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Article
Cite This: Inorg. Chem. XXXX, XXX, XXX-XXX
pubs.acs.org/IC
Molecular and Crystal Structures of Uranyl Nitrate Coordination
Polymers with Double-Headed 2‑Pyrrolidone Derivatives
Hiroyuki Kazama,† Satoru Tsushima,†,‡ Yasuhisa Ikeda,† and Koichiro Takao*,†
†
Laboratory for Advanced Nuclear Energy, Institute of Innovative Research, Tokyo Institute of Technology, 2-12-1-N1-32
O-okayama, Meguro-ku, Tokyo 152-8550, Japan
‡
Institute of Resource Ecology, Helmholtz Zentrum Dresden-Rossendorf, P.O. Box 510119, 01314 Dresden, Germany
S Supporting Information
*
ABSTRACT: Double-headed 2-pyrrolidone derivatives (DHNRPs)
were designed and synthesized as bridging ligands for the efficient
and selective separation of UO22+ from a HNO3 solution by
precipitation. The building blocks, UO2(NO3)2 and DHNRPs, were
successfully connected to form an infinite 1D coordination polymer.
The solubility of [UO2(NO3)2(DHNRP)]n is no longer correlated to
the hydrophobicity of the ligand but is exclusively governed by the
ligand symmetry and packing efficiency. The newly designed
DHNRP family can be used to establish a new spent nuclear fuel
reprocessing scheme.
■
INTRODUCTION
The chemistry of actinides is highly relevant to various chemical
processes in the nuclear fuel cycle.1 Especially in the reprocessing
of spent nuclear fuels, coordination chemistry governs the
selective separation and efficient recovery of fertile or fissile
materials like Th, U, and Pu. Although the most popular
reprocessing method commonly employed in the current U/Pu
fuel cycle is a solvent extraction like PUREX involving tri-n-butyl
phosphate as an extractant, there is still enough space to explore a
diversity of separation methods for attaining more simplicity and
versatility. Particularly, a U/Th fuel cycle is attracting special
attention as one of the alternative nuclear energy systems to
overcome the upcoming scarcity of uranium resources, while the
reprocessing method of spent ThO2 fuels is not developed and
experienced very well.2,3
Previously, we found that several N-alkylated 2-pyrrolidone
derivatives (NRPs; Figure 1, left) are able to selectively and
efficiently precipitate UVI and PuVI from a HNO3 solution.4−8
These hexavalent actinides are usually present as actinyl ions
(AnO22+, where An = U and Pu), which form sparingly soluble
bis(nitrato) complexes with NRPs like AnO2(NO3)2(NRP)2
(Figure 1, right). In contrast, tetravalent actinides (An4+) and
other simulated fission products (FPs) remain dissolved.9−11 On
the basis of these findings, we have proposed a precipitationbased reprocessing process for spent nuclear fuels, where the
most important aim is the efficient and selective recovery of U
and Pu through precipitation with appropriately selected
NRPs.9,10 A similar concept for nuclear fuel recycling was also
proposed by Burns and Moyer.12 This principle may also be
directly applied to a wet reprocessing process of spent ThO2 fuels
in the U/Th fuel cycle because its main purpose is the separation
of UO22+ of fissile 233U from Th4+ and other FPs.
In our former developments, we focused on optimization of
the hydrophobicity of NRPs to control the solubility of
AnO2(NO3)2(NRP)2. Higher hydrophobicity generally affords
lower solubility, while the selectivity for AnO22+ is also getting
worse at the same time. Furthermore, the solubility is also
affected by the packing efficiency of AnO2(NO3)2(NRP)2 in the
crystal structure, which was assessed with a compactness
parameter (Cp).6 This quantity was defined as a mean volume
occupied by a single C atom of an N substituent on NRP.
However, there is a limit to improving the packing efficiency (i.e.,
to reducing Cp) because the closest contact between the
neighboring complexes is simply defined by its collision radius
unless any specific interactions are formed. Therefore, it is
necessary to innovate the concept of the molecular design of
NRP as a selective and efficient precipitant for AnO22+.
Figure 1. Schematic structures of NRP (left) and AnO2(NO3)2(NRP)2
(right).
© XXXX American Chemical Society
Received: September 1, 2017
A
DOI: 10.1021/acs.inorgchem.7b02250
Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
was performed also for L3, while no deposits were observed.
After concentration of the mixture through spontaneous
evaporation, yellow crystals were finally obtained (64% yield).
