A dinuclear uranium(IV) complex of the chelating ligand 1,2,3,4-tetra­methyl-5-(2-pyridyl)­cyclo­penta­diene

The ligand 1,2,3,4-tetra­methyl-5-(2-pyridyl)­cyclo­penta­diene (cp*py) forms a dinuclear complex with U^IV, i.e. di-μ-oxo-bis­{chloro­(diethyl ether-κO)[(η⁵,κN)-1,2,3,4-tetra­methyl-5-(2-pyridyl)­cyclo­penta­dienyl]uranium(IV)}, [U₂Cl₂O₂(C₁₄H₁₆N)₂(C₄H₁₀O)₂], in which cp*py acts as a chelating ligand, being bound to the metal atom by the cyclo­penta­dienyl unit and also by the N atom of the pyridyl ring.

S1. Comment

In the course of our studies on the uranium-complexing properties of the ligand tetramethyl-5-(2-pyridyl)cyclopentadiene, denoted cp*py, in view of obtaining uranium-containing heterobimetallic species, we obtained the title compound (I), which is a dinuclear U(IV) complex presenting some interesting features.

The asymmetric unit in (I) comprises one neutral complex molecule, which possesses approximate inversion symmetry. The ligand cp*py acts as a chelating ligand, as in another previously described U(IV)-cp*py complex (Moisan et al., 2001a). Whereas several examples have been reported in which the two ligating sites of cp*py are bound to different metal atoms (Neumann et al., 1997), these uranium complexes are the first examples in which cp*py (or its equivalent without methyl groups, cppy) is bound by the η⁵-cp* ring and the N atom to the same metal centre. The mean U—C bond length is 2.78 (8) Å, U···centroid distances are 2.509 and 2.519 Å for U1 and U2, respectively, and the mean U—N bond length 2.57 (3) Å: the U—C distance in particular is slightly longer than in the previous complex [mean U—C 2.72 (9), U—N 2.553 (9) Å]. Such a coordination mode of cp*py bringing the N atom closer to U results in a distortion which is evidenced by the displacement of atoms C2, C5 and C16, C19 out of the corresponding tetramethylcyclopentadienyl mean planes. These displacements are of 1.76 (6), 0.52 (4), 1.69 (5) and 0.47 (4) Å, respectively, slightly larger than in the previous complex [1.62 (3) and 0.42 (2) Å] because of the larger U—C bond lengths. The dihedral angles between the five- and six-membered rings are 74 (1) and 73 (1)° for the two ligands, slightly greater than in the previous compound [71.7 (4)°], probably for the same reason. The two cyclopentadienyl rings in (I) are nearly parallel with a dihedral angle of 3(1)°, as are the pyridyl units, with a dihedral angle of 4.0 (9)°, in accord with the presence of a pseudo-symmetry centre.

U1 and U2 are each also bound to a chloride ion, with a mean bond length of 2.62 (2) Å and to a diethyl ether molecule, with a mean U—O bond length of 2.15 (4) Å, much smaller than the mean U—O(diethylether) bond length found from the Cambridge Structural Database (Allen & Kennard, 1993), which is 2.50 (3) Å. Two µ₂-oxo ions bridge the two metal atoms, with a mean U—O bond length of 2.10 (3) Å and a mean U—O—U angle of 108.6 (4)°, in good agreement with the mean values for structures of bis(µ₂-oxo)-bridged uranium(IV) dimers found in the CSD [2.14 (4) Å and 106.7 (5)°].

