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Uranyl Ion Complexes with Ammoniobenzoates as
Assemblers for Cucurbit[6]uril Molecules
Pierre Thuéry
CEA, IRAMIS, UMR 3299 CEA/CNRS, SIS2M, Laboratoire de Chimie de Coordination des
Eléments f, Bât. 125, 91191 Gif-sur-Yvette, France
ABSTRACT: The crystal structures of the complexes formed under hydrothermal conditions by uranyl ions with 4aminobenzoic
(HL1),
4-amino-3-methylbenzoic
(HL2),
4-(aminomethyl)benzoic
(HL3)
and
3-amino-5-
hydroxybenzoic (HL4) acids, in the presence of cucurbit[6]uril (CB6), have been determined. These ligands have
been chosen because, in their zwitterionic form, they display both a metal-complexing carboxylate group and an
ammonium group able to associate with CB6 through ion-dipole and hydrogen bonding interactions. The complexes
[H2NMe2]2[(UO2)2(L1)2O(OH)(H2O)]2·CB6·15H2O (1) and [H2NMe2]2[(UO2)2(L2)2O(OH)(H2O)]2·CB6·17H2O (2)
were obtained in the presence of dimethylformamide, which gives dimethylammonium ions in situ. The latter are held
at the CB6 portals while the tetranuclear uranyl complex with the aminobenzoate anions is not bound to CB6. The
neutral, ammonium-containing form of the ligand is present in [UO2(HL3)(OH)(HCOO)(H2O)]2·2CB6·2DMF·
14H2O (3), in which the di(µ2-hydroxo)-bridged, dinuclear uranyl complex displays two diverging, monodentate HL3
ligands. The latter are associated to two CB6 molecules to give a dumbbell-shaped supramolecular assembly. Three
CB6 molecules are assembled around a tetranuclear uranyl complex in [(UO2)4(HL3)2(L3)O2(OH)2(H2O)4]·2CB6·
0.5CB8·HL3·NO3·20H2O (4), with two of them being bridging and giving rise to a one-dimensional, linear
supramolecular architecture. Finally, the 3-amino substituted ligand HL4 gives the highly symmetric complex
[UO2(HL4)(L4)2]·3CB6·16H2O (5), in which the uranyl ion is chelated by three carboxylate groups. Three CB6
molecules are assembled around the planar complex to give a triangular, discrete species. In compounds 3–5, the
usual packing of CB6 molecules into columns or layers is not retained as it is frequently in the presence of uranyl–
organic complexes. This is due to the CB6-assembling role of the heterodifunctional ligands, which hold the CB6
molecules at the periphery of mono-, di- or tetranuclear uranyl complexes of quite usual, planar geometry.
1
Introduction
The affinity of cucurbiturils1 for ammonium ions, originating in charge–dipole and
hydrogen bonding interactions, is central to the use of these macrocycles in the design of
supramolecular systems. The host–guest complexes formed by cucurbit[6]uril (CB6, Scheme 1)
with alkyl- and aryl-substituted ammonium cations, for which hydrophobic effects allow for the
inclusion of the substituents, were investigated early.2 CB6 complexation of diaminoalkanes2a,c,3
proved to be particularly important since it paved the way for the synthesis of polyrotaxanes and
molecular necklaces involving metal ion coordination by functional groups located at both ends
of the included species.4 Molecules comprising a single ammonium group may also be of interest
for the building of metal–organic supramolecular assemblies since, if they are properly
functionalized, they can be used as linkers between the metal ion and the CB6 moiety. Recently,
iminodiacetic acid, in its zwitterionic form, was shown to be able to complex a lanthanide ion
through its carboxylate group while being attached to CB6 by its ammonium function, with the
unusual consequence of the uncomplexed carboxylic acid group being included in the CB6
cavity.5 α-Amino-acids in their zwitterionic form are also heterofunctional molecules suitable as
metal ion/CB6 linkers, as shown in the chiral, columnar one-dimensional assemblies obtained
with lanthanide ions, in which the latter are bound to both carboxylate and CB6 moieties.6
Attempts at obtaining similar complexes with the uranyl ion, which is readily complexed by
carboxylates and also by cucurbiturils,7 were unsuccessful. This led to the search of other suitable
aminocarboxylic acids, and the family of aminobenzoic acids appeared of interest for the
variations it provides on the relative positions of the functional groups, and the presence of
additional substituents. Uranyl ion complexes with 4-aminobenzoic (HL1), 4-amino-3-
2
methylbenzoic (HL2), 4-(aminomethyl)benzoic (HL3) and 3-amino-5-hydroxybenzoic (HL4)
acids (Scheme 2), could be crystallized in the presence of CB6 molecules, and the structures of
the compounds obtained, which display novel features among the family of uranyl–cucurbituril
compounds, are reported herein.
