Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027513/fa1040sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027513/fa1040Isup2.hkl |
CCDC reference: 231039
p-tert-Butyltetrahomodioxacalix[4]arene was synthesized using the method of Dhawan & Gutsche (1983), and U(OTf)4 (OTf is OSO2CF3) was synthesized using the method of Berthet et al. (1999). Complex (I) was synthesized by reaction of p-tert-butyltetrahomodioxacalix[4]arene with one equivalent of U(OTf)4 in pyridine. The oxidation of the metal centre from UIV to UVI, in the form of the uranyl ion, can be attributed either to adventitious traces of oxygen, possibly entering the reaction flask during prolonged heating at 383 K, or to the water molecules eliminated during the nucleophilic attack on the benzylic C atoms by pyridine. Single crystals of (I) were obtained by slow diffusion of tetrahydrofuran into the mother solution.
The 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 with Uiso(H) = 1.2 (CH or CH2) or 1.5 (CH3) times Ueq of the parent atom. Some restraints on displacement parameters were applied for two F atoms and for the C atoms of the pyridine molecule. The highest positive and negative electron-density residuals are located 0.87 and 0.95 Å, respectively, from the U atom.
Data collection: EVALCCD (Duisenberg et al., 2003); cell refinement: EVALCCD; data reduction: EVALCCD; 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.
[UO2(C33H38N2O2)2](CF3O3S)2·2C5H5N | Z = 1 |
Mr = 1715.68 | F(000) = 870 |
Triclinic, P1 | Dx = 1.511 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7189 (9) Å | Cell parameters from 13391 reflections |
b = 11.1479 (13) Å | θ = 2.5–25.7° |
c = 17.0975 (16) Å | µ = 2.29 mm−1 |
α = 102.472 (6)° | T = 100 K |
β = 106.903 (6)° | Needle, light orange |
γ = 94.800 (6)° | 0.40 × 0.10 × 0.05 mm |
V = 1885.0 (3) Å3 |
Nonius KappaCCD area-detector diffractometer | 6934 independent reflections |
Radiation source: fine-focus sealed tube | 5444 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
ϕ and ω scans | θmax = 25.7°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.698, Tmax = 0.892 | k = −13→12 |
13391 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0328P)2] where P = (Fo2 + 2Fc2)/3 |
6934 reflections | (Δ/σ)max = 0.001 |
481 parameters | Δρmax = 1.54 e Å−3 |
36 restraints | Δρmin = −2.30 e Å−3 |
[UO2(C33H38N2O2)2](CF3O3S)2·2C5H5N | γ = 94.800 (6)° |
Mr = 1715.68 | V = 1885.0 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.7189 (9) Å | Mo Kα radiation |
b = 11.1479 (13) Å | µ = 2.29 mm−1 |
c = 17.0975 (16) Å | T = 100 K |
α = 102.472 (6)° | 0.40 × 0.10 × 0.05 mm |
β = 106.903 (6)° |
Nonius KappaCCD area-detector diffractometer | 6934 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5444 reflections with I > 2σ(I) |
Tmin = 0.698, Tmax = 0.892 | Rint = 0.089 |
13391 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 36 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.54 e Å−3 |
6934 reflections | Δρmin = −2.30 e Å−3 |
481 parameters |
