Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103015786/ob1134sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103015786/ob1134Isup2.hkl |
CCDC reference: 224487
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.
The ammonium and hydroxy H atoms were found in difference Fourier maps and were introduced as riding atoms, with isotropic displacement parameters equal to 1.2Ueq 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 1.2Ueq (CH, CH2) or 1.5Ueq (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.
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).
[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) Å3 | 0.38 × 0.12 × 0.05 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0088P)2 + 25.0468P] where P = (Fo2 + 2Fc2)/3 |
12756 reflections | (Δ/σ)max = 0.001 |
806 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
[Li(C5H5N)2(H2O)2][UO2(C46H58NO4)]·3C5H5N·H2O | V = 6792.8 (9) Å3 |
Mr = 1415.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.8644 (16) Å | µ = 2.45 mm−1 |
b = 16.6147 (13) Å | T = 100 K |
c = 19.7150 (14) Å | 0.38 × 0.12 × 0.05 mm |
β = 96.321 (5)° |
Nonius Kappa-CCD diffractometer | 12756 independent reflections |
Absorption correction: part of the refinement model (ΔF) (DELABS in PLATON; Spek, 2003) | 7934 reflections with I > 2σ(I) |
Tmin = 0.698, Tmax = 0.872 | Rint = 0.096 |
45959 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0088P)2 + 25.0468P] where P = (Fo2 + 2Fc2)/3 |
12756 reflections | Δρmax = 0.82 e Å−3 |
806 parameters | Δρmin = −1.03 e Å−3 |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
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···O3i | 0.91 | 1.84 | 2.735 (7) | 166 |
O9—H9A···O8 | 0.87 | 2.12 | 2.922 (8) | 153 |
O9—H9B···O2i | 0.89 | 1.95 | 2.808 (8) | 161 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Li(C5H5N)2(H2O)2][UO2(C46H58NO4)]·3C5H5N·H2O |
Mr | 1415.45 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 20.8644 (16), 16.6147 (13), 19.7150 (14) |
β (°) | 96.321 (5) |
V (Å3) | 6792.8 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.45 |
Crystal size (mm) | 0.38 × 0.12 × 0.05 |
Data collection | |
Diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | Part of the refinement model (ΔF) (DELABS in PLATON; Spek, 2003) |
Tmin, Tmax | 0.698, 0.872 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45959, 12756, 7934 |
Rint | 0.096 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.126, 1.03 |
No. of reflections | 12756 |
No. of parameters | 806 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0088P)2 + 25.0468P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.82, −1.03 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL and PLATON (Spek, 2003).
U—O1 | 2.301 (5) | U—O6 | 1.796 (5) |
U—O2 | 2.262 (5) | Li—O7 | 1.914 (15) |
U—O3 | 2.243 (5) | Li—O8 | 1.906 (15) |
U—O4 | 2.272 (5) | Li—N3 | 2.064 (16) |
U—O5 | 1.805 (5) | Li—N4 | 2.089 (16) |
O1—U—O2 | 87.56 (17) | O7—Li—O8 | 113.2 (8) |
O2—U—O3 | 81.30 (17) | O7—Li—N3 | 110.4 (7) |
O3—U—O4 | 87.73 (17) | O7—Li—N4 | 113.9 (8) |
O4—U—O1 | 102.91 (17) | O8—Li—N3 | 111.6 (8) |
O1—U—N1 | 55.79 (15) | O8—Li—N4 | 108.4 (7) |
O4—U—N1 | 57.05 (15) | N3—Li—N4 | 98.6 (7) |
O5—U—O6 | 176.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O6 | 0.92 | 2.17 | 3.083 (8) | 173.3 |
O7—H7A···O1 | 0.90 | 1.92 | 2.799 (7) | 168.0 |
O7—H7B···N5 | 0.91 | 1.89 | 2.793 (9) | 169.0 |
O8—H8A···N6 | 0.95 | 1.82 | 2.732 (9) | 159.4 |
O8—H8B···O3i | 0.91 | 1.84 | 2.735 (7) | 166.2 |
O9—H9A···O8 | 0.87 | 2.12 | 2.922 (8) | 153.2 |
O9—H9B···O2i | 0.89 | 1.95 | 2.808 (8) | 161.0 |
Symmetry code: (i) −x+1, y+1/2, −z+1/2. |
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···Oether distance is shorter [3.534 (8) Å; Harrowfield et al., 1991], and even shorter U···Oether 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].