Experimental Section
Synthesis. Caution! Because uranium is a radioactive and chemically toxic element, uraniumcontaining samples must be handled with suitable care and protection.
UO2(NO3)2·6H2O was purchased from Prolabo, CsNO3 from Acros, 4-amino-3methylbenzoic and 4-(aminomethyl)benzoic acids from Aldrich, and 4-aminobenzoic acid, 3amino-5-hydroxybenzoic acid hydrochloride and cucurbit[6]uril pentahydrate from Fluka.
Elemental analyses were performed by MEDAC Ltd., UK.
[H2NMe2]2[(UO2)2(L1)2O(OH)(H2O)]2·CB6·15H2O (1). CB6·5H2O (11 mg, 0.01
mmol), a 10-fold excess of UO2(NO3)2·6H2O (50 mg, 0.10 mmol) and HL1 (14 mg, 0.10 mmol),
DMF (0.5 mL), and demineralized water (1.2 mL) were placed in a 15 mL tightly closed glass
vessel and heated at 180 °C under autogenous pressure. Light yellow crystals of complex 1
appeared within 24 h (17 mg, 55% yield on the basis of CB6). Anal. calcd for C68H112N30O49U4:
C, 26.47; H, 3.66; N, 13.62. Found: C, 26.00; H, 3.19; N, 13.58%.
[H2NMe2]2[(UO2)2(L2)2O(OH)(H2O)]2·CB6·17H2O (2). CB6·5H2O (11 mg, 0.01
mmol), a 10-fold excess of UO2(NO3)2·6H2O (50 mg, 0.10 mmol) and HL2 (15 mg, 0.10 mmol),
DMF (0.5 mL), and demineralized water (1.2 mL) were placed in a 15 mL tightly closed glass
3
vessel and heated at 180 °C under autogenous pressure. Light yellow crystals of complex 2
appeared within one week.
[UO2(HL3)(OH)(HCOO)(H2O)]2·2CB6·2DMF·14H2O (3). CB6·5H2O (11 mg, 0.01
mmol), a 10-fold excess of UO2(NO3)2·6H2O (50 mg, 0.10 mmol) and HL3 (15 mg, 0.10 mmol),
DMF (0.5 mL), and demineralized water (1.2 mL) were placed in a 15 mL tightly closed glass
vessel and heated at 180 °C under autogenous pressure. Light yellow crystals of complex 3,
mixed with a white powder, appeared in low yield within one week.
[(UO2)4(HL3)2(L3)O2(OH)2(H2O)4]·2CB6·0.5CB8·HL3·NO3·20H2O (4). CB6·5H2O
(11 mg, 0.01 mmol), a 10-fold excess of UO2(NO3)2·6H2O (50 mg, 0.10 mmol), HL3 (15 mg,
0.10 mmol) and CsNO3 (20 mg, 0.10 mmol), and demineralized water (1.5 mL) were placed in a
15 mL tightly closed glass vessel and heated at 180 °C under autogenous pressure. Light yellow
crystals of complex 4, mixed with a white powder, appeared in very low yield within one week.
[UO2(HL4)(L4)2]·3CB6·16H2O (5). CB6·5H2O (11 mg, 0.01 mmol), a 10-fold excess of
UO2(NO3)2·6H2O (50 mg, 0.10 mmol) and HL4·HCl (19 mg, 0.10 mmol), and demineralized
water (1.5 mL) were placed in a 15 mL tightly closed glass vessel and heated at 180 °C under
autogenous pressure. Light yellow crystals of complex 5, mixed with a brownish amorphous
powder, appeared in very low yield overnight. Attempts to increase the yield by prolonged
heating were unsuccessful.
