C18	121.9 (7)	C52—N3—Li	124.4 (7)
C16—C17—C12	123.5 (7)	N3—C52—C53	123.7 (9)
C16—C17—H17	118.3	N3—C52—H52	118.1
C12—C17—H17	118.3	C53—C52—H52	118.1
C21—C18—C16	112.1 (7)	C52—C53—C54	119.2 (9)
C21—C18—C20	108.5 (8)	C52—C53—H53	120.4
C16—C18—C20	110.9 (7)	C54—C53—H53	120.4
C21—C18—C19	107.6 (7)	C53—C54—C55	118.7 (8)
C16—C18—C19	108.5 (7)	C53—C54—H54	120.7
C20—C18—C19	109.3 (7)	C55—C54—H54	120.7
C18—C19—H19A	109.5	C56—C55—C54	118.1 (9)
C18—C19—H19B	109.5	C56—C55—H55	120.9
H19A—C19—H19B	109.5	C54—C55—H55	120.9
C18—C19—H19C	109.5	N3—C56—C55	124.5 (8)
H19A—C19—H19C	109.5	N3—C56—H56	117.8
H19B—C19—H19C	109.5	C55—C56—H56	117.8
C18—C20—H20A	109.5	C57—N4—C61	116.8 (8)
C18—C20—H20B	109.5	C57—N4—Li	119.5 (7)
H20A—C20—H20B	109.5	C61—N4—Li	123.1 (7)
C18—C20—H20C	109.5	N4—C57—C58	124.1 (8)
H20A—C20—H20C	109.5	N4—C57—H57	118.0
H20B—C20—H20C	109.5	C58—C57—H57	118.0
C18—C21—H21A	109.5	C57—C58—C59	118.3 (9)
C18—C21—H21B	109.5	C57—C58—H58	120.9
H21A—C21—H21B	109.5	C59—C58—H58	120.9
C18—C21—H21C	109.5	C60—C59—C58	118.8 (8)
H21A—C21—H21C	109.5	C60—C59—H59	120.6
H21B—C21—H21C	109.5	C58—C59—H59	120.6
C23—C22—C14	116.3 (6)	C61—C60—C59	118.6 (8)
C23—C22—H22A	108.2	C61—C60—H60	120.7
C14—C22—H22A	108.2	C59—C60—H60	120.7
C23—C22—H22B	108.2	N4—C61—C60	123.5 (9)
C14—C22—H22B	108.2	N4—C61—H61	118.3
H22A—C22—H22B	107.4	C60—C61—H61	118.3
C24—C23—C28	118.8 (7)	C66—N5—C62	117.1 (9)
C24—C23—C22	122.2 (7)	N5—C62—C63	124.0 (9)
C28—C23—C22	118.9 (7)	N5—C62—H62	118.0
O3—C24—C23	121.4 (7)	C63—C62—H62	118.0
O3—C24—C25	118.0 (7)	C62—C63—C64	117.9 (10)
C23—C24—C25	120.5 (7)	C62—C63—H63	121.0
C26—C25—C24	117.9 (7)	C64—C63—H63	121.0
C26—C25—C33	122.5 (7)	C65—C64—C63	117.8 (10)
C24—C25—C33	119.6 (7)	C65—C64—H64	121.1
C25—C26—C27	123.8 (7)	C63—C64—H64	121.1
C25—C26—H26	118.1	C64—C65—C66	119.9 (9)
C27—C26—H26	118.1	C64—C65—H65	120.0
C26—C27—C28	115.3 (7)	C66—C65—H65	120.0
C26—C27—C29	120.7 (7)	N5—C66—C65	123.2 (10)
C28—C27—C29	124.0 (7)	N5—C66—H66	118.4
C23—C28—C27	123.7 (8)	C65—C66—H66	118.4
C23—C28—H28	118.1	C71—N6—C67	116.4 (9)
C27—C28—H28	118.1	N6—C67—C68	122.9 (9)
C32—C29—C31	108.8 (6)	N6—C67—H67	118.6
C32—C29—C27	108.5 (6)	C68—C67—H67	118.6
C31—C29—C27	110.1 (6)	C69—C68—C67	119.5 (10)
C32—C29—C30	108.8 (6)	C69—C68—H68	120.2
C31—C29—C30	107.8 (7)	C67—C68—H68	120.2
C27—C29—C30	112.7 (6)	C68—C69—C70	118.5 (10)
C29—C30—H30A	109.5	C68—C69—H69	120.7
C29—C30—H30B	109.5	C70—C69—H69	120.7
H30A—C30—H30B	109.5	C71—C70—C69	118.8 (10)
C29—C30—H30C	109.5	C71—C70—H70	120.6
H30A—C30—H30C	109.5	C69—C70—H70	120.6
H30B—C30—H30C	109.5	N6—C71—C70	123.8 (10)
C29—C31—H31A	109.5	N6—C71—H71	118.1
C29—C31—H31B	109.5	C70—C71—H71	118.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6	0.92	2.17	3.083 (8)	173
O7—H7A···O1	0.90	1.92	2.799 (7)	168
O7—H7B···N5	0.91	1.89	2.793 (9)	169
O8—H8A···N6	0.95	1.82	2.732 (9)	159
O8—H8B···O3^i	0.91	1.84	2.735 (7)	166
O9—H9A···O8	0.87	2.12	2.922 (8)	153
O9—H9B···O2^i	0.89	1.95	2.808 (8)	161

Symmetry code: (i) −x+1, y+1/2, −z+1/2.