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 Patterson map interpretation and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. Some restraints on displacement parameters were applied for two F atoms and the C atoms of the pyridine molecule. All H atoms were introduced at calculated positions and were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (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 | 1.0000 | 0.5000 | 0.5000 | 0.01041 (11) | |
O1 | 1.0676 (3) | 0.4168 (3) | 0.3900 (2) | 0.0123 (8) | |
O2 | 0.9008 (3) | 0.6317 (3) | 0.4274 (2) | 0.0123 (8) | |
O3 | 0.8479 (3) | 0.3940 (3) | 0.4549 (2) | 0.0115 (8) | |
N1 | 0.9121 (4) | 0.1470 (4) | 0.3543 (3) | 0.0105 (10) | |
N2 | 0.5670 (4) | 0.6292 (4) | 0.4057 (3) | 0.0096 (10) | |
C1 | 0.9924 (5) | 0.2594 (5) | 0.2609 (3) | 0.0097 (12) | |
C2 | 1.0222 (5) | 0.3862 (5) | 0.3058 (3) | 0.0115 (12) | |
C3 | 1.0089 (5) | 0.4771 (5) | 0.2585 (3) | 0.0114 (12) | |
C4 | 0.9699 (5) | 0.4384 (5) | 0.1714 (3) | 0.0127 (12) | |
H4 | 0.9641 | 0.4991 | 0.1413 | 0.015* | |
C5 | 0.9386 (5) | 0.3140 (5) | 0.1257 (3) | 0.0133 (13) | |
C6 | 0.9517 (5) | 0.2257 (5) | 0.1734 (3) | 0.0130 (12) | |
H6 | 0.9326 | 0.1417 | 0.1455 | 0.016* | |
C7 | 0.8939 (6) | 0.2796 (5) | 0.0294 (3) | 0.0195 (14) | |
C8 | 0.7809 (6) | 0.3475 (6) | −0.0053 (4) | 0.0256 (15) | |
H8A | 0.7063 | 0.3218 | 0.0109 | 0.038* | |
H8B | 0.7567 | 0.3277 | −0.0658 | 0.038* | |
H8C | 0.8084 | 0.4355 | 0.0171 | 0.038* | |
C9 | 1.0096 (6) | 0.3156 (6) | −0.0010 (4) | 0.0296 (16) | |
H9A | 0.9802 | 0.2971 | −0.0616 | 0.044* | |
H9B | 1.0791 | 0.2692 | 0.0176 | 0.044* | |
H9C | 1.0418 | 0.4030 | 0.0218 | 0.044* | |
C10 | 0.8443 (8) | 0.1388 (6) | −0.0080 (4) | 0.0397 (18) | |
H10A | 0.7699 | 0.1151 | 0.0090 | 0.067* | |
H10B | 0.9137 | 0.0932 | 0.0123 | 0.067* | |
H10C | 0.8183 | 0.1204 | −0.0685 | 0.067* | |
C11 | 1.0353 (5) | 0.6151 (5) | 0.3038 (3) | 0.0111 (12) | |
H11A | 1.0833 | 0.6254 | 0.3631 | 0.013* | |
H11B | 1.0907 | 0.6598 | 0.2802 | 0.013* | |
C12 | 0.9091 (5) | 0.6715 (5) | 0.2964 (3) | 0.0099 (12) | |
C13 | 0.8485 (5) | 0.6754 (5) | 0.3596 (3) | 0.0078 (11) | |
C14 | 0.7318 (5) | 0.7288 (5) | 0.3504 (3) | 0.0091 (12) | |
C15 | 0.6783 (5) | 0.7712 (5) | 0.2791 (3) | 0.0107 (12) | |
H15 | 0.6015 | 0.8061 | 0.2743 | 0.013* | |
C16 | 0.7338 (5) | 0.7640 (5) | 0.2146 (3) | 0.0096 (12) | |
C17 | 0.8516 (5) | 0.7152 (5) | 0.2275 (3) | 0.0109 (12) | |
H17 | 0.8939 | 0.7122 | 0.1869 | 0.013* | |
C18 | 0.6720 (5) | 0.8006 (5) | 0.1310 (3) | 0.0135 (13) | |
C19 | 0.6329 (6) | 0.6834 (5) | 0.0582 (3) | 0.0215 (14) | |
H19A | 0.5685 | 0.6262 | 0.0662 | 0.032* | |
H19B | 0.7095 | 0.6452 | 0.0569 | 0.032* | |
H19C | 0.5962 | 0.7053 | 0.0059 | 0.032* | |
C20 | 0.7717 (6) | 0.8914 (5) | 0.1156 (4) | 0.0199 (14) | |
H20A | 0.7323 | 0.9118 | 0.0630 | 0.030* | |
H20B | 0.8483 | 0.8538 | 0.1133 | 0.030* | |
H20C | 0.7970 | 0.9659 | 0.1607 | 0.030* | |
C21 | 0.5499 (5) | 0.8610 (5) | 0.1314 (3) | 0.0191 (14) | |
H21A | 0.4834 | 0.8027 | 0.1366 | 0.029* | |
H21B | 0.5165 | 0.8853 | 0.0796 | 0.029* | |
H21C | 0.5727 | 0.9330 | 0.1782 | 0.029* | |
C22 | 1.0116 (5) | 0.1625 (5) | 0.3101 (3) | 0.0156 (13) | |