Crystallography. The data were collected at 150(2) K on a Nonius Kappa-CCD area
detector diffractometer8 using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The
crystals were introduced into glass capillaries with a protecting “Paratone-N” oil (Hampton
Research) coating. The unit cell parameters were determined from ten frames, then refined on all
data. The data (combinations of ϕ- and ω-scans giving complete data sets up to θ = 28.7° (25.7°
4
for 4) and a minimum redundancy of 4 for 90% of the reflections) were processed with
HKL2000.9 Absorption effects were corrected empirically with the program SCALEPACK.9 The
structures were solved by direct methods (1–4) or Patterson map interpretation (5) with SHELXS97, expanded by subsequent Fourier-difference synthesis and refined by full-matrix least-squares
on F2 with SHELXL-97.10 All non-hydrogen atoms were refined with anisotropic displacement
parameters. Some lattice water molecules were given 0.5 occupancy factors in order to retain
acceptable displacement parameters and/or to account for too close contacts. The hydrogen atoms
bound to oxygen and nitrogen atoms in 1–3 and 5 were found on Fourier-difference maps, except
for those of N15 in 1 (which were introduced at ideal positions) and those of some solvent water
molecules, but they were neither found, nor introduced, in 4; the carbon-bound hydrogen atoms
were introduced at calculated positions. All hydrogen atoms were treated as riding atoms with an
isotropic displacement parameter equal to 1.2 (OH, NH, CH, CH2) or 1.5 (CH3) times that of the
parent atom. Due to the low quality of the crystals and the large size of the asymmetric unit (2530
parameters refined), the structure of 4 could not be determined with a high degree of precision;
several parts of this structure are badly resolved and restraints on bond lengths, angles and/or
displacement parameters had to be applied, particularly in the uncoordinated HL3 molecule, and
two aromatic rings were refined as idealized hexagons; large voids in the lattice likely indicate
the presence of other, unresolved water solvent molecules.
Crystal data and structure refinement parameters are given in Table 1 and selected bond
lengths and angles in Table 2. The molecular plots were drawn with ORTEP-311 and the
polyhedral representations with VESTA.12
5
Results and Discussion
The
complexes
[H2NMe2]2[(UO2)2(L1)2O(OH)(H2O)]2·CB6·15H2O
(1)
and
[H2NMe2]2[(UO2)2(L2)2O(OH)(H2O)]2·CB6·17H2O (2) both involve benzoic acid with an amino
group in the para position, with an additional methyl group in the meta position being present in
2. The latter has little influence and both compounds can be considered to be isomorphous. Both
were obtained with dimethylformamide (DMF) being added in the reaction medium, so as to
improve dissolution. Under the conditions used, DMF undergoes hydrolysis to give formic acid
and dimethylamine, as was often previously observed, not necessarily under hydrothermal
conditions, but always in the presence of metal ions which are possibly catalysts for this
reaction.7f,g,13 As a consequence, dimethylammonium or formate ions are often present in the
complexes formed,7f,g and this is the case in 1 and 2, which contain H2NMe2+ counterions. The
centrosymmetric, bis(µ3-oxo)-centered tetranuclear uranyl complex found in both compounds,
and represented in Figure 1 for complex 1, is a frequent motif in uranyl chemistry, which is found
in many molecular species7a,14 and also in coordination polymers including CB6.7f The uranyl
ions in 1 and 2 are laterally bridged by two hydroxide ions and two κ2-O,Oʹ-L1– anions. Two
other L1– ligands are chelating U1 and its image by the inversion center, while two water
molecules complete the coordination sphere of the other two uranium atoms, all metal atoms
being thus in pentagonal bipyramidal environments. The U–O bond lengths, averaged over both
complexes, for oxo, hydroxo, bridging carboxylate, chelating carboxylate and water ligands,
which amount to 2.25(4), 2.37(4), 2.40(4), 2.51(4) and 2.487(5) Å, respectively, are
unexceptional. The four amino groups point towards the exterior of the nearly planar tetranuclear
6
unit, but, being unprotonated, they are not involved in any interaction with the CB6 molecules.