If the cyclopentadienyl ring is represented by its centroid and the difference in nature between the donor atoms is neglected, the U ions are in very distorted octahedral environments, with the common edge O1···O2. U1, U2, O1 and O2 define a plane with a maximum deviation of 0.03 (2) Å. This plane is nearly orthogonal to that defined by U1, U2, Cl1 and Cl2 [maximum deviation 0.054 (9) Å], with a dihedral angle of 80.4 (5)°. N1 and N2 are close to the second plane, with deviations of 0.15 (2) and -0.02 (2) Å, but O3, O4 and the centroids of the cyclopentadienyl rings are more distant from the first one, with deviations in the range 0.22 (3)–1.00 (2) Å. The U···U distance, 3.401 (2) Å, matches the mean distance in the three dinuclear, bis(µ₂-oxo)-bridged, U(IV) complexes reported in the CSD [3.43 (7) Å]. This U···U distance is much larger than that corresponding to a U—U single bond (2.85 Å, Cayton et al., 1991), indicating that no bonding interaction is present between the metal atoms in (I).

S2. Experimental

The lithium salt of the ligand cp*py has been synthesized by a procedure described in the literature (Siemeling et al., 1995). The reaction of two equivalents of Li(cp*py) with UCl₄ in THF at ambient temperature gives the complex UCl₂(cp*py)₂ (Moisan et al., 2001b). Single crystals of (I) were obtained from a solution of UCl₂(cp*py)₂ in THF/Et₂O, in the presence of adventitious traces of oxygen.

S3. Refinement

The atoms of the diethylether units have been refined with anisotropic displacement ellipsoids restrained to an approximate isotropic behaviour. All hydrogen 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 a displacement parameter equal to 1.2 (CH, CH₂) or 1.5 (CH₃) times that of the parent atom. The methyl groups have been refined as rigid rotating units.

Computing details

Data collection: kappaCCD software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL and PARST97 (Nardelli, 1995).

Figures

Fig. 1. The title molecule with the atom-numbering scheme. H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 10% probability level.

(I)

Crystal data

C36H52Cl2N2O4U2	F(000) = 2128
Mr = 1123.76	Dx = 1.908 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.6695 (8) Å	Cell parameters from 20390 reflections
b = 18.2129 (12) Å	θ = 3.2–25.7°
c = 19.1940 (13) Å	µ = 8.44 mm^−1
β = 106.420 (4)°	T = 100 K
V = 3913.0 (5) Å^3	Parallelepiped, black
Z = 4	0.35 × 0.15 × 0.10 mm

Data collection

Nonius kappaCCD diffractometer	7087 independent reflections
Radiation source: fine-focus sealed tube	2097 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
Detector resolution: 18 pixels mm^-1	θmax = 25.7°, θmin = 3.2°
ϕ scans	h = −14→14
Absorption correction: empirical (using intensity measurements) PLATON DELABS (Spek, 2000)	k = −22→22
Tmin = 0.108, Tmax = 0.430	l = −23→23
20386 measured reflections

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)] = 0.087	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.184	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0166P)^2] where P = (Fo^2 + 2Fc^2)/3
7087 reflections	(Δ/σ)max = 0.001
427 parameters	Δρmax = 0.81 e Å^−3
60 restraints	Δρmin = −1.13 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. A 180° range in ϕ was scanned during data collection, with 2° ϕ steps. Crystal-to-detector distance fixed at 28 mm.

