Layered Uranyl Coordination Polymers Rigidly Pillared by

Publication Date (Web): October 12, 2012. Copyright ... Synopsis. Four new uranyl phosphonate coordination polymers have been prepared under mild hydr...
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Layered Uranyl Coordination Polymers Rigidly Pillared by Diphosphonates Pius O. Adelani‡ and Thomas E. Albrecht-Schmitt*,† †

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States

‡

S Supporting Information *

ABSTRACT: The hydrothermal reaction of uranyl nitrate and 1,4-benzenebisphosphonic acid in the presence of monovalent and divalent metal hydroxides results in the formation of four new uranyl coordination polymers: Ag 2 {(UO 2 )[C6H4(PO3H)2]2} (AgUbbp), Cs{(UO2)[C6H4(PO3H0.5)2]} (CsUbbp), [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) (BaUbbp), and [Sr(H 2 O) 3 ]{(UO 2 ) 2 [C 6 H 4 (PO 3 ) 2 ](OH)2(H2O)}·3(H2O) (SrUbbp). AgUbbp and CsUbbp complexes are constructed from UO6 units with tetragonal bipyramidal coordination geometries, whereas BaUbbp and SrUbbp complexes contain UO7 units with pentagonal bipyramidal coordination environments. The pH and the monovalent/divalent metal cations have significant effects on the topology of these structures. These compounds fluoresce at room temperature owing to emission from the uranyl units.

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absence of structure-directing agents.3b,c,11 Herein, we report the syntheses and spectroscopic properties of uranyl phenyldiphosphonate compounds, Ag2{(UO2)[C6H4(PO3H)2]2} (AgUbbp), Cs{(UO2)[C6H4(PO3H0.5)2]} (CsUbbp), [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) (BaUbbp), and [Sr(H 2 O) 3 ]{(UO 2 ) 2 [C 6 H 4 (PO 3 ) 2 ](OH) 2 (H 2 O)}·3(H 2 O) (SrUbbp).

INTRODUCTION The structural chemistry of uranyl arylphosphonates is remarkably rich and has resulted in a variety of atypical architectures, such as the elliptical uranyl phenyldiphosphonate nanotubules in Cs 3.62 H 0.38 {(UO 2 ) 4 [C 6 H 4 (PO 2 OH) 2 ] 3 [C6H4(PO3)2]F2}.1,2 Some of these compounds are functional and selective ion exchange has already been observed in this family.2 In addition, the incorporation of metal and organoammonium cations as structure-directing agents has enriched the structural topologies of uranyl arylphosphonates.3 Moreover, the structural complexity has been further enhanced through the design of multifunctional carboxyphenylphosphonate ligand derivatives.4 Recently, we stabilized uranyl heteropolyoxometalate with a diethyl(2-ethoxycarbonylphenyl)phosphonate ligand, using the transition metal as linkers.4d Phosphonates have been utilized in nuclear waste management and separation processes.5 Uranyl complexes of different oxoanions have demonstrated a wide range of important applications in ion exchange, ionic conductivity, intercalation chemistry, photochemistry, nonlinear optical materials, and catalysis.1,2,6−9 The solid-state coordination chemistry of uranium is dominated by uranium in the +6 oxidation state, which is found within the uranyl dication, UO22+. These two oxo atoms are less reactive toward oxoanions because of their covalent interactions with the uranium center. U(VI) is typically coordinated by four to six ligands in the equatorial plane, resulting in tetragonal, pentagonal, and hexagonal bipyramidal coordination geometries.10 We have demonstrated in our previous reports that rigid 1,4-benzenebisphosphonates can be used to construct pillared uranyl structures in the presence or © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Syntheses. UO2(NO3)·6H2O (98%, International Bio-Analytical Industries), 1,4-benzenebisphosphonic acid (95%, Epsilon Chimie), HF (48 wt %, Aldrich), CsOH·H2O (96%, Alfa), Ba(OH)2 (94−98%, Alfa), Sr(OH)2·8H2O (Alfa), LiOH (98%, Alfa), and AgNO3 (99.7%, J.T. Baker) were used as received. Reactions were conducted in PTFElined Parr 4749 autoclaves with a 23 mL internal volume. Distilled and Millipore filtered water with a resistance of 18.2 MΩ·cm was used in all reactions. Caution! While the uranium compound used in these studies contained depleted uranium salts, precautions are needed for handling radioactive materials, and all studies should be conducted in a laboratory dedicated to studies of radioactive materials. Ag2{(UO2)[C6H4(PO3H)2]2} (AgUbbp). UO2(NO3)·6H2O (50.2 mg, 0.1 mmol), 1,4-benzenebisphosphonic acid (47.6 mg, 0.2 mmol), 1.0 mL of water, HF (∼25 μL), LiOH (5.0 mg, 2.0 mmol), and AgNO3 (33.7 mg, 2.0 mmol) were loaded into a 23 mL autoclave. After heating for 3−5 days at 200 °C, the autoclave was then cooled at an average rate of 5 °C/h to 25 °C. The resulting yellow product was washed with distilled water and ethanol and allowed to air dry at room temperature. Yellow tablets of AgUbbp were isolated as pure phase (yield = 76% based on uranium). Received: September 21, 2012 Revised: October 8, 2012