Instead, they form hydrogen bonds with carboxylate oxygen atoms, uranyl oxo groups and water
molecules. The two portals of the centrosymmetric CB6 molecules are occupied by the
dimethylammonium counterions, which are hydrogen bonded to two carbonyl groups [N···O and
H···O distances, and N–H···O angles are in the ranges 2.801(12)–2.903(6), 1.98–2.10 Å, and
150–154°, respectively]. Although both amine and ammonium groups are hydrogen bond donors,
it is unsurprising that CB6 associates preferentially with the ionic species through charge–dipole
interactions, since the latter are predominant in CB6–ammonium host-guest complexes.2 The lack
of association between the uranyl complex and CB6 is thus a consequence of the use of DMF.
Unfortunately, no crystalline material could be obtained in these cases, when the reaction was
performed in pure water. The packing in 1 and 2 displays a parallel arrangement of the CB6
molecules, which are stacked in columns directed along the a axis, while the uranyl complex
moieties are tilted with respect to one another so as to build a herringbone pattern when viewed
down the c axis (Figure 1). When projected onto the bc plane, the uranyl complexes appear to be
arranged in a square grid pattern, with the CB6 column axis coinciding with the center of the grid
voids.
The
complex
with
the
4-aminomethyl
substituted
ligand
HL3,
[UO2(HL3)(OH)(HCOO)(H2O)]2·2CB6·2DMF·14H2O (3), was also obtained in the presence of
DMF, but, fortunately, dimethylammonium ions are not present in the final compound, which
however contains formate anions, the other product of DMF hydrolysis. Only one uranyl ion is
present in the asymmetric unit, which is bound to a monodentate carboxylate group from the HL3
ligand and one from the formate ion, while bridging hydroxide ions result in the formation of a
centrosymmetric dimer (Figure 2). One water molecule completes the five-coordinate equatorial
7
environment. The average U–O bond lengths for carboxylate and hydroxo ligands are 2.377(17)
and 2.32(2) Å, respectively. Intramolecular hydrogen bonds link the hydroxide ion to the
uncomplexed carboxylate oxygen atom of HL3 and the water molecule to the uncoordinated
oxygen atom of formate. The HL3 ligand is in its zwitterionic form and this, together with the
absence of other ammonium groups, enables HL3 to come into contact with CB6 through its
ammonium substituent. The nitrogen atom N1 is at a distance of 0.082(5) Å from the portal mean
plane and it forms hydrogen bonds with the carbonyl atoms O9 and O11, and with the oxygen
atom of a DMF molecule included in the CB6 cavity [N···O and H···O distances, and N–H···O
angles are in the ranges 2.705(7)–2.890(6), 1.99–2.17 Å, and 126–159°, respectively]. Large,
dumbbell-shaped supramolecular assemblies are thus formed, which consist in two terminal CB6
molecules held by the central binuclear uranyl moiety. These assemblies are tilted with respect to
one another and they are stacked to form layers in which neighbouring CB6 molecules are located
such that the free portal of one is directed towards the side of the other, so that CH···O hydrogen
bonds are formed (shorter C···O and H···O distances, 3.07 and 2.20 Å, respectively).
Another synthesis with the same ligand HL3, in the absence of DMF, but with CsNO3
being added, gave the complex [(UO2)4(HL3)2(L3)O2(OH)2(H2O)4]·2CB6·0.5CB8·HL3·NO3·
20H2O (4). Only few crystals of quite poor quality were obtained, and the large structure (284
independent non-hydrogen atomic positions) could only be determined with moderate accuracy.
The main features are however unambiguous and deserve some comments in the present context.
CB8 is present in the final compound, as in previously reported complexes obtained from CB6,7a,f
which likely indicates the presence of the former as an impurity in CB6, and accounts for the low
yield observed. The asymmetric unit corresponds to one formula unit, in which the uranyl ions are
assembled into a bis(µ3-oxo)-centered tetranuclear cluster devoid of any true symmetry (Figure
8
3). Atom U1 is chelated by a carboxylate group, while two other L3–/HL3 ligands are bridging the
pairs of atoms U1, U2 and U3, U4. Two hydroxide ions (O11, O12) provide additional bridging.