Structure solved by direct methods and expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms have been refined anisotropically. All hydrogen atoms were introduced at calculated positions as riding atoms, with a displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. Some restraints on displacement parameters have been applied to the atoms of the diethylether units.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
U1	0.10341 (11)	0.16882 (6)	0.30735 (7)	0.0598 (4)
U2	0.34633 (12)	0.28100 (6)	0.34764 (7)	0.0628 (4)
Cl1	0.2239 (7)	0.0498 (4)	0.3624 (4)	0.073 (2)
Cl2	0.2217 (7)	0.3978 (4)	0.2973 (5)	0.084 (3)
O1	0.2213 (16)	0.2268 (9)	0.3909 (9)	0.064 (5)
O2	0.2338 (17)	0.2209 (9)	0.2659 (9)	0.071 (6)
O3	0.0370 (18)	0.1138 (12)	0.2064 (11)	0.089 (7)
O4	0.412 (2)	0.3357 (13)	0.4522 (12)	0.109 (8)
N1	−0.028 (2)	0.2777 (13)	0.2452 (13)	0.071 (7)
N2	0.4801 (18)	0.1733 (11)	0.4032 (12)	0.051 (6)
C1	−0.025 (3)	0.3243 (16)	0.1930 (15)	0.074 (9)
H1	0.0446	0.3297	0.1788	0.089*
C2	−0.123 (4)	0.3639 (19)	0.1605 (19)	0.109 (13)
H2	−0.1172	0.3987	0.1263	0.131*
C3	−0.234 (3)	0.3562 (15)	0.1746 (16)	0.081 (10)
H3	−0.3007	0.3838	0.1503	0.097*
C4	−0.239 (3)	0.3032 (14)	0.2287 (14)	0.061 (8)
H4	−0.3091	0.2919	0.2400	0.073*
C5	−0.128 (3)	0.2692 (16)	0.2638 (17)	0.070 (9)
C6	−0.107 (2)	0.2157 (14)	0.3248 (16)	0.060 (8)
C7	−0.127 (2)	0.1405 (13)	0.3157 (15)	0.060 (8)
C8	−0.057 (2)	0.1044 (14)	0.3775 (14)	0.077 (10)
C9	0.005 (2)	0.1561 (15)	0.4267 (14)	0.057 (8)
C10	−0.023 (2)	0.2259 (14)	0.3920 (13)	0.042 (6)
C11	−0.219 (3)	0.0995 (15)	0.2516 (15)	0.083 (10)
H11A	−0.1974	0.0487	0.2515	0.124*
H11B	−0.2193	0.1215	0.2061	0.124*
H11C	−0.2977	0.1032	0.2581	0.124*
C12	−0.062 (3)	0.0237 (13)	0.3878 (13)	0.071 (9)
H12A	0.0174	0.0050	0.4068	0.106*
H12B	−0.0995	0.0008	0.3419	0.106*
H12C	−0.1076	0.0134	0.4212	0.106*
C13	0.094 (3)	0.1447 (15)	0.5033 (14)	0.082 (10)
H13A	0.0512	0.1436	0.5391	0.123*
H13B	0.1508	0.1844	0.5139	0.123*
H13C	0.1362	0.0991	0.5043	0.123*
C14	0.017 (2)	0.3007 (13)	0.4240 (14)	0.069 (10)
H14A	0.0863	0.2953	0.4650	0.104*
H14B	−0.0462	0.3232	0.4394	0.104*
H14C	0.0363	0.3310	0.3880	0.104*
C15	0.487 (3)	0.1226 (15)	0.4575 (15)	0.059 (9)
H15	0.4186	0.1118	0.4714	0.070*
C16	0.589 (3)	0.0889 (13)	0.4906 (14)	0.059 (8)
H16	0.5885	0.0540	0.5259	0.070*
C17	0.697 (3)	0.1025 (17)	0.4756 (16)	0.094 (11)
H17	0.7672	0.0777	0.4984	0.113*
C18	0.690 (4)	0.1564 (19)	0.4237 (19)	0.109 (13)
H18	0.7599	0.1703	0.4130	0.130*
C19	0.584 (3)	0.1904 (15)	0.387 (2)	0.074 (11)
C20	0.562 (3)	0.2454 (18)	0.3309 (16)	0.072 (9)