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Table 1. Crystallographic Data for Ag2{(UO2)[C6H4(PO3H)2]2} (AgUbbp), Cs{(UO2)[C6H4(PO3H0.5)2]} (CsUbbp), [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) (BaUbbp), and [Sr(H2O)3]{(UO2)2[C6H4(PO3)2](OH)2(H2O)}·3(H2O) (SrUbbp) formula mass color and habit space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å) Z T (K) λ (Å) ρcalcd (g cm−3) μ (Mo Kα) (mm−1) R(F) for Fo2 > 2σ(Fo2)a Rw(Fo2)b a

AgUbbp

CsUbbp

BaUbbp

SrUbbp

957.87 yellow, tablet P21/m (No. 11) 6.3558(12) 20. 655(4) 7.8807(14) 90 92.286(2) 90 1033.8(3) 2 100 0.71073 3.077 10.072 0.020 0.043

637.98 yellow, needle P21/n (No. 14) 5.5196(7) 15.681(2) 14.5816(19) 90 99.321(2) 90 1245.4(3) 4 100 0.71073 3.403 16.198 0.022 0.047

1559.49 yellow, tablet P1̅ (No. 2) 9.5213(9) 10.5817(10) 18.3319(18) 95.927(1) 99.681(1) 114.194(1) 1630.0(3) 2 100 0.71073 3.177 16.345 0.025 0.063

941.71 yellow, tablet Cmcm (No. 63) 7.1190(8) 14.1051(16) 17.698(2) 90 90 90 1777.1(3) 4 100 0.71073 3.541 21.423 0.034 0.093

R(F) = ∑||Fo| − |Fc||/∑|Fo|. bR(F2o) = [∑w(F2o − F2c )2/∑w(F4o)]1/2.

Cs{(UO 2 )[C 6 H 4 (PO 3 H 0 . 5 ) 2 ]} (CsUbbp), [Ba(H 2 O) 3 ]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) (BaUbbp), and [Sr(H2O)3]{(UO 2 ) 2 [C 6 H 4 (PO 3 ) 2 ](OH) 2 (H 2 O)}·3(H 2 O) (SrUbbp). UO2(NO3)·6H2O (50.2 mg, 0.1 mmol), 1,4-benzenebisphosphonic acid (47.6 mg, 0.2 mmol), 1.0 mL of water, HF (∼25 μL), and alkali/ alkali earth metal hydroxides-CsOH·H2O (30.3 mg, 1.8 mmol), Ba(OH)2 (34.0 mg, 2.0 mmol), or Sr(OH)2·8H2O (53.5 mg, 2.0 mmol) were loaded into a 23 mL autoclave. Following the procedure above, we isolated yellow tablets of CsUbbp and BaUbbp as pure phase (yields are CsUbbp = 67% and BaUbbp = 61% based on uranium), whereas crystals of SrUbbp were isolated with powder (the crystals formed about 60% of the products). Crystallographic Studies. Single crystals of AgUbbp, CsUbbp, BaUbbp, and SrUbbp were mounted on cryoloops and optically aligned on a Bruker APEXII Quazar CCD X-ray diffractometer using a digital camera. Initial intensity measurements were performed using an IμS X-ray source and a 30 W microfocused sealed tube (Mo Kα, λ = 0.71073 Å) with a monocapillary collimator. Standard APEXII software was used for determination of the unit cells and data collection control. The intensities of reflections of a sphere were collected by a combination of four sets of exposures (frames). Each set had a different φ angle for the crystal, and each exposure covered a range of 0.5° in ω. A total of 1464 frames were collected with an exposure time per frame of 10−40 s, depending on the crystal. SAINT software was used for data integration including Lorentz and polarization corrections. Semiempirical absorption corrections were applied using the program SADABS.13 The program suite SHELXTL was used for space group determination (XPREP), direct methods structure solution (XS), and least-squares refinement (XL).14 The positions of H atoms around the P−O groups were included using a riding model. The final refinements included anisotropic displacement parameters for all atoms except H. Selected crystallographic information is listed in Table 1 and the Supporting Information, Tables S2−S5. Atomic coordinates, bond distances, and additional structural information are provided in the Supporting Information (CIF). Powder X-ray Diffraction (XRD). Powder XRD patterns of all the compounds, AgUbbp, CsUbbp, BaUbbp, and SrUbbp, were collected on a Bruker θ−θ diffractometer equipped with a Lynxeye onedimensional solid-state detector and Cu Kα radiation at room temperature over the angular range from 5° to 60° (2θ) with a scanning step width of 0.02° and a fixed counting time of 1 s/step. The experimental powder patterns were compared with those simulated