Curiously, instead of another chelating HL3 ligand, two water molecules complete the
coordination sphere of U4. U2 and U3 are also bound to one water molecule each, all uranium
atoms being thus in pentagonal bipyramidal environments. The average U–O bond lengths for
oxo, hydroxo, bridging carboxylate, chelating carboxylate and water ligands are unexceptional, at
2.27(4), 2.34(5), 2.39(6), 2.495(13) and 2.50(6) Å, respectively. Although this tetranuclear motif
is very close to that encountered in complexes 1 and 2, apart from the missing chelating ligand,
the protonation of two amine groups out of three (for charge balance) and the absence of other
ammonium ions in the reaction medium enable L3–/HL3–CB6 interactions to take place, as in
complex 3. Three CB6 molecules are thus held around the tetranuclear unit, with one of them,
corresponding to N3, being the image of that bonded to N2 through a glide plane followed by
translations along the a and b axes. The ammonium nitrogen atoms are not all identically located
with respect to the portals, with distances of 0.346(12), 1.79(3) and 0.081(12) Å for N1, N2 and
N3, respectively. As a consequence, N1 and N3 make three and N2 only two possible hydrogen
bonding contacts with carbonyl oxygen atoms, with N···O distances in the range 2.80(3)–2.97(2)
Å. However, the hydrogen atoms were not found in this structure and it cannot be known with
certainty if N2 is the unprotonated atom (which is likely) or if the protons are disordered over the
three amine groups. Due to the bridging CB6 molecule bound to one cluster by each of its two
portals, a one-dimensional supramolecular assembly is built, which runs along the [2 0 ī] axis
(Figure 3). When viewed along the chain axis, the arrangement consists in a central row of
tetranuclear clusters surrounded on each side by the bridging CB6 molecules, and with the
pendent CB6 located in two rows close to one another on the same side of the chain. The
9
compound also contains an independent CB8 molecule located around an inversion center, with
two included and probably hydrogen bonded (but very badly resolved) HL3 molecules (Figure 3),
which are involved together in a π-stacking interaction (centroid···centroid distance 3.76 Å, offset
0.39 Å). The stacking of the one-dimensional assemblies and CB8 molecules results in a very
intricate packing.
The fourth ligand used, HL4, is the only one in which the amine group is not in the para
position with respect to the carboxylic group. Instead, the amine and hydroxyl groups occupy
both meta positions. In the complex obtained, [UO2(HL4)(L4)2]·3CB6·16H2O (5), which
crystallizes in the hexagonal system, the uranyl ion is located on a six-fold roto-inversion axis and
it is chelated by three equivalent carboxylate groups (Figure 4), with an unexceptional average U–
O bond length of 2.465(12) Å; the uranium environment is thus hexagonal bipyramidal. Three
protons were found on atom N1 during structure refinement (as well as the hydroxylic proton),
whereas charge balance requires one protonated and two deprotonated ligands. It was assumed
that the extra proton was disordered over the three amine sites, and the occupancy factors of the
protons were chosen accordingly. The neutral [UO2(HL4)(L4)2] complex is located in a symmetry
plane, which bisects the CB6 molecule. The latter is associated with the ammonium/amine group,
with the nitrogen atom located at 0.161(4) Å from the mean portal plane (on the exterior side) and
involved in possible hydrogen bonds with four carbonyl groups [N···O and H···O distances, and
N–H···O angles are 2.963(4), 2.18 Å, and 136° for the bifurcated bond with O5 and its symmetry
equivalent, and 2.895(3), 2.07 Å, and 155° for the two bonds with O7 and its symmetry
equivalent]. The hydroxyl group is hydrogen bonded to a solvent water molecule, which is
possibly bound itself to a carbonyl group, thus probably bringing only a very minor contribution
10
to the HL4/CB6 interactions. The packing of these supramolecular trimeric units displays
cylindrical channels along the c axis, which are occupied by the solvent molecules (Figure 4).