C21	0.572 (3)	0.3227 (16)	0.3404 (14)	0.055 (7)
C22	0.503 (3)	0.3590 (15)	0.2785 (18)	0.073 (9)
C23	0.445 (3)	0.3013 (18)	0.228 (2)	0.091 (11)
C24	0.474 (3)	0.2348 (14)	0.2592 (15)	0.067 (9)
C25	0.662 (3)	0.3572 (16)	0.4015 (17)	0.106 (12)
H25A	0.6282	0.4007	0.4163	0.159*
H25B	0.7310	0.3701	0.3867	0.159*
H25C	0.6838	0.3234	0.4415	0.159*
C26	0.496 (2)	0.4400 (12)	0.2675 (14)	0.067 (9)
H26A	0.5339	0.4642	0.3127	0.100*
H26B	0.4142	0.4547	0.2507	0.100*
H26C	0.5366	0.4534	0.2321	0.100*
C27	0.353 (2)	0.3212 (15)	0.1539 (15)	0.080 (9)
H27A	0.3949	0.3350	0.1196	0.119*
H27B	0.3039	0.3614	0.1607	0.119*
H27C	0.3032	0.2794	0.1358	0.119*
C28	0.437 (2)	0.1606 (12)	0.2232 (15)	0.076 (10)
H28A	0.3803	0.1679	0.1765	0.114*
H28B	0.4005	0.1317	0.2531	0.114*
H28C	0.5057	0.1354	0.2174	0.114*
C29	0.003 (3)	0.0347 (15)	0.1959 (16)	0.084 (11)
H29A	−0.0737	0.0300	0.1594	0.101*
H29B	−0.0048	0.0142	0.2410	0.101*
C30	0.099 (3)	−0.0071 (16)	0.1716 (17)	0.098 (11)
H30A	0.0996	0.0094	0.1241	0.147*
H30B	0.0826	−0.0587	0.1701	0.147*
H30C	0.1761	0.0021	0.2053	0.147*
C31	0.028 (3)	0.1530 (18)	0.1367 (18)	0.107 (12)
H31A	0.0701	0.1250	0.1088	0.128*
H31B	0.0665	0.2004	0.1475	0.128*
C32	−0.104 (3)	0.1650 (17)	0.0891 (16)	0.100 (11)
H32A	−0.1556	0.1691	0.1201	0.151*
H32B	−0.1287	0.1241	0.0568	0.151*
H32C	−0.1087	0.2093	0.0613	0.151*
C33	0.414 (3)	0.4186 (19)	0.4632 (19)	0.122 (14)
H33A	0.4869	0.4314	0.5005	0.146*
H33B	0.4177	0.4422	0.4184	0.146*
C34	0.310 (3)	0.4484 (15)	0.4844 (16)	0.095 (11)
H34A	0.2374	0.4359	0.4479	0.142*
H34B	0.3165	0.5008	0.4890	0.142*
H34C	0.3082	0.4275	0.5301	0.142*
C35	0.425 (3)	0.2941 (16)	0.5206 (17)	0.092 (11)
H35A	0.3918	0.2452	0.5095	0.111*
H35B	0.3819	0.3189	0.5501	0.111*
C36	0.554 (3)	0.2889 (16)	0.5613 (16)	0.104 (12)
H36A	0.5958	0.2612	0.5333	0.155*
H36B	0.5629	0.2649	0.6070	0.155*
H36C	0.5880	0.3374	0.5697	0.155*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.0621 (9)	0.0551 (7)	0.0622 (7)	−0.0005 (7)	0.0176 (7)	0.0027 (7)
U2	0.0657 (9)	0.0557 (7)	0.0683 (8)	0.0022 (7)	0.0209 (7)	0.0001 (7)
Cl1	0.072 (6)	0.059 (5)	0.093 (6)	−0.001 (4)	0.029 (5)	−0.005 (5)
Cl2	0.075 (7)	0.064 (5)	0.112 (7)	0.013 (5)	0.026 (6)	0.006 (5)
O1	0.071 (15)	0.053 (11)	0.075 (13)	−0.019 (11)	0.031 (12)	−0.018 (11)
O2	0.091 (16)	0.046 (10)	0.088 (14)	−0.030 (11)	0.044 (13)	−0.019 (11)
O3	0.081 (18)	0.102 (17)	0.088 (17)	−0.002 (14)	0.030 (14)	−0.013 (15)
O4	0.112 (11)	0.107 (10)	0.112 (11)	0.001 (9)	0.037 (9)	−0.005 (9)
N1	0.062 (11)	0.073 (10)	0.076 (10)	−0.004 (9)	0.018 (8)	−0.004 (9)