from single-crystal data using the Mercury program to determine their purity. Spectroscopic Properties. Fluorescence data for all the compounds were acquired from single crystals using a Craic Technologies UV−vis-NIR microspectrophotometer with a fluorescence attachment. Excitation was achieved using 365 nm light from a mercury lamp for the fluorescence spectroscopy. Infrared spectra were collected from single crystals of all the compounds using a SensIR Technology IlluminatIR FT-IR microspectrometer. A single crystal of each of the compounds was placed on a glass slide, and the spectrum was collected with a diamond ATR objective.

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RESULTS AND DISCUSSION Syntheses. AgUbbp, CsUbbp, BaUbbp, and SrUbbp were prepared using a stoichiometric ratio of 1:2:2 (uranium/1,4benzenebisphosphonic acid/metal cations). HF was added as a mineralizing agent, and the amount must be carefully controlled to avoid isolation of uranium(IV) fluorides as the predominant product. The absence of HF in the reactions resulted to the isolation of powder as predominant products. The addition of hydroxide as starting materials raises the pH to the 2−4 range, which is higher than has been used in previous studies by our group. Structure of Ag2{(UO2)[C6H4(PO3H)2]2} (AgUbbp). AgUbbp consists of one crystallographically unique uranyl group in the form of a tetragonal bipyramidal geometry, two diphosphonate ligands, and two independent silver metal cations. The uranyl ions are linked through the phosphonate groups into uranyl-phosphonate (U-P) chains, as shown in Figure 1. These layers of U-P chains are arranged in a sinusoidal waveform pattern. The “yl” oxo atoms of the uranyl groups are coordinated to the silver metal ions, as they often do with alkali metal ions.2,3d,4b In addition, the silver metal ions are paired to form dimers (see Figure 2). The uranyl center has a nearly linear [OUO]2+ bond angle of 177.63(15)°, and the UO bond lengths are 1.783(3) and 1.797(3) Å. The additional four oxygen atoms are from the phosphonate groups in the tetragonal plane. They are coordinated to the uranyl center with bond distances ranging from 2.268(2) to 2.278(2) Å. The calculated bond-valence sum B

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bipyramidal geometry and a diphosphonate ligand. The uranyl groups are connected through the diphosphonate ligand into undulating layered U-P chains, as shown in the overall structure (see Figure 3). The Cs+ cations are seated between the layers

Figure 1. Polyhedral representation of the layered uranyl phosphonate chains in Ag2{(UO2)[C6H4(PO3H)2]2}; Ag+ cations are seated between the chains. The structure is constructed from UO6 units: tetragonal bipyramids = green, silver = dark blue, oxygen = red, phosphorus = magenta, carbon = black, and hydrogen = white.