Conclusion
Among the five uranyl ion complexes with amino- or ammoniobenzoates reported herein,
three display ammonium–CB6 associations, these being absent in the cases where the amine
group is unprotonated and a competing ammonium species is present. These associations
originate in ion-dipole and hydrogen bonding interactions, but the hydrophobic effects which are
present for the much used diaminoalkane derivatives are absent since no part of the molecule is
included in the CB6 cavity. The supramolecular assemblies thus formed display different
geometries, being either dimeric and dumbbell-shaped (3), one-dimensional polymeric with both
bridging and pendent CB6 molecules (4), or discrete and triangular (5). These assemblies, and
particularly the polymeric one, are reminiscent of the species generated through molecular
recognition in the molecular tectonics approach.15 In complexes 3–5, the arrangement of the
amino/ammoniobenzoate ligands around the uranyl ion governs the location of the CB6
molecules, and it is notable that the frequent arrangement of CB6 into columns or sheets is not
found here. This is in contrast to the architectures often observed in compounds comprising
uranyl ion complexes and coordinated or free CB6 molecules, in which the typical geometries of
both subunits are retained. Due to the strong tendency for uranyl ions to give planar or undulated
ribbons or sheets, owing to the equatorial positioning of its ligands, it is frequent to observe in
such compounds an alternation of uranyl–organic sheets and CB6 layers or columns.7f,g The
present ligands are different from those used in the previous studies since they are
11
heterodifunctional and able to bridge the metal ions and CB6 molecules (as iminodiacetic acid
and α-amino acids in the case of lanthanide ions5,6). They give mono-, di- or tetranuclear uranyl
complexes of quite usual, planar geometry, around which the CB6 molecules are arranged. The
overall architecture is imposed by the uranyl complexes, which can thus be viewed as efficient
assemblers of CB6 units.
Acknowledgment. The Direction de l’Energie Nucléaire of the CEA is thanked for its financial
support through the Basic Research Program RBPCH.
Associated Content
Supporting Information. Tables of crystal data, atomic positions and displacement parameters,
anisotropic displacement parameters, and bond lengths and bond angles in CIF format. This
information is available free of charge via the Internet at http://pubs.acs.org.
Author Information
Corresponding Author
E-mail: [email protected].
12
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14
Vicens, J. J. Chem. Soc., Dalton Trans. 1999, 2589. (d) Gerasko, O. A.; Samsonenko, D. G.;
Sharonova, A. A.; Virovets, A. V.; Lipkowski, J.; Fedin, V. P. Russ. Chem. Bull. 2002, 51,
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Crawford, M. J.; Mayer, P.; Nöth, H.; Suter, M. Inorg. Chem. 2004, 43, 6860. (g) Harrowfield,
J. M.; Skelton, B. W.; White, A. H. C. R. Chimie 2005, 8, 169. (h) Charushnikova, I. A.; Krot,
N. N.; Polyakova, I. N.; Makarenkov, V. I. Radiokhimiya 2005, 47, 219. (i) Borkowski, L. A.;
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M. A.; Romerosa, A.; Colacio, E. Dalton Trans. 2009, 9578.