N2	0.036 (12)	0.047 (11)	0.071 (13)	−0.010 (10)	0.016 (11)	0.013 (11)
C1	0.072 (17)	0.077 (15)	0.066 (15)	−0.007 (14)	0.009 (14)	0.017 (14)
C2	0.112 (15)	0.112 (15)	0.107 (15)	−0.003 (9)	0.035 (10)	0.004 (9)
C3	0.082 (13)	0.077 (13)	0.081 (13)	0.004 (9)	0.017 (9)	0.000 (9)
C4	0.05 (2)	0.08 (2)	0.052 (18)	0.030 (16)	0.002 (16)	0.001 (16)
C5	0.076 (17)	0.061 (15)	0.073 (16)	0.011 (14)	0.022 (14)	0.009 (14)
C6	0.039 (19)	0.069 (19)	0.07 (2)	−0.032 (17)	0.015 (17)	−0.012 (19)
C7	0.058 (12)	0.061 (11)	0.061 (11)	0.012 (9)	0.017 (9)	−0.007 (9)
C8	0.092 (18)	0.060 (15)	0.087 (17)	−0.016 (14)	0.040 (15)	0.009 (14)
C9	0.052 (15)	0.066 (15)	0.059 (14)	0.001 (13)	0.023 (13)	−0.006 (13)
C10	0.038 (14)	0.048 (12)	0.047 (13)	0.010 (11)	0.024 (11)	0.000 (12)
C11	0.083 (17)	0.074 (16)	0.101 (17)	−0.014 (14)	0.041 (15)	0.010 (14)
C12	0.10 (3)	0.08 (2)	0.036 (17)	0.012 (19)	0.029 (18)	0.021 (16)
C13	0.07 (3)	0.11 (3)	0.07 (2)	0.035 (19)	0.03 (2)	0.012 (19)
C14	0.08 (2)	0.08 (2)	0.07 (2)	0.003 (17)	0.05 (2)	0.013 (17)
C15	0.05 (2)	0.08 (2)	0.06 (2)	−0.035 (17)	0.032 (18)	−0.047 (17)
C16	0.075 (17)	0.041 (13)	0.052 (14)	−0.004 (13)	0.005 (13)	0.019 (12)
C17	0.099 (19)	0.111 (19)	0.080 (17)	−0.010 (15)	0.036 (15)	0.016 (15)
C18	0.111 (17)	0.108 (17)	0.101 (17)	0.002 (13)	0.020 (13)	0.022 (13)
C19	0.08 (3)	0.041 (17)	0.12 (3)	−0.034 (17)	0.06 (3)	−0.028 (19)
C20	0.086 (18)	0.074 (16)	0.054 (15)	0.016 (14)	0.015 (14)	−0.007 (14)
C21	0.060 (16)	0.058 (14)	0.035 (13)	−0.003 (13)	−0.008 (12)	0.009 (13)
C22	0.06 (2)	0.053 (18)	0.10 (3)	0.016 (16)	0.01 (2)	0.01 (2)
C23	0.10 (2)	0.080 (17)	0.095 (18)	0.004 (15)	0.032 (15)	0.009 (15)
C24	0.058 (16)	0.087 (17)	0.065 (15)	−0.010 (14)	0.031 (13)	0.013 (14)
C25	0.091 (19)	0.110 (19)	0.117 (19)	−0.021 (15)	0.029 (16)	−0.005 (15)
C26	0.07 (2)	0.036 (15)	0.09 (2)	0.006 (16)	0.016 (19)	−0.001 (17)
C27	0.064 (17)	0.095 (17)	0.081 (16)	−0.004 (14)	0.022 (14)	0.022 (14)
C28	0.07 (2)	0.049 (17)	0.12 (3)	0.024 (17)	0.04 (2)	0.014 (19)
C29	0.10 (3)	0.06 (2)	0.09 (2)	−0.026 (19)	0.02 (2)	−0.050 (19)
C30	0.106 (19)	0.083 (17)	0.105 (18)	0.003 (15)	0.030 (16)	−0.006 (15)
C31	0.11 (2)	0.110 (19)	0.097 (18)	0.006 (16)	0.029 (16)	0.007 (16)
C32	0.096 (19)	0.117 (18)	0.084 (17)	−0.019 (16)	0.017 (15)	−0.018 (15)
C33	0.125 (18)	0.115 (17)	0.126 (18)	0.000 (13)	0.036 (13)	−0.013 (13)
C34	0.097 (19)	0.088 (17)	0.102 (18)	0.017 (15)	0.032 (15)	−0.022 (15)
C35	0.095 (14)	0.094 (14)	0.089 (13)	0.006 (9)	0.028 (10)	−0.004 (9)
C36	0.104 (14)	0.113 (14)	0.094 (14)	0.003 (9)	0.029 (10)	0.003 (9)