The results of the characterization of these compounds are
described in ref 16 and the SI. Elemental analysis revealed that
the molecular formulas of these compounds are
[UO 2 (NO 3 ) 2 (L1)] (1), [UO 2 (NO 3 ) 2 (L2)] (2), and
[UO2(NO3)2(L3)] (3). The stoichiometry of UO22+, NO3−,
and DHNRP is always 1:2:1, implying formation of the
coordination polymers. In the Raman and IR spectra, the
characteristic vibration modes of UO22+ and DHNRPs were
observed. A low-energy shift of the CO stretching vibration
compared with free DHNRP indicates that its carbonyl O atom
certainly binds to UO22+.
The molecular and crystal structures of compounds 1−3 were
determined by single-crystal X-ray diffraction. As shown in
Figure 3, the infinite 1D coordination polymers of UO2(NO3)2
units and bridging DHNRPs were successfully confirmed in all of
the compounds studied here. In accordance with this, the
formulas of these compounds are written more correctly as
[UO2(NO3)2(DHNRP)]n. The coordination structures around
the U center in these compounds are quite similar to each other.
The interatomic distances between U and axial O are 1.769(2) Å
in 1, 1.772(4) and 1.776(4) Å in 2, and 1.763(4) and 1.766(4) Å
in 3. The OUO bond angles in UO22+ are 180.0(2)° in 1,
179.3(2)° in 2, and 180.0(2)° in 3, showing that the linearity of
UO22+ in these compounds is retained. Furthermore, UO22+ is
surrounded by two bidentate NO3− and two monodentate
pyrrolidone rings of DHNRP to form a hexagonal equatorial
plane in trans geometry. In Figure 3b, only the R,R enantiomer of
L2 is displayed, while the S,S isomer is also present in the crystal
structure of 2 to make it racemic. The mean U−ONO3 bond
lengths are 2.55 Å in 1, 2.51 Å in 2, and 2.54 Å in 3. The U−
ODHNRP bond distances are 2.362(2) Å in 1, 2.395(4) and
2.402(4) Å in 2, and 2.356(3) and 2.365(4) Å in 3. The CO−
U bond angles are 134.4(2)° in 1, 145.4(3) and 135.1(4)° in 2,
and 134.4(3) and 143.0(4)° in 3. The structural parameters
discussed here are also commonly found in various
UO2(NO3)2L2 (L = monodentate ligand).5,6,17−20
Looking at these structural parameters, one can find that the
U−ONO3 lengths in 2 are shorter than those of the other
compounds, while U−ODHNRP in 2 is longer than others at the
same time. This trend can be ascribed to steric effects between
NO3− and the C−H moiety vicinal to N in DHNRP. In fact, the
interatomic distance from ONO3 to the spatially closest H is 2.264
Å in 2, which is much shorter than those in 1 (2.378 Å) and 3
(2.528 Å). Although the H···ONO3 distance shorter than the sum
of the van der Waals radii of O and H (1.52 + 1.20 = 2.72 Å)21
suggests that a short contact is actually present between NO3−
and C−H in these complexes, its extent in 2 seems to be stronger
than those in 1 and 3. As a matter of fact, the C−H···ONO3 angle
in 2 (172.4°) also implies the presence of the C−H···O hydrogen
bond.22,23 In contrast, such a discussion cannot be easily applied
to 1 and 3 because of the narrower angles (143.9° for 1 and
133.8° for 3). In the molecular structure of 2, the pyrrolidone
rings are forced to stack with their faces toward each other
because of the trans-1,2-cyclohexylene group. As a result, this
bridging moiety tends to lean over NO3− to form the C−H···
ONO3 hydrogen bond.
Although the molecular arrangements in 1−3 are similar to
each other at a glance, several differences are also observable. The
Figure 2 shows one of the promising solutions, where two 2pyrrolidone moieties are cross-linked by a bridging moiety, R′.
Figure 2. General structure of the DHNRP studied here.
This double-headed NRP (DHNRP) allows one to connect
AnO2(NO3)2 units to form a 1D chain coordination polymer,
which can be much less soluble than the AnO2(NO3)2(NRP)2
reported so far. Covalent bonds connecting the 2-pyrrolidone
groups may afford a closer approach of the AnO2(NO3)2
moieties beyond the limit arising from the van der Waals radii.