H22A | 1.0087 | 0.0833 | 0.2719 | 0.019* | |
H22B | 1.0988 | 0.1841 | 0.3518 | 0.019* | |
C23 | 0.7839 (5) | 0.1447 (5) | 0.3147 (3) | 0.0156 (13) | |
H23 | 0.7579 | 0.1598 | 0.2613 | 0.019* | |
C24 | 0.6898 (5) | 0.1201 (5) | 0.3521 (4) | 0.0147 (13) | |
H24 | 0.6006 | 0.1152 | 0.3234 | 0.018* | |
C25 | 0.7301 (5) | 0.1030 (5) | 0.4329 (4) | 0.0156 (13) | |
H25 | 0.6684 | 0.0883 | 0.4598 | 0.019* | |
C26 | 0.8632 (5) | 0.1079 (5) | 0.4733 (3) | 0.0149 (13) | |
H26 | 0.8919 | 0.0968 | 0.5277 | 0.018* | |
C27 | 0.9526 (5) | 0.1294 (5) | 0.4324 (3) | 0.0133 (12) | |
H27 | 1.0420 | 0.1317 | 0.4592 | 0.016* | |
C28 | 0.6676 (5) | 0.7416 (5) | 0.4187 (3) | 0.0097 (12) | |
H28A | 0.6244 | 0.8148 | 0.4203 | 0.012* | |
H28B | 0.7354 | 0.7540 | 0.4729 | 0.012* | |
C29 | 0.6002 (5) | 0.5153 (5) | 0.3915 (3) | 0.0139 (13) | |
H29 | 0.6831 | 0.5057 | 0.3864 | 0.017* | |
C30 | 0.5136 (5) | 0.4123 (5) | 0.3842 (3) | 0.0163 (13) | |
H30 | 0.5385 | 0.3337 | 0.3755 | 0.020* | |
C31 | 0.3907 (5) | 0.4258 (5) | 0.3900 (3) | 0.0161 (13) | |
H31 | 0.3306 | 0.3569 | 0.3844 | 0.019* | |
C32 | 0.3576 (5) | 0.5433 (6) | 0.4042 (4) | 0.0197 (14) | |
H32 | 0.2745 | 0.5539 | 0.4085 | 0.024* | |
C33 | 0.4464 (5) | 0.6452 (5) | 0.4120 (3) | 0.0149 (13) | |
H33 | 0.4236 | 0.7245 | 0.4215 | 0.018* | |
S | 0.33942 (13) | 1.01717 (13) | 0.37917 (9) | 0.0139 (3) | |
O4 | 0.4118 (4) | 1.1382 (3) | 0.3915 (3) | 0.0257 (10) | |
O5 | 0.4192 (4) | 0.9245 (4) | 0.4012 (2) | 0.0252 (10) | |
O6 | 0.2238 (4) | 1.0181 (4) | 0.4055 (2) | 0.0235 (10) | |
F1 | 0.1907 (5) | 0.8577 (4) | 0.2408 (3) | 0.0635 (13) | |
F2 | 0.2045 (3) | 1.0451 (4) | 0.2305 (2) | 0.0411 (10) | |
F3 | 0.3672 (3) | 0.9471 (3) | 0.2296 (2) | 0.0338 (9) | |
C34 | 0.2720 (6) | 0.9630 (6) | 0.2643 (4) | 0.0244 (15) | |
N3 | 0.5516 (6) | 0.2339 (6) | 0.1749 (4) | 0.0473 (17) | |
C35 | 0.6116 (8) | 0.3440 (8) | 0.1833 (4) | 0.045 (2) | |
H35 | 0.7016 | 0.3534 | 0.1906 | 0.054* | |
C36 | 0.5528 (9) | 0.4447 (8) | 0.1822 (5) | 0.054 (2) | |
H36 | 0.6013 | 0.5206 | 0.1870 | 0.064* | |
C37 | 0.4240 (9) | 0.4369 (8) | 0.1742 (5) | 0.059 (2) | |
H37 | 0.3822 | 0.5068 | 0.1747 | 0.071* | |
C38 | 0.3539 (8) | 0.3192 (9) | 0.1650 (5) | 0.060 (2) | |
H38 | 0.2642 | 0.3075 | 0.1585 | 0.072* | |
C39 | 0.4256 (8) | 0.2230 (8) | 0.1663 (5) | 0.052 (2) | |
H39 | 0.3816 | 0.1446 | 0.1607 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U | 0.00956 (18) | 0.01204 (19) | 0.01036 (18) | 0.00416 (13) | 0.00436 (14) | 0.00172 (13) |
O1 | 0.012 (2) | 0.014 (2) | 0.013 (2) | 0.0070 (16) | 0.0060 (17) | 0.0028 (17) |
O2 | 0.011 (2) | 0.020 (2) | 0.010 (2) | 0.0086 (17) | 0.0079 (17) | 0.0045 (17) |
O3 | 0.0098 (19) | 0.012 (2) | 0.016 (2) | 0.0038 (16) | 0.0076 (17) | 0.0055 (17) |
N1 | 0.009 (2) | 0.008 (2) | 0.015 (3) | 0.0048 (19) | 0.006 (2) | 0.000 (2) |
N2 | 0.006 (2) | 0.014 (3) | 0.009 (2) | 0.0027 (19) | 0.002 (2) | 0.002 (2) |
C1 | 0.009 (3) | 0.013 (3) | 0.015 (3) | 0.007 (2) | 0.009 (2) | 0.009 (2) |
C2 | 0.006 (3) | 0.020 (3) | 0.010 (3) | 0.003 (2) | 0.005 (2) | 0.001 (2) |
C3 | 0.012 (3) | 0.010 (3) | 0.017 (3) | 0.005 (2) | 0.010 (3) | 0.006 (2) |