Figure 3. Polyhedral representation of the layered uranyl phosphonate chains in Cs{(UO2)[C6H4(PO3H0.5)2]}; Cs+ cations are arranged between the chains: UO6 units = green, cesium = blue, oxygen = red, phosphorus = magenta, carbon = black, and hydrogen = white.

and stitched the uranyl and phosphonate groups together so that the overall charged balance is maintained. A view of each of the chains along the b axis shows uranyl chains that are pillared by a rigid diphosphonate moiety (Figure 4). This structural

Figure 2. Illustration of the sheets in Ag2{(UO2)[C6H4(PO3H)2]2} viewed along the [bc] plane. Legend as that in Figure 1.

for the uranium center is 5.92, which agrees with the formal oxidation state of U(VI).10a,12 The P(1)−O(5) and P(2)−O(7) bond distances are 1.554(2) and 1.562(3) Å, respectively. They are terminal P−OH bonds and are longer than the other P−O bonds that range from 1.518(2) to 1.524(2) Å. Each of the two Ag+ ions is coordinated to a uranyl oxo atom through the apical position and the basal plane to four phosphonate oxygen atoms to form a square pyramidal geometry. The Ag−O bond distances range from 2.447(2) to 2.487(2) Å and 2.419(2) to 2.438(2) Å for Ag(1) and Ag(2), respectively. The average distance between Ag(1) and Ag(2) is 3.367(8) Å. Structure of Cs{(UO2)[C6H4(PO3H0.5)2]} (CsUbbp). The structure of CsUbbp comprises a uranyl center with tetragonal

Figure 4. Depiction of the sheets in Cs{(UO2)[C6H4(PO3H0.5)2]} viewed along the [ac] plane. Legend as that in Figure 3.

arrangement is in contrast to those reported in uranyl diphosphonate nanotubules where we utilized Cs+ as the structure-directing agent.2 In view of the different structural topologies observed, we speculate that these reactions are pHdependent. The uranium center is characteristically bound to two axial oxygen atoms to form a UO22+ cation, with an average UO bond distance of 1.783(3) Å. The additional four oxygen atoms from the phosphonate ligand are bound to the uranyl cation in C

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the equatorial plane with the U−O bond distances ranging from 2.258(3) to 2.599(3) Å. These distances result in a calculated bond-valence sum of 5.89 for U(1), which is consistent with U(VI).10a,12 Two of the phosphonate oxygen atoms are bound to the uranyl cation in a monodentate manner with the P−O bond distances ranging from 1.519(3) to 1.535(3) Å. The oxygen atoms involved in the considerably longer P−O bonds are not coordinated to the uranium center but formed long contacts with cesium cations. These bond distances are shorter relative to the literature reports for fully protonated phosphonate groups.2−4 This is indicative of a halfoccupied protonated group, and this agreed with charge balance considerations. The Cs(1) cations form nine long contacts that range from 3.085(3) to 3.497(3) Å with three “yl” oxo atoms and six phosphonate oxygen atoms. Structure of [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) (BaUbbp). The structure of BaUbbp differs from those constructed from monovalent metal cations, AgUbbp and CsUbbp. Instead of uranyl phosphonate chains, this compound contains UO7 units that are bridged by the phosphonate group to form a pillared layered three-dimensional framework with channels that are filled with water molecules, as shown in Figure 5. A view along the [ab] plane shows the edge-sharing

Figure 6. Illustration of the uranyl sheets that are linked through the phosphonate moiety in [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O) viewed along the [ab] plane. Legend as that in Figure 5.