Furthermore, having two amide groups in a single molecule is
beneficial to decreasing the hydrophobicity of DHNRP. As a
result, both of efficiency and selectivity of the AnVI precipitation
can be achieved simultaneously. While the ethylene-bridged
structure has been reported previously,13,14 any further developments have not been achieved at all. In this article, the synthesis
and characterization of UO2(NO3)2 complexes with several
DHNRPs are described together with their solubility to
demonstrate the effectiveness of our new molecular design for
NRP toward the simple and versatile reprocessing for spent
nuclear fuels.
■
RESULTS AND DISCUSSION
Here, we selected DHNRPs including trans-1,4-cyclohexylene
(L1), trans-1,2-cyclohexylene (L2), and propylene (L3) groups
as a bridging moiety R′. Compounds L1−L3 were prepared
through Scheme 1.6,15 Consequently, L1 and L2 were obtained
Scheme 1. Preparation of DHNRP
as colorless solids, while L3 was an oily product. All DHNRPs
prepared here were identified by 1H and 13C NMR and IR
spectroscopy. Furthermore, L1 and L2 were also characterized
by elemental analysis and single-crystal X-ray diffraction. The
details are described in the Supporting Information (SI). The
hydrophobicity of DHNRPs was assessed in terms of the
logarithmic partition coefficients in a 1-octanol/water biphasic
system (log Po/w). As a result, the log Po/w values of L1−L3 were
−0.07, 0.35, and −0.74, respectively. These values are smaller
than those of the single-headed NRPs [Figure 1; R = n-butyl
(0.70), isobutyl (0.59), and cyclohexyl (1.10)] reported
previously,8 demonstrating the lower hydrophobicity of the
DHNRPs prepared here.
In 1.0 M HNO3(aq), DHNRP (0.25 M) and UO22+(0.25 M)
were slowly mixed in a glass tube (see the SI). As a result, yellow
crystals deposited in the samples of L1 and L2 within several
hours (99% and 92% yields, respectively). The same experiment
B
DOI: 10.1021/acs.inorgchem.7b02250
Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
Figure 3. ORTEP drawings of (a) 1, (b) 2, and (c) 3) at the 50% probability level. H atoms were omitted for clarity.
most critical one is the size of an asymmetric unit. Compound 1
consists of only one U, one axial O, one NO3−, and half of a L1
molecule. This asymmetric unit is the smallest in the compounds
studied here. The asymmetric unit of compound 2 comprises the
larger group of components, i.e., UO22+, two NO3−, and a whole
molecule of L2. Compound 3 shows the largest asymmetric unit
containing two U, two axial O, two NO3−, and a whole molecule
of L3. Interestingly, compounds 1−3 belong to P1̅ (No. 2),
where only two kinds of symmetry operators, (x, y, z) and (−x,
−y, −z), are available. Therefore, their crystallographic
symmetries are actually the same. On the other hand, the
difference in the size of the asymmetric unit is clearly observed as
mentioned above. Such a difference most likely arises from the
symmetry of DHNRPs connecting the UO2(NO3)2 units. Thus,
L1 in C2h is the most symmetric in the tested DHNRPs, while
both L2 and L3 in C2 are lower in symmetry. The compactness
parameters (Cp) of 1−3 were estimated as 15.6, 18.8, and 21.3 Å3,
respectively. These values are much smaller than those of
UO2(NO3)2(NRP)2 (Figure 1; 24.0−28.9 Å3),6 indicating that
connecting 2-pyrrolidone moieties through covalent bonds
efficiently helps to improve the packing efficiency as expected.