Geometric parameters (Å, º)

U1—O1	2.081 (17)	C14—H14B	0.9600
U1—O2	2.129 (16)	C14—H14C	0.9600
U1—O3	2.12 (2)	C15—C16	1.33 (3)
U1—N1	2.59 (2)	C15—H15	0.9300
U1—Cl1	2.637 (7)	C16—C17	1.39 (4)
U1—C6	2.71 (3)	C16—H16	0.9300
U1—C7	2.78 (3)	C17—C18	1.38 (4)
U1—C8	2.85 (3)	C17—H17	0.9300
U1—C9	2.84 (2)	C18—C19	1.39 (4)
U1—C10	2.69 (2)	C18—H18	0.9300
U2—O1	2.116 (15)	C19—C20	1.44 (4)
U2—O2	2.054 (17)	C20—C21	1.42 (3)
U2—O4	2.18 (2)	C20—C24	1.48 (4)
U2—N2	2.55 (2)	C21—C22	1.40 (3)
U2—Cl2	2.604 (8)	C21—C25	1.47 (3)
U2—C20	2.70 (3)	C22—C23	1.46 (4)
U2—C21	2.79 (3)	C22—C26	1.49 (3)
U2—C22	2.92 (3)	C23—C24	1.35 (4)
U2—C23	2.87 (3)	C23—C27	1.56 (4)
U2—C24	2.69 (3)	C24—C28	1.52 (4)
U1—U2	3.4013 (18)	C25—H25A	0.9600
O3—C29	1.49 (3)	C25—H25B	0.9600
O3—C31	1.49 (3)	C25—H25C	0.9600
O4—C35	1.49 (3)	C26—H26A	0.9600
O4—C33	1.52 (3)	C26—H26B	0.9600
N1—C1	1.32 (3)	C26—H26C	0.9600
N1—C5	1.32 (3)	C27—H27A	0.9600
N2—C19	1.37 (3)	C27—H27B	0.9600
N2—C15	1.38 (3)	C27—H27C	0.9600
C1—C2	1.35 (4)	C28—H28A	0.9600
C1—H1	0.9300	C28—H28B	0.9600
C2—C3	1.40 (4)	C28—H28C	0.9600
C2—H2	0.9300	C29—C30	1.54 (3)
C3—C4	1.43 (3)	C29—H29A	0.9700
C3—H3	0.9300	C29—H29B	0.9700
C4—C5	1.41 (3)	C30—H30A	0.9600
C4—H4	0.9300	C30—H30B	0.9600
C5—C6	1.49 (3)	C30—H30C	0.9600
C6—C7	1.39 (3)	C31—C32	1.56 (4)
C6—C10	1.40 (3)	C31—H31A	0.9700
C7—C8	1.40 (4)	C31—H31B	0.9700
C7—C11	1.58 (3)	C32—H32A	0.9600
C8—C9	1.38 (4)	C32—H32B	0.9600
C8—C12	1.49 (3)	C32—H32C	0.9600
C9—C10	1.43 (3)	C33—C34	1.49 (3)
C9—C13	1.56 (3)	C33—H33A	0.9700
C10—C14	1.51 (3)	C33—H33B	0.9700
C11—H11A	0.9600	C34—H34A	0.9600
C11—H11B	0.9600	C34—H34B	0.9600
C11—H11C	0.9600	C34—H34C	0.9600
C12—H12A	0.9600	C35—C36	1.49 (4)
C12—H12B	0.9600	C35—H35A	0.9700
C12—H12C	0.9600	C35—H35B	0.9700
C13—H13A	0.9600	C36—H36A	0.9600
C13—H13B	0.9600	C36—H36B	0.9600
C13—H13C	0.9600	C36—H36C	0.9600