centers range from 2.255(4) to 2.535(4) Å, 2.232(4) to 2.487(4) Å, and 2.310(4) to 2.659(4) Å. The bridging μ2-O atoms from the phosphonate ligand are characterized with longer U−O bond distances relative to monodentate oxygen atoms. The calculated bond-valence sums for U(1), U(2), and U(3) are 6.05, 6.10, and 5.99, respectively; these are consistent with U(VI).10a,12 Two crystallographically distinct phosphonate ligands are coordinated to uranyl cations; one of these ligands is disordered and has been resolved accordingly. The P−O bond distances range from 1.505(4) to 1.556(4) Å. The Ba2+ cation forms 10 long contacts that range from 2.726(6) to 3.186(4) Å with the uranyl oxo atom, oxygen atoms from phosphonate, and the disordered water molecules. Structure of [Sr(H2O)3]{(UO2)2[C6H4(PO3)2](OH)2(H2O)}·3(H2O) (SrUbbp). This complex is constructed from uranyl cations that occur in pentagonal bipyramidal coordination geometries. The uranyl cations are bridged through the phosphonate moiety into a layered one-dimensional uranyl chain; these chains are subsequently cross-linked by the rigid phenyl spacers into pillared layered networks (Figure 7). Figure 8 shows the sharing of edges between the pentagonal bipyramids, and these dimers are joined into sheets of uranyl polyhedra through the PO3 groups. The voids in this structure are filled with water molecules. The uranyl cation is bound to two “yl” oxygen atoms with an average UO bond distance of 1.796(9) Å and an [OU O]2+ bond angle of 176.4(3)°. The U−O bond distances along the equatorial plane range from 2.272(7) to 2.374(3) Å. The calculated bond-valence sum of 6.11 from these bonds is consistent with U(VI).10a,12 All the oxygen atoms of the phosphonate are fully deprotonated with P−O bond distances ranging from 1.523(7) to 1.526(5) Å. The presence of the Sr2+ cation is important for balancing the overall charges, and it forms 11 long contacts with uranyl oxo atoms, oxygen atoms of phosphonates, hydroxides, and water molecules. The Sr−O bond distances range from 2.411(6) to 2.808(5) Å. The shorter Sr−O bond length represents the bridging μ3-O atom of the hydroxide moiety. Comments on the Coordination Environments of Uranyl Diphosphonates. The structural topology and coordination patterns in AgUbbp/CsUbbp and BaUbbp/ SrUbbp contrast sharply. This is largely due to the distinction

Figure 5. Depiction of the pillared layered three-dimensional framework structure of [Ba(H2O)3]{(UO2)3[C6H4(PO3)2]2(O)}·5(H2O): UO7 units = green, barium = dark orange, oxygen = red, phosphorus = magenta, carbon = black, and hydrogen = white.

uranyl dimers that are subsequently connected into sheets of uranyl polyhedra through the phosphonate ligands (Figure 6). The structural topology of BaUbbp is similar to those reported in our previous work with 1,4-benzenebisphosphonic acid, in which the rigid phenyl spacer allows for the isolation of pillared compounds that are most often layered.3b,c,e,11 The structure of BaUbbp is constructed from three crystallographically unique uranyl centers. For the three uranium centers, the [OUO] 2+ bond angles are 178.91(19), 177.39(18), and 179.33(17)°, while the average UO bond distances are 1.775(4), 1.782(4), and 1.773(4) Å for U(1), U(2), and U(3), respectively. The five U−O bond distances along the equatorial plane of each of the three uranyl D

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Figure 8. View of the uranyl sheets that are linked through the phosphonate moiety in [Sr(H 2 O) 3 ]{(UO 2 ) 2 [C 6 H 4 (PO 3 ) 2 ](OH)2(H2O)}·3(H2O) viewed along the b axis. Legend as that in Figure 7.

under similar conditions where we utilized organoammonium or alkali metal cations as structure-directing agents.2,3b,c Instead of the common pillared layered structures, we observed chains of layered uranyl diphosphonates that are constructed from UO6 units. The phosphonate groups are fully deprotonated at the high pH condition. For instance, the oxygen atoms of the phosphonate moiety are bound to the uranyl cations to yield extended sheets of layered uranyl coordination polymer, Cs{(UO2)[C6H4(PO3H0.5)2]}. The anionic layers are stitched together by the Ag+/Cs+ metal cations. The structures of BaUbbp and SrUbbp are constructed from UO7 units, and the overall structures are pillared layered three-dimensional frameworks. This is similar to most of the structures we have reported where the voids are filled with organoammonium/ alkali metal cations except that the cations herein are intertwined between the layers of uranyl diphosphonates.2,3b,c For instance, the voids in BaUbbp and SrUbbp are filled with water molecules only. Spectroscopic Properties. Uranyl complexes normally emit green light centered near 520 nm, and this is a chargetransfer-based emission that is vibronically coupled to both bending and stretching modes of the uranyl cation.13 However, not all uranyl-containing compounds fluoresce. Other factors can contribute to the quenching of the emission, and the mechanisms of the emission from uranyl complexes are yet to be well-understood.8c All four compounds show interesting emission spectra (∼497, 521, 543, 584, and 611 nm) similar to those reported in our previous work with 1,4-benzenebisphosphonic acid and carboxyphenylphosphonic acid as ligands.2b,3d,e,4a These four uranyl compounds exhibit a slight red shift of 34 nm compared to UO2(NO3)2·6H2O (487, 509, 532, 558, 586, and 612 nm), as shown in Figure S1 (Supporting Information). Several vibrational modes were observed for all the four compounds, as shown in Figure S2 (Supporting Information). The low wavenumber regions of the IR spectra are dominated by peaks indicative of the O−P−O bending, phenyl ring, and P−C stretching vibrations (700−770 cm −1 ), and the asymmetric and symmetric stretching modes of the uranyl cation, UO22+, are observed around 815−985 cm−1. The asymmetric and symmetric stretching modes of PO and P− O range from 1005 to 1201 cm−1. The peaks around 1356− 1404 cm−1 are at expected values for phenyl ring stretching vibrations. Bands around 1609−1635 cm−1 can be attributed to H2O bending, whereas the high-energy regions correspond to the C−H stretches (2844−2965 cm−1) and O−H stretches (3500−3600 cm−1) of free water molecules. The comprehensive description and peak assignments for both fluorescence and IR spectra are given in our previous work.2b,3d,e,4a