C4 | 0.017 (3) | 0.013 (3) | 0.015 (3) | 0.009 (2) | 0.011 (3) | 0.007 (2) |
C5 | 0.014 (3) | 0.019 (3) | 0.010 (3) | 0.002 (3) | 0.009 (3) | 0.003 (3) |
C6 | 0.014 (3) | 0.012 (3) | 0.017 (3) | 0.006 (2) | 0.010 (3) | 0.003 (2) |
C7 | 0.025 (3) | 0.020 (3) | 0.011 (3) | 0.002 (3) | 0.005 (3) | 0.002 (3) |
C8 | 0.026 (4) | 0.033 (4) | 0.015 (3) | 0.004 (3) | 0.003 (3) | 0.004 (3) |
C9 | 0.031 (4) | 0.049 (5) | 0.012 (3) | 0.018 (3) | 0.009 (3) | 0.007 (3) |
C10 | 0.060 (4) | 0.031 (3) | 0.019 (3) | 0.001 (3) | 0.002 (3) | 0.004 (3) |
C11 | 0.012 (3) | 0.014 (3) | 0.007 (3) | 0.000 (2) | 0.004 (2) | 0.000 (2) |
C12 | 0.009 (3) | 0.007 (3) | 0.013 (3) | 0.000 (2) | 0.006 (2) | −0.002 (2) |
C13 | 0.006 (3) | 0.006 (3) | 0.010 (3) | −0.002 (2) | 0.002 (2) | −0.001 (2) |
C14 | 0.007 (3) | 0.007 (3) | 0.013 (3) | 0.000 (2) | 0.004 (2) | 0.002 (2) |
C15 | 0.007 (3) | 0.012 (3) | 0.018 (3) | 0.006 (2) | 0.007 (3) | 0.006 (2) |
C16 | 0.010 (3) | 0.006 (3) | 0.012 (3) | 0.000 (2) | 0.005 (2) | −0.001 (2) |
C17 | 0.012 (3) | 0.011 (3) | 0.012 (3) | 0.000 (2) | 0.009 (3) | 0.001 (2) |
C18 | 0.015 (3) | 0.015 (3) | 0.012 (3) | 0.003 (2) | 0.006 (3) | 0.002 (2) |
C19 | 0.022 (3) | 0.026 (4) | 0.015 (3) | 0.004 (3) | 0.002 (3) | 0.006 (3) |
C20 | 0.026 (3) | 0.023 (4) | 0.019 (3) | 0.009 (3) | 0.012 (3) | 0.012 (3) |
C21 | 0.017 (3) | 0.027 (4) | 0.012 (3) | 0.009 (3) | 0.000 (3) | 0.006 (3) |
C22 | 0.017 (3) | 0.017 (3) | 0.017 (3) | 0.003 (3) | 0.014 (3) | 0.002 (3) |
C23 | 0.021 (3) | 0.015 (3) | 0.014 (3) | 0.008 (3) | 0.009 (3) | 0.001 (3) |
C24 | 0.010 (3) | 0.009 (3) | 0.021 (3) | −0.001 (2) | 0.004 (3) | −0.004 (3) |
C25 | 0.019 (3) | 0.011 (3) | 0.021 (3) | 0.004 (3) | 0.014 (3) | 0.002 (3) |
C26 | 0.023 (3) | 0.013 (3) | 0.015 (3) | 0.006 (3) | 0.012 (3) | 0.006 (2) |
C27 | 0.015 (3) | 0.012 (3) | 0.013 (3) | 0.000 (2) | 0.007 (3) | 0.001 (2) |
C28 | 0.010 (3) | 0.007 (3) | 0.010 (3) | −0.001 (2) | 0.003 (3) | 0.000 (2) |
C29 | 0.010 (3) | 0.015 (3) | 0.021 (3) | 0.009 (2) | 0.007 (3) | 0.009 (3) |
C30 | 0.019 (3) | 0.015 (3) | 0.017 (3) | 0.004 (3) | 0.010 (3) | 0.004 (3) |
C31 | 0.012 (3) | 0.021 (3) | 0.017 (3) | 0.000 (3) | 0.004 (3) | 0.008 (3) |
C32 | 0.010 (3) | 0.029 (4) | 0.024 (3) | 0.004 (3) | 0.009 (3) | 0.010 (3) |
C33 | 0.010 (3) | 0.022 (3) | 0.015 (3) | 0.011 (3) | 0.002 (3) | 0.008 (3) |
S | 0.0143 (8) | 0.0141 (8) | 0.0174 (8) | 0.0054 (6) | 0.0094 (7) | 0.0054 (6) |
O4 | 0.033 (2) | 0.013 (2) | 0.034 (3) | −0.0023 (19) | 0.018 (2) | 0.0048 (19) |
O5 | 0.028 (2) | 0.026 (3) | 0.026 (2) | 0.019 (2) | 0.007 (2) | 0.010 (2) |
O6 | 0.020 (2) | 0.038 (3) | 0.024 (2) | 0.010 (2) | 0.016 (2) | 0.017 (2) |
F1 | 0.073 (3) | 0.065 (3) | 0.033 (2) | −0.033 (2) | 0.008 (2) | 0.002 (2) |
F2 | 0.038 (2) | 0.074 (3) | 0.027 (2) | 0.034 (2) | 0.0172 (17) | 0.0258 (19) |
F3 | 0.033 (2) | 0.052 (3) | 0.024 (2) | 0.0226 (19) | 0.0198 (18) | 0.0046 (18) |
C34 | 0.023 (3) | 0.023 (4) | 0.034 (4) | −0.001 (3) | 0.018 (3) | 0.009 (3) |
N3 | 0.043 (4) | 0.040 (4) | 0.050 (4) | 0.002 (3) | −0.002 (4) | 0.018 (3) |