The recovery efficiency of AnO22+ (An = U and Pu) is highly
important in the recycle of nuclear fuel materials through spent
fuel reprocessing. In the precipitation-based reprocessing
method, we proposed that the solubility of
[UO2(NO3)2(DHNRP)]n is the most essential. In this context,
compounds 1−3 were soaked in 3.0 M HNO3(aq) at 298 K to
determine their solubility. The obtained results were summarized
in Table 1, together with several quantities that may affect the
solubility of [UO2(NO3)2(DHNRP)]n. As seen from Table 1, the
hydrophobicity referring to log Po/w is not directly correlated to
the solubility of compounds 1−3. This situation is much different
from the former series of UO2(NO3)2(NRP)2 (Figure 1) that we
studied previously. In contrast, [UO2(NO3)2(DHNRP)]n tends
to become more soluble with increasing Cp. This means that the
Table 1. Solubility of [UO2(NO3)2(DHNRP)]n in 3.0 M
HNO3(aq) at 298 K and Related Parameters
1
2
3
solubility/mM
log Po/w
Cp/Å3
ligand symmetry
2.49
14.8
102
−0.07
0.35
−0.74
15.6
18.8
21.3
C2h
C2
C2
packing efficiency is a dominant factor to govern the solubility of
[UO2(NO3)2(DHNRP)]n. It is worth noting that compound 1
(2.49 mM) is much less soluble compared with any of
UO2(NO3)2(NRP)2 reported so far (18−137 mM)8 despite
the much lower hydrophobicity of the ligand (log Po/w = −0.07
for L1; log Po/w = 0.20−1.10 for NRPs; R = propyl, n-butyl,
isobutyl, cyclohexyl). The solubility of uranyl oxalate, a wellknown uranyl precipitate, is ca. 50 mM in 3 M HNO3(aq),24
which is even higher than 1 and 2. This means that L1 and L2 are
superior to oxalate as effective precipitants for UO22+ in
HNO3(aq).
■
CONCLUSION
In conclusion, the formation of 1D chain coordination polymers
of uranyl nitrate complexes was successfully observed. The
solubility of these complexes was liberated from the hydrophobicity of additional monodentate ligands by adopting the new
concept of molecular design, DHNRP, to form a coordination
polymer and closer packing. Further investigations are currently
ongoing, e.g., design and optimization of DHNRP structure,
synthesis and characterization of their UO2(NO3)2 complexes,
interaction of DHNRPs with tetravalent metal ions like Th4+,
U4+, Ce4+, and Zr4+, and selective separation of UO22+ from An4+
and other FPs to give a prospect to a simple and versatile
reprocessing method for spent nuclear fuels in both U/Pu and
U/Th fuel cycles. Recently, sophisticated polyactinide complexes
like oxo/hydroxo clusters,25−28 metal−(in)organic frameC
DOI: 10.1021/acs.inorgchem.7b02250
Inorg. Chem. XXXX, XXX, XXX−XXX
Article
Inorganic Chemistry
works,29−33 and topological clusters34−36 are extensively studied.
A series of DHNRPs that we designed here is a promising
building block to exploring a new aspect of the actinide
coordination chemistry exclusively oriented to spent fuel
reprocessing.
■
Derivatives: Cocrystallization Potentiality of UVI and PuVI. Cryst.
Growth Des. 2010, 10, 2033−2036.
(8) Takao, K.; Noda, K.; Nogami, M.; Sugiyama, Y.; Harada, M.;
Morita, Y.; Nishimura, K.; Ikeda, Y. Solubility of Uranyl Nitrate
Precipitates with N-Alkyl-2-pyrrolidone Derivatives (Alkyl = n-Propyl,
n-Butyl, iso-Butyl, and Cyclohexyl). J. Nucl. Sci. Technol. 2009, 46, 995−
999.
(9) Koshino, N.; Harada, M.; Morita, Y.; Kiikuchi, T.; Ikeda, Y.
Development of a simple reprocessing process using selective
precipitant for uranyl ions: Fundamental studies for evaluating the
precipitant performance. Prog. Nucl. Energy 2005, 47, 406−413.
(10) Morita, Y.; Takao, K.; Kim, S.-Y.; Kawata, Y.; Harada, M.;
Nogami, M.; Nishimura, K.; Ikeda, Y. Development of Advanced
Reprocessing System Based on Precipitation Method Using Pyrrolidone
Derivatives as Precipitants -Precipitation Behavior of U(VI), Pu(IV),
and Pu(VI) by Pyrrlidone Derivatives with Low Hydrophobicity-. J.
Nucl. Sci. Technol. 2009, 46, 1129−1136.
(11) Suzuki, T.; Kawasaki, T.; Takao, K.; Harada, M.; Nogami, M.;
Ikeda, Y. A study on selective precipitation ability of cyclic urea to U(VI)
for developing reprocessing system based on precipitation method. J.
Nucl. Sci. Technol. 2012, 49, 1010−1017.
(12) Burns, J. D.; Moyer, B. A. Group Hexavalent Actinide Separations:
A New Approach to Used Nuclear Fuel Recycling. Inorg. Chem. 2016,
55, 8913−8919.
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Conversion of atmospheric dioxygen to a μ-η2,η2-peroxo bridge in a
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(16) Caution! 238U is an emitter, and therefore standard precautions for
handling radioactive materials should be followed. Characterization of 1.