15. Hosseini, M. W. Acc. Chem. Res. 2005, 38, 313.
15
Table 1. Crystal Data and Structure Refinement Details
1
chemical formula
M (g mol−1)
cryst syst
space group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
Dcalcd (g cm−3)
µ(Mo Kα) (mm−1)
F(000)
reflns collcd
indep reflns
obsd reflns [I > 2σ(I)]
Rint
params refined
R1
wR2
S
∆ρmin (e Å−3)
∆ρmax (e Å−3)
C68H112N30O49U4
3086.00
monoclinic
P21/n
12.2719(2)
23.9584(4)
16.5871(3)
90
90.4637(6)
90
4876.70(14)
2
2.102
6.735
2980
161399
12613
10042
0.054
696
0.039
0.108
1.064
−1.29
2.57
2
C72H124N30O51U4
3178.13
monoclinic
P21/n
12.4840(6)
23.8021(12)
17.3035(7)
90
92.533(3)
90
5136.6(4)
2
2.055
6.399
3084
163660
13259
9563
0.045
716
0.041
0.102
1.000
−1.48
1.35
3
C96H140N52O56U2
3394.66
monoclinic
P21/n
13.1650(4)
16.6185(5)
28.8324(10)
90
98.013(2)
90
6246.4(3)
2
1.805
2.710
3424
175553
16109
11644
0.052
939
0.040
0.104
0.997
−1.06
2.36
16
4
C128H181N69O79U4
4902.54
monoclinic
P21/c
17.8308(8)
29.1315(10)
36.6998(18)
90
98.238(3)
90
18866.6(14)
4
1.726
3.534
9728
371503
35661
16972
0.097
2530
0.103
0.314
0.991
−4.58
7.10
5
C129H159N75O63U
4006.34
hexagonal
P63/m
24.2936(6)
24.2936(6)
15.6891(3)
90
90
120
8018.9(5)
2
1.659
1.132
4108
141493
7138
5970
0.051
447
0.042
0.127
1.068
−0.87
1.59
Table 2. Environment of the Uranium Atoms in Compounds 1–5: Selected Bond Lengths (Å) and Angles (deg)a
1
2
3
a
U1–O1
U1–O2
U1–O5
U1–O6
U1–O7
U1–O8
U1–O9
U2–O3
U2–O4
U2–O5
U2–O5i
U2–O6i
U2–O10
U2–O11
U1–O1
U1–O2
U1–O5
U1–O6
U1–O7
U1–O8
U1–O9
U2–O3
U2–O4
U2–O5
U2–O5i
U2–O6i
U2–O10
U2–O11
U–O1
U–O2
U–O3
U–O5
U–O7
U–O7i
U–O8
1.788(4)
1.793(4)
2.215(4)
2.321(4)
2.468(4)
2.572(4)
2.347(4)
1.794(4)
1.803(4)
2.252(4)
2.295(4)
2.403(4)
2.451(4)
2.481(4)
1.796(3)
1.797(3)
2.185(3)
2.339(4)
2.480(3)
2.527(4)
2.377(3)
1.798(4)
1.789(3)
2.264(3)
2.310(3)
2.416(4)
2.437(3)
2.492(4)
1.784(3)
1.780(3)
2.360(3)
2.394(3)
2.298(2)
2.339(3)
2.486(3)
O1–U1–O2
O5–U1–O6
O6–U1–O7
O7–U1–O8
O8–U1–O9
O9–U1–O5
173.35(19)
70.21(14)
72.66(14)
51.96(12)
80.40(15)
85.16(15)
O3–U2–O4
O5–U2–O5i
O5i–U2–O6i
O6i–U2–O11
O11–U2–O10
O10–U2–O5
173.58(19)
71.05(16)
67.45(14)
72.83(15)
70.82(15)
78.49(14)
O1–U1–O2
O5–U1–O6
O6–U1–O7
O7–U1–O8
O8–U1–O9
O9–U1–O5
173.65(16)
70.61(13)
76.10(12)
52.21(12)
75.44(12)
85.68(13)
O3–U2–O4
O5–U2–O5i
O5i–U2–O6i
O6i–U2–O11
O11–U2–O10
O10–U2–O5
172.58(16)
70.62(14)
67.23(12)
75.21(12)
71.47(13)
76.05(12)
O1–U–O2
O3–U–O8
O8–U–O5
O5–U–O7i
O7i–U–O7
O7–U–O3
177.89(12)
71.06(10)
72.14(10)
72.48(10)
67.79(11)
76.53(9)
U1–O1
U1–O2
U1–O9
U1–O11
U1–O13
U1–O14
U1–O15
U2–O3
U2–O4
U2–O9
U2–O10
U2–O12
U2–O16
U2–O19
U3–O5
U3–O6
U3–O9
U3–O10
U3–O11
U3–O17
U3–O20
U4–O7
U4–O8
U4–O10
U4–O12
U4–O18
U4–O21
U4–O22
U–O1
U–O2
U–O3
4
5
1.790(10)
1.817(10)
2.203(9)
2.310(9)
2.482(10)
2.508(9)
2.370(11)
1.748(10)
1.752(10)
2.237(9)
2.339(10)
2.400(13)
2.463(14)
2.496(13)
1.819(9)
1.787(9)
2.277(8)
2.263(11)
2.384(9)
2.432(9)
2.515(10)
1.779(9)
1.728(9)
2.288(11)
2.278(13)
2.309(12)
2.40(2)
2.578(16)
1.775(4)
2.453(3)
2.477(3)
Symmetry codes: 1: i = –x, 2 – y, 2 – z; 2: i = 1 – x, 1 – y, 1 – z; 3: i = 2 – x, 1 – y, 1 – z; 5: i = x, y, 3/2 – z; j = 1 – y, x – y + 1, z.