between monovalent (Ag+/Cs+) and divalent (Ba2+/Sr2+) metal cations, as demonstrated in our previous work where we examined the effect of the hard/soft acid/base predictions on the coordination of uranium(VI) and softer metal cations to carboxyphosphonate.4b The phosphonate oxygen atom is exclusively coordinated in a bidentate pattern to a pair of Ag+ or Cs+ metal cations, and bound to both Ba2+/Sr2+ metal and uranyl cations in a bidentate fashion via bridging μ2-O atoms. In addition, these observations are partly due to the slight increase in the pH of the reaction (pH > 3). The resulting topologies in AgUbbp and CsUbbp have never been reported in our previous work with 1,4-benzenebisphosphonic acid, especially

CONCLUSIONS The preparation of the series of uranyl coordination polymers described herein allows us to examine the influence of monovalent and divalent metal cations on the resulting topologies of uranyl diphosphonates. All of these four compounds are layered, and the use of rigid phenyl spacers allows for the synthesis of pillared layered three-dimensional networks in BaUbbp and SrUbbp. The crystal structures of AgUbbp and CsUbbp reveal the presence of the less-common six-coordinate geometries, whereas BaUbbp and SrUbbp show the common seven-coordinate geometries around the uranyl centers. The incorporation of the monovalent and divalent

Figure 7. Depiction of the pillared layered three-dimensional network in [Sr(H2O)3]{(UO2)2[C6H4(PO3)2](OH)2(H2O)}·3(H2O): UO7 units = green, strontium = yellow, oxygen = red, phosphorus = magenta, carbon = black, and hydrogen = white.

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(9) (a) Cao, G.; Hong, H.-G.; Mallouk, T. E. Acc. Chem. Res. 1992, 25, 420. (b) Clearfield, A. Curr. Opin. Solid State Mater. Sci. 2003, 6, 495. (c) Mao, J.-G. Coord. Chem. Rev. 2007, 251, 1493. (10) (a) Burns, P. C.; Ewing, R. C.; Hawthorne, F. C. Can. Mineral. 1997, 35, 1551. (b) Burns, P. C.; Miller, M. L.; Ewing, R. C. Can. Mineral. 1996, 34, 845. (c) Burns, P. C. Can. Mineral. 2005, 43, 1839. (11) Adelani, P. O.; Albrecht-Schmitt, T. E. J. Solid State Chem. 2011, 184, 2368. (12) Brese, N. E.; O’Keeffe, M. Acta Crystallogr., Sect. B: Struct. Sci. 1991, B47, 192. (13) Liu, G.; Beitz, J. V. In The Chemistry of the Actinide and Transactinide Elements; Morss, L. R., Edelstein, N. M., Fuger, J., Eds.; Springer: Heidelberg, 2006. (14) Frisch, M.; Cahill, C. L. Dalton Trans. 2005, 1518.

metal cations in these structures results in considerable diversity in the architectures.

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ASSOCIATED CONTENT

S Supporting Information *

Bond-valence sums, selected interatomic distances (Å) and angles (deg), and infrared and fluorescence spectra. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful for support provided by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, Heavy Elements Chemistry Program, U.S. Department of Energy, under Grant DE-FG0201ER16026.

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dx.doi.org/10.1021/cg301387p | Cryst. Growth Des. XXXX, XXX, XXX−XXX