Anal. Calcd for C14H22N4O10U: C, 26.10; H, 3.44; N, 8.69. Found: C,
26.30; H, 3.34; N, 8.65. Crystallographic data for 1: fw = 644.38, 0.400 ×
0.300 × 0.200 mm3, triclinic, P1̅ (No. 2), a = 5.8962(4) Å, b = 7.6330(6)
Å, c = 11.0279(9) Å, α = 76.841(5)°, β = 84.480(6)°, γ = 76.229(5)°, V =
468.93(6) Å3, Z = 1, T = 93 K, Dcalcd = 2.282 g cm−3, μ = 87.199 cm−1,
GOF = 1.042, R (I > 2σ) = 0.0174, wR (all) = 0.0393. IR (ATR, cm−1):
1589 (>CO), 927 (UO22+, asymmetric). Raman (cm−1): 852 (UO22+,
symmetric). Characterization of 2. Anal. Calcd for C14H22N4O10U: C,
26.10; H, 3.44; N, 8.69. Found: C, 26.03; H, 3.31; N, 8.45.
Crystallographic data for 2: fw = 644.38, 0.400 × 0.300 × 0.300 mm3,
triclinic, P1̅ (No. 2), a = 9.9552(7) Å, b = 10.0507(7) Å, c = 10.1794(7)
Å, α = 90.900(6)°, β = 106.750(8)°, γ = 90.412(6)°, V = 975.12(12) Å3,
Z = 2, T = 93 K, Dcalcd = 2.194 g cm−3, μ = 83.868 cm−1, GOF = 1.073, R
(I > 2σ) = 0.0344, wR (all) = 0.0792. IR (ATR, cm−1): 1597 (>CO),
931 (UO22+, asymmetric). Raman (cm−1): 854 (UO22+, symmetric).
Characterization of 3. Anal. Calcd for C11H18N4O10U: C, 21.86; H, 2.94;
N, 9.27. Found: C, 21.71; H, 3.11; N, 8.87. Crystallographic data for 3:
fw = 604.31, 0.300 × 0.200 × 0.200 mm3, triclinic, P1̅ (No. 2), a =
5.9980(10) Å, b = 11.534(2) Å, c = 13.224(2) Å, α = 100.169(7)°, β =
95.142(7)°, γ = 100.614(7)°, V = 878.0(3) Å3, Z = 2, T = 183 K, Dcalcd =
2.286 g cm−3, μ = 93.065 cm−1, GOF = 1.057, R (I > 2σ) = 0.0298, wR
(all) = 0.0831. IR (ATR, cm−1): 1609 (>CO), 929 (UO22+,
asymmetric). Raman (cm−1): 852 (UO22+, symmetric).
(17) Ikeda, Y.; Wada, E.; Harada, M.; Chikazawa, T.; Kikuchi, T.;
Mineo, H.; Morita, Y.; Nogami, M.; Suzuki, K. A study on pyrrolidone
derivatives as selective precipitant for uranyl ion in HNO3. J. Alloys
Compd. 2004, 374, 420−425.
(18) Koshino, N.; Harada, M.; Nogami, M.; Morita, Y.; Kikuchi, T.;
Ikeda, Y. A structural study on uranyl(VI) nitrate complexes with cyclic
amides: N-n-butyl-2-pyrrolidone, N-cyclohexylmethyl-2-pyrrolidone,
and 1,3-dimethyl-2-imidazolidone. Inorg. Chim. Acta 2005, 358,
1857−1864.
ASSOCIATED CONTENT
S Supporting Information
*
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorgchem.7b02250.
Details of the synthesis and characterization of L1−L3 and
1−3 (PDF)
Accession Codes
CCDC 1573161−1573163 contain the supplementary crystallographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: ktakao@lane.iir.titech.ac.jp. Tel and Fax: +81 3 5734
2968.
ORCID
Koichiro Takao: 0000-0002-0952-1334
Author Contributions
The manuscript was written through contributions of all authors.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Prof. Emer. Hirotake Moriyama for stimulating
discussion and his helpful advice. This work is the result of the
“Fundamental Study on Simple Reprocessing Method for Spent
Thorium Fuels by Using Uranium-Selective Precipitant” (Project
271501) entrusted to the Tokyo Institute of Technology by
MEXT, Japan.
■
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E
DOI: 10.1021/acs.inorgchem.7b02250
Inorg. Chem. XXXX, XXX, XXX−XXX
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