C35 | 0.040 (5) | 0.067 (6) | 0.026 (4) | 0.004 (4) | 0.013 (4) | 0.005 (4) |
C36 | 0.074 (4) | 0.047 (4) | 0.037 (4) | −0.003 (3) | 0.014 (3) | 0.014 (3) |
C37 | 0.084 (4) | 0.062 (4) | 0.032 (4) | 0.047 (4) | 0.011 (3) | 0.010 (3) |
C38 | 0.044 (4) | 0.095 (5) | 0.041 (4) | 0.014 (4) | 0.012 (3) | 0.018 (4) |
C39 | 0.055 (4) | 0.054 (4) | 0.044 (4) | −0.014 (3) | 0.008 (3) | 0.026 (3) |
U—O1 | 2.252 (3) | C19—H19A | 0.9600 |
U—O2 | 2.260 (3) | C19—H19B | 0.9600 |
U—O3 | 1.790 (3) | C19—H19C | 0.9600 |
O1—C2 | 1.334 (6) | C20—H20A | 0.9600 |
O2—C13 | 1.344 (6) | C20—H20B | 0.9600 |
N1—C23 | 1.340 (6) | C20—H20C | 0.9600 |
N1—C27 | 1.343 (7) | C21—H21A | 0.9600 |
N1—C22 | 1.493 (6) | C21—H21B | 0.9600 |
N2—C29 | 1.338 (6) | C21—H21C | 0.9600 |
N2—C33 | 1.351 (6) | C22—H22A | 0.9700 |
N2—C28 | 1.516 (6) | C22—H22B | 0.9700 |
C1—C6 | 1.386 (7) | C23—C24 | 1.381 (7) |
C1—C2 | 1.415 (7) | C23—H23 | 0.9300 |
C1—C22 | 1.499 (7) | C24—C25 | 1.383 (8) |
C2—C3 | 1.418 (7) | C24—H24 | 0.9300 |
C3—C4 | 1.382 (7) | C25—C26 | 1.383 (7) |
C3—C11 | 1.527 (7) | C25—H25 | 0.9300 |
C4—C5 | 1.396 (7) | C26—C27 | 1.374 (7) |
C4—H4 | 0.9300 | C26—H26 | 0.9300 |
C5—C6 | 1.399 (7) | C27—H27 | 0.9300 |
C5—C7 | 1.525 (7) | C28—H28A | 0.9700 |
C6—H6 | 0.9300 | C28—H28B | 0.9700 |
C7—C8 | 1.524 (8) | C29—C30 | 1.375 (7) |
C7—C9 | 1.533 (8) | C29—H29 | 0.9300 |
C7—C10 | 1.545 (8) | C30—C31 | 1.368 (7) |
C8—H8A | 0.9600 | C30—H30 | 0.9300 |
C8—H8B | 0.9600 | C31—C32 | 1.374 (8) |
C8—H8C | 0.9600 | C31—H31 | 0.9300 |
C9—H9A | 0.9600 | C32—C33 | 1.376 (8) |
C9—H9B | 0.9600 | C32—H32 | 0.9300 |
C9—H9C | 0.9600 | C33—H33 | 0.9300 |
C10—H10A | 0.9600 | S—O6 | 1.436 (4) |
C10—H10B | 0.9600 | S—O5 | 1.439 (4) |
C10—H10C | 0.9600 | S—O4 | 1.440 (4) |
C11—C12 | 1.523 (7) | S—C34 | 1.825 (6) |
C11—H11A | 0.9700 | F1—C34 | 1.311 (7) |
C11—H11B | 0.9700 | F2—C34 | 1.339 (7) |
C12—C17 | 1.371 (7) | F3—C34 | 1.328 (7) |
C12—C13 | 1.409 (7) | N3—C35 | 1.296 (9) |
C13—C14 | 1.413 (7) | N3—C39 | 1.307 (10) |
C14—C15 | 1.386 (7) | C35—C36 | 1.334 (10) |
C14—C28 | 1.508 (7) | C35—H35 | 0.9300 |
C15—C16 | 1.388 (7) | C36—C37 | 1.341 (11) |
C15—H15 | 0.9300 | C36—H36 | 0.9300 |
C16—C17 | 1.394 (7) | C37—C38 | 1.410 (12) |
C16—C18 | 1.547 (7) | C37—H37 | 0.9300 |
C17—H17 | 0.9300 | C38—C39 | 1.371 (11) |
C18—C21 | 1.523 (7) | C38—H38 | 0.9300 |
C18—C19 | 1.527 (7) | C39—H39 | 0.9300 |
C18—C20 | 1.528 (8) | ||
O1—U—O2 | 89.33 (12) | C19—C18—C16 | 108.7 (4) |
O1—U—O2i | 90.67 (12) | C20—C18—C16 | 110.6 (4) |
O1—U—O3 | 90.75 (14) | C18—C19—H19A | 109.5 |
O2—U—O3 | 87.85 (14) | C18—C19—H19B | 109.5 |
O1—U—O3i | 89.25 (14) | H19A—C19—H19B | 109.5 |
O2—U—O3i | 92.15 (14) | C18—C19—H19C | 109.5 |
O3—U—O2i | 92.15 (14) | H19A—C19—H19C | 109.5 |
O3i—U—O3 | 180.00 | H19B—C19—H19C | 109.5 |
O3—U—O1i | 89.25 (14) | C18—C20—H20A | 109.5 |
O1—U—O1i | 180.00 | C18—C20—H20B | 109.5 |
O1i—U—O2 | 90.67 (12) | H20A—C20—H20B | 109.5 |
O2—U—O2i | 180.00 | C18—C20—H20C | 109.5 |
C2—O1—U | 139.0 (3) | H20A—C20—H20C | 109.5 |
C13—O2—U | 157.2 (3) | H20B—C20—H20C | 109.5 |
C23—N1—C27 | 120.7 (5) | C18—C21—H21A | 109.5 |
C23—N1—C22 | 120.3 (4) | C18—C21—H21B | 109.5 |