C14—H14A	0.9600
O1—U1—O2	71.0 (6)	C18—C17—H17	123.1
O1—U1—O3	159.0 (7)	C16—C17—H17	123.1
O1—U1—N1	98.3 (7)	C17—C18—C19	123 (4)
O3—U1—N1	85.7 (8)	C17—C18—H18	118.6
O2—U1—N1	83.2 (8)	C19—C18—H18	118.6
O2—U1—O3	89.1 (7)	N2—C19—C18	120 (3)
O1—U1—Cl1	86.9 (5)	N2—C19—C20	110 (3)
O3—U1—Cl1	89.6 (6)	C18—C19—C20	130 (3)
O2—U1—Cl1	99.2 (5)	C21—C20—C19	127 (3)
N1—U1—Cl1	174.8 (5)	C21—C20—C24	105 (3)
O2—U2—O1	71.8 (6)	C19—C20—C24	123 (3)
O2—U2—O4	158.5 (7)	C22—C21—C20	111 (3)
O1—U2—O4	87.4 (7)	C22—C21—C25	126 (3)
O2—U2—N2	95.3 (7)	C20—C21—C25	123 (3)
O1—U2—N2	83.4 (7)	C21—C22—C23	106 (3)
O4—U2—N2	87.3 (8)	C21—C22—C26	126 (3)
O2—U2—Cl2	89.0 (6)	C23—C22—C26	128 (3)
O1—U2—Cl2	98.8 (5)	C24—C23—C22	110 (3)
O4—U2—Cl2	89.0 (7)	C24—C23—C27	129 (3)
N2—U2—Cl2	175.6 (5)	C22—C23—C27	121 (3)
U1—O1—U2	108.3 (7)	C23—C24—C20	109 (3)
U1—O2—U2	108.8 (7)	C23—C24—C28	126 (3)
C31—O3—C29	113 (2)	C20—C24—C28	125 (3)
C31—O3—U1	120.5 (19)	C21—C25—H25A	109.5
C29—O3—U1	126.4 (18)	C21—C25—H25B	109.5
C35—O4—C33	113 (2)	H25A—C25—H25B	109.5
C35—O4—U2	120.2 (18)	C21—C25—H25C	109.5
C33—O4—U2	125 (2)	H25A—C25—H25C	109.5
C1—N1—C5	120 (3)	H25B—C25—H25C	109.5
C1—N1—U1	134 (2)	C22—C26—H26A	109.5
C5—N1—U1	104 (2)	C22—C26—H26B	109.5
C19—N2—C15	117 (3)	H26A—C26—H26B	109.5
C19—N2—U2	102.0 (19)	C22—C26—H26C	109.5
C15—N2—U2	136.8 (17)	H26A—C26—H26C	109.5
N1—C1—C2	119 (3)	H26B—C26—H26C	109.5
N1—C1—H1	120.4	C23—C27—H27A	109.5
C2—C1—H1	120.4	C23—C27—H27B	109.5
C1—C2—C3	125 (4)	H27A—C27—H27B	109.5
C1—C2—H2	117.6	C23—C27—H27C	109.5
C3—C2—H2	117.6	H27A—C27—H27C	109.5
C2—C3—C4	116 (3)	H27B—C27—H27C	109.5
C2—C3—H3	122.2	C24—C28—H28A	109.5
C4—C3—H3	122.2	C24—C28—H28B	109.5
C5—C4—C3	115 (3)	H28A—C28—H28B	109.5
C5—C4—H4	122.4	C24—C28—H28C	109.5
C3—C4—H4	122.4	H28A—C28—H28C	109.5
N1—C5—C4	125 (3)	H28B—C28—H28C	109.5