17
O1–U1–O2
O9–U1–O11
O11–U1–O13
O13–U1–O14
O14–U1–O15
O15–U1–O9
176.8(5)
72.6(3)
72.8(3)
51.3(3)
72.7(4)
90.5(4)
O3–U2–O4
O9–U2–O10
O10–U2–O12
O12–U2–O19
O19–U2–O16
O16–U2–O9
176.7(4)
70.8(3)
69.3(4)
72.8(4)
68.5(4)
79.0(4)
O5–U3–O6
O9–U3–O10
O10–U3–O17
O17–U3–O20
O20–U3–O11
O11–U3–O9
174.8(5)
71.5(3)
78.8(4)
68.2(3)
71.6(3)
69.9(3)
O7–U4–O8
O10–U4–O12
O12–U4–O21
O21–U4–O22
O22–U4–O18
O18–U4–O10
170.6(7)
72.3(4)
70.8(6)
67.4(6)
70.2(5)
80.5(4)
O1–U–O1i
O2–U–O3
O3–U–O2j
180
52.75(9)
67.25(9)
Figure Captions
Figure 1. Top: View of the uranyl complex in 1. Displacement ellipsoids are drawn at the 50%
probability level. Carbon-bound hydrogen atoms are omitted. Symmetry code: i = –x, 2 – y, 2 – z.
Middle and bottom: Two views of the packing. The uranium coordination polyhedra are shown.
Solvent molecules and hydrogen atoms are omitted.
Figure 2. Top: View of the supramolecular assembly in 3. Displacement ellipsoids are drawn at
the 30% probability level. Carbon-bound hydrogen atoms are omitted. Hydrogen bonds are shown
as dashed lines. Symmetry code: i = 2 – x, 1 – y, 1 – z. Bottom: View of one sheet down the [–3 0
2] axis with water solvent molecules and hydrogen atoms omitted.
Figure 3. Top: View of the supramolecular assembly in 4. Symmetry code: i = x + 1, 3/2 – y, z –
1/2. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted,
and possible hydrogen bonds are shown as dashed lines. Middle: View of the one-dimensional
arrangement. Bottom left: The same viewed end-on. Bottom right: View of the CB8 molecule
with included HL3. Symmetry code: i = 1 – x, 2 – y, 1 – z.
Figure 4. Top: View of the supramolecular assembly in 5. Displacement ellipsoids are drawn at
the 50% probability level. Carbon-bound hydrogen atoms are omitted. Hydrogen bonds are shown
as dashed lines. Symmetry codes: i = x, y, 3/2 – z; j = 1 – y, x – y + 1, z; k = y – x, 1 – x, z.
Bottom: View of the packing with solvent molecules and hydrogen atoms omitted.
18
Scheme 1. Cucurbit[6]uril
Scheme 2. The aminobenzoic acids under study
19
Figure 1
20
Figure 2
21
Figure 3
22
Figure 4
23
For Table of Contents Use Only
Uranyl Ion Complexes with Ammoniobenzoates as
Assemblers for Cucurbit[6]uril Molecules
Pierre Thuéry
In their zwitterionic form, several aminobenzoic acids are able to complex the uranyl ion through
their carboxylate group, to give mono-, di- or tetranuclear, planar complexes, while being
associated to CB6 molecules through ion-dipole and hydrogen bonding interactions involving
their ammonium substituents. Discrete or one-dimensional supramolecular assemblies are thus
created.
24