C27—N1—C22 | 118.9 (4) | H21A—C21—H21B | 109.5 |
C29—N2—C33 | 120.6 (5) | C18—C21—H21C | 109.5 |
C29—N2—C28 | 119.7 (4) | H21A—C21—H21C | 109.5 |
C33—N2—C28 | 119.7 (4) | H21B—C21—H21C | 109.5 |
C6—C1—C2 | 120.7 (5) | N1—C22—C1 | 114.6 (4) |
C6—C1—C22 | 120.7 (5) | N1—C22—H22A | 108.6 |
C2—C1—C22 | 118.6 (5) | C1—C22—H22A | 108.6 |
O1—C2—C1 | 119.8 (5) | N1—C22—H22B | 108.6 |
O1—C2—C3 | 122.1 (5) | C1—C22—H22B | 108.6 |
C1—C2—C3 | 118.0 (5) | H22A—C22—H22B | 107.6 |
C4—C3—C2 | 118.9 (5) | N1—C23—C24 | 120.8 (5) |
C4—C3—C11 | 121.0 (5) | N1—C23—H23 | 119.6 |
C2—C3—C11 | 120.1 (5) | C24—C23—H23 | 119.6 |
C3—C4—C5 | 124.1 (5) | C23—C24—C25 | 119.1 (5) |
C3—C4—H4 | 117.9 | C23—C24—H24 | 120.5 |
C5—C4—H4 | 117.9 | C25—C24—H24 | 120.5 |
C4—C5—C6 | 116.1 (5) | C26—C25—C24 | 119.2 (5) |
C4—C5—C7 | 120.6 (5) | C26—C25—H25 | 120.4 |
C6—C5—C7 | 123.3 (5) | C24—C25—H25 | 120.4 |
C1—C6—C5 | 122.2 (5) | C27—C26—C25 | 119.5 (5) |
C1—C6—H6 | 118.9 | C27—C26—H26 | 120.3 |
C5—C6—H6 | 118.9 | C25—C26—H26 | 120.3 |
C8—C7—C5 | 110.6 (5) | N1—C27—C26 | 120.7 (5) |
C8—C7—C9 | 109.0 (5) | N1—C27—H27 | 119.6 |
C5—C7—C9 | 109.6 (5) | C26—C27—H27 | 119.6 |
C8—C7—C10 | 107.4 (5) | C14—C28—N2 | 112.9 (4) |
C5—C7—C10 | 111.8 (5) | C14—C28—H28A | 109.0 |
C9—C7—C10 | 108.4 (5) | N2—C28—H28A | 109.0 |
C7—C8—H8A | 109.5 | C14—C28—H28B | 109.0 |
C7—C8—H8B | 109.5 | N2—C28—H28B | 109.0 |
H8A—C8—H8B | 109.5 | H28A—C28—H28B | 107.8 |
C7—C8—H8C | 109.5 | N2—C29—C30 | 121.0 (5) |
H8A—C8—H8C | 109.5 | N2—C29—H29 | 119.5 |
H8B—C8—H8C | 109.5 | C30—C29—H29 | 119.5 |
C7—C9—H9A | 109.5 | C31—C30—C29 | 119.6 (5) |
C7—C9—H9B | 109.5 | C31—C30—H30 | 120.2 |
H9A—C9—H9B | 109.5 | C29—C30—H30 | 120.2 |
C7—C9—H9C | 109.5 | C30—C31—C32 | 118.8 (5) |
H9A—C9—H9C | 109.5 | C30—C31—H31 | 120.6 |
H9B—C9—H9C | 109.5 | C32—C31—H31 | 120.6 |
C7—C10—H10A | 109.5 | C31—C32—C33 | 120.6 (5) |
C7—C10—H10B | 109.5 | C31—C32—H32 | 119.7 |
H10A—C10—H10B | 109.5 | C33—C32—H32 | 119.7 |
C7—C10—H10C | 109.5 | N2—C33—C32 | 119.5 (5) |
H10A—C10—H10C | 109.5 | N2—C33—H33 | 120.3 |
H10B—C10—H10C | 109.5 | C32—C33—H33 | 120.3 |
C12—C11—C3 | 112.7 (4) | O6—S—O5 | 115.3 (2) |
C12—C11—H11A | 109.1 | O6—S—O4 | 114.9 (2) |
C3—C11—H11A | 109.1 | O5—S—O4 | 115.2 (3) |
C12—C11—H11B | 109.1 | O6—S—C34 | 103.4 (3) |
C3—C11—H11B | 109.1 | O5—S—C34 | 102.7 (3) |
H11A—C11—H11B | 107.8 | O4—S—C34 | 102.8 (3) |
C17—C12—C13 | 119.6 (5) | F1—C34—F3 | 108.5 (5) |
C17—C12—C11 | 120.7 (5) | F1—C34—F2 | 107.0 (5) |
C13—C12—C11 | 119.7 (4) | F3—C34—F2 | 106.4 (5) |
O2—C13—C12 | 121.3 (4) | F1—C34—S | 111.6 (4) |
O2—C13—C14 | 120.8 (5) | F3—C34—S | 111.3 (4) |
C12—C13—C14 | 117.8 (5) | F2—C34—S | 111.7 (4) |
C15—C14—C13 | 119.8 (5) | C35—N3—C39 | 116.9 (7) |
C15—C14—C28 | 120.4 (4) | N3—C35—C36 | 124.3 (8) |
C13—C14—C28 | 119.8 (4) | N3—C35—H35 | 117.8 |
C16—C15—C14 | 123.3 (5) | C36—C35—H35 | 117.8 |
C16—C15—H15 | 118.4 | C35—C36—C37 | 120.2 (8) |
C14—C15—H15 | 118.4 | C35—C36—H36 | 119.9 |
C15—C16—C17 | 115.3 (5) | C37—C36—H36 | 119.9 |
C15—C16—C18 | 125.0 (4) | C36—C37—C38 | 117.8 (8) |
C17—C16—C18 | 119.6 (5) | C36—C37—H37 | 121.1 |