N1—C5—C6	109 (3)	O3—C29—C30	109 (2)
C4—C5—C6	126 (3)	O3—C29—H29A	109.9
C7—C6—C10	107 (3)	C30—C29—H29A	109.9
C7—C6—C5	124 (3)	O3—C29—H29B	109.9
C10—C6—C5	124 (2)	C30—C29—H29B	109.9
C6—C7—C8	109 (3)	H29A—C29—H29B	108.3
C6—C7—C11	128 (2)	C29—C30—H30A	109.5
C8—C7—C11	123 (2)	C29—C30—H30B	109.5
C9—C8—C7	109 (2)	H30A—C30—H30B	109.5
C9—C8—C12	128 (3)	C29—C30—H30C	109.5
C7—C8—C12	123 (2)	H30A—C30—H30C	109.5
C8—C9—C10	106 (2)	H30B—C30—H30C	109.5
C8—C9—C13	130 (3)	O3—C31—C32	114 (3)
C10—C9—C13	124 (2)	O3—C31—H31A	108.8
C6—C10—C9	109 (2)	C32—C31—H31A	108.8
C6—C10—C14	124 (2)	O3—C31—H31B	108.8
C9—C10—C14	127 (2)	C32—C31—H31B	108.8
C7—C11—H11A	109.5	H31A—C31—H31B	107.7
C7—C11—H11B	109.5	C31—C32—H32A	109.5
H11A—C11—H11B	109.5	C31—C32—H32B	109.5
C7—C11—H11C	109.5	H32A—C32—H32B	109.5
H11A—C11—H11C	109.5	C31—C32—H32C	109.5
H11B—C11—H11C	109.5	H32A—C32—H32C	109.5
C8—C12—H12A	109.5	H32B—C32—H32C	109.5
C8—C12—H12B	109.5	C34—C33—O4	114 (3)
H12A—C12—H12B	109.5	C34—C33—H33A	108.7
C8—C12—H12C	109.5	O4—C33—H33A	108.7
H12A—C12—H12C	109.5	C34—C33—H33B	108.7
H12B—C12—H12C	109.5	O4—C33—H33B	108.7
C9—C13—H13A	109.5	H33A—C33—H33B	107.6
C9—C13—H13B	109.5	C33—C34—H34A	109.5
H13A—C13—H13B	109.5	C33—C34—H34B	109.5
C9—C13—H13C	109.5	H34A—C34—H34B	109.5
H13A—C13—H13C	109.5	C33—C34—H34C	109.5
H13B—C13—H13C	109.5	H34A—C34—H34C	109.5
C10—C14—H14A	109.5	H34B—C34—H34C	109.5
C10—C14—H14B	109.5	O4—C35—C36	109 (3)
H14A—C14—H14B	109.5	O4—C35—H35A	109.8
C10—C14—H14C	109.5	C36—C35—H35A	109.8
H14A—C14—H14C	109.5	O4—C35—H35B	109.8
H14B—C14—H14C	109.5	C36—C35—H35B	109.8
C16—C15—N2	121 (2)	H35A—C35—H35B	108.3
C16—C15—H15	119.3	C35—C36—H36A	109.5
N2—C15—H15	119.3	C35—C36—H36B	109.5
C15—C16—C17	124 (3)	H36A—C36—H36B	109.5
C15—C16—H16	117.9	C35—C36—H36C	109.5
C17—C16—H16	117.9	H36A—C36—H36C	109.5
C18—C17—C16	114 (3)	H36B—C36—H36C	109.5