C12—C17—C16 | 124.1 (5) | C38—C37—H37 | 121.1 |
C12—C17—H17 | 118.0 | C39—C38—C37 | 116.2 (8) |
C16—C17—H17 | 118.0 | C39—C38—H38 | 121.9 |
C21—C18—C19 | 108.8 (5) | C37—C38—H38 | 121.9 |
C21—C18—C20 | 108.3 (5) | N3—C39—C38 | 124.6 (8) |
C19—C18—C20 | 108.4 (5) | N3—C39—H39 | 117.7 |
C21—C18—C16 | 111.9 (4) | C38—C39—H39 | 117.7 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [UO2(C33H38N2O2)2](CF3O3S)2·2C5H5N |
Mr | 1715.68 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.7189 (9), 11.1479 (13), 17.0975 (16) |
α, β, γ (°) | 102.472 (6), 106.903 (6), 94.800 (6) |
V (Å3) | 1885.0 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.29 |
Crystal size (mm) | 0.40 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.698, 0.892 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13391, 6934, 5444 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.096, 1.03 |
No. of reflections | 6934 |
No. of parameters | 481 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.54, −2.30 |
Computer programs: EVALCCD (Duisenberg et al., 2003), EVALCCD, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.
U—O1 | 2.252 (3) | U—O3 | 1.790 (3) |
U—O2 | 2.260 (3) | ||
O1—U—O2 | 89.33 (12) | O2—U—O3 | 87.85 (14) |
O1—U—O3 | 90.75 (14) |
In their polyphenoxide form, homooxacalixarenes (Masci, 2001), as well as the more widespread calixarenes, are ligands well suited to uranyl ion [dioxouranium(VI)] complexation (Thuéry et al., 2001). In order to extend the investigation of uranium complexes of homooxacalixarenes to lower oxidation states of this cation, we have recently studied the reaction of UCl4 with p-tert-butyltetrahomodioxacalix[4]arene, p-tert-butylhexahomotrioxacalix[6]arene and p-tert-butyloctahomotetraoxacalix[8]arene in pyridine, with the unexpected result of homooxacalixarene cleavage to give the diphenoxide species bis[5-tert-butyl-2-oxido-3-(1-pyridiniomethyl)-phenyl]methane (L), and subsequent isolation of the 1:1 or 1:2 UIV/L complexes (Salmon et al., 2003). The proposed mechanism involves nucleophilic attack of pyridine on the ether bridges, likely assisted by initial U coordination to the ether O atoms. In the course of a similar study with U(OSO2CF3)4 and p-tert-butyltetrahomodioxacalix[4]arene as starting materials, further oxidation of the metal centre, due either to oxygen contamination or the presence of water released by the cleavage reaction, resulted in the isolation of the present uranyl complex, (I), and its structure is presented here. \sch
The asymmetric unit in (I) contains half a complex molecule, with the U atom located on a centre of symmetry, and a trifluoromethanesulfonate counterion and a pyridine solvent molecule. The U atom is bound (Fig. 1, Table 1) to two phenoxide O atoms from each neutral doubly zwitterionic ligand, with a mean U—O bond length of 2.256 (6) Å, typical of such phenoxide complexes (Thuéry et al., 2001). The O(phenoxide)-U—O(phenoxide) and O(oxo)-U—O(phenoxide) angles are close to 90° [87.85 (14)–92.15 (14)°], and the equatorial environment of the uranyl ion is thus a rather regular square.
We have previously reported the crystal structure of the 1:2 uranyl complex of another diphenoxide species, in which the cationic pyridiniomethyl groups present in L are replaced by neutral hydroxymethyl substituents. That structure comprises three independent molecules, either centrosymmetric or pseudo-centrosymmetric, in which the U environment is close to that of (I); in one of these molecules, however, this environment is somewhat less regular, due to the presence of an intramolecular O(hydroxyl)···O(phenoxide) hydrogen bond between the two ligands (Thuéry et al., 2002). The two phenoxide rings in (I), as well as in the previous complex, adopt a `butterfly' conformation and are located on either side of the uranyl equatorial plane. The dihedral angles in (I) between the two phenoxide rings of each ligand and this plane are 43.94 (14) and 25.8 (2)° and, between the two phenoxide rings, 69.66 (17)°, whereas the corresponding values in the previous complex are 36.9 (6)–52.4 (5)° and 71.4 (6)–79.6 (7)°, respectively. The ligand L in its 1:1 and 1:2 UIV complexes adopts a similar conformation, with dihedral angles between the two aromatic rings larger than in (I), at 76.3 (2) and 76.2 (4)°. Even if these diphenoxide species give complexes with comparable overall arrangements, the differences in finer geometric details evidence the flexibility of these ligands and their ability to adapt themselves to differing coordination requirements [as between UIV and UVI cations] or differing weak interactions.
The two pyridiniomethyl arms of each ligand in (I) are directed away from the uranyl equatorial plane, i.e. towards the concave side of the diphenoxide ligand. The aromatic ring containing atom N2 is involved in two weak but significant π–π stacking interactions, one with its counterpart in the neighbouring molecule at (1 − x, 1 − y, 1 − z) [centroid-centroid distance 3.59 Å, interplanar spacing 3.38 Å, centroid offset 1.21 Å] and the other, weaker, with the solvent pyridine molecule [centroid-centroid distance 4.00 Å, interplanar spacing 3.58 Å, centroid offset 1.78 Å, dihedral angle between the two rings 10.51 (17)°, shortest interatomic contact C29···C36 = 3.368 (9) Å, equal to twice the out-of-plane van der Waals radius of C (1.7 Å)].
The pyridine solvent molecule is located in the `cup' defined by the two phenoxide rings of the ligand (Fig. 2), in which it is held by two C—H···π interactions, the first between atom H35 and the aromatic ring C1—C6 bound to atom O1 [H35···centroid distance 2.90 Å, C35—H35···centroid angle 173°], and the second between atom H36 and the aromatic ring C12—C17 bound to atom O2 [H36···centroid distance 2.77 Å, C36–H36···centroid angle 148°]. In the previous uranyl ion complex with a diphenoxide species, a comparable position was occupied by a HDABCO cation (DABCO is 1,4-diazabicyclo[2.2.2]octane), but in that case the cation was primarily held by a strong N—H···O(oxo) hydrogen bond with the central uranyl ion and by cation···π interactions involving the phenoxide rings (Thuéry et al., 2002). Another weak CH···π interaction may be considered in (I), between an H atom of the tert-butyl group bound to the phenoxide ring bearing atom O2 and the pyridine molecule at (1 − x, 1 − y, −z) [H19C···centroid distance 2.89 Å, C19—H19C···centroid angle 155°].
The present result provides a new example of homooxacalixarene cleavage in the presence of pyridine and UIV salts, UCl4 being replaced in this case by U(OSO2CF3)4. Further oxidation of the metal centre leads to the second example of a diphenoxide complex of the uranyl ion. However, we have also reported that some triphenols complex this ion in their diphenoxide form (Thuéry et al., 2002, and references therein). Direct reaction of uranyl salts with p-R-tetrahomodioxacalix[4]arene (where R is methyl, tert-butyl or phenyl), in the presence of bases such as amines or alkali metal hydroxides, does not result in homooxacalixarene cleavage, even in the presence of pyridine. In these cases, `internal' tetraphenoxide-coordinated uranyl complexes are obtained, which differ in their counterions, solvent environment and supramolecular arrangement (Thuéry & Masci, 2003, and references therein). The homooxacalixarene in all these complexes is in a cone conformation and, as a consequence, all the phenoxide rings are on the same side of the uranyl equatorial plane, which is at variance with the centrosymmetrical geometry of complex (I). In these homooxacalixarene complexes, the mean U—O(phenoxide) bond length of 2.28 (2) Å (eight compounds) appears slightly larger, albeit with little significance, than that in (I) or in the previous uranyl diphenoxide complex [2.25 (2) Å], which may be due to the geometrical constraints imposed by the cyclic nature of the homooxacalixarene. The range of O(phenoxide)-U—O(phenoxide) angles is also larger in the macrocyclic complexes [82.1 (3)–97.7 (3)°], in conjunction with very different O···O distances between adjacent phenoxide groups [mean values 3.10 (2) Å for groups separated by a methylenic link and 3.34 (3) Å for groups separated by an ether link, compared with O1···O2 3.171 (5) and O1···O2' 3.209 (5) Å in (I)], which is due to the presence of the two ether links, which act as spacers.