2019·VOLUME 234·ISSUE 2

ISSN 2194-4946 · e-ISSN 2196-7105

ZEITSCHRIFT FÜR
KRISTALLOGRAPHIE
CRYSTALLINE
MATERIALS

TOR
T FAC
IMPAC 017
2

EDITOR-IN-CHIEF 1.263
Rainer Pöttgen

www.degruyter.com/zkri

Oleg I. Siidra*, Evgeny V. Nazarchuk, Dmitry O. Charkin, Nikita V. Chukanov, Alexander Yu.
Zakharov, Stepan N. Kalmykov, Yuriy A. Ikhalaynen and Mikhail I. Sharikov
Open-framework sodium uranyl selenate
and sodium uranyl sulfate with protonated
morpholino-N-acetic acid
https://doi.org/10.1515/zkri-2018-2103
Received June 3, 2018; accepted September 5, 2018; published
online September 27, 2018
Abstract: The reaction of sodium N-morpholine acetate
with selenic and sulfuric acid and uranyl nitrate results
in the formation of two novel open-framework com-
pounds, |Na(Hmfa) |[(UO2)2(SeO4)3(H2O)](H2O)2 (NaUSe)
and [Na2(SO3OH)(Hmfa)] |(UO2)(SO4)2 | (NaUS), respec-
tively. Despite identical synthetic procedures, sulfate
structure dramatically differs from selenate compound.
Their common feature is an open-framework featur-
ing two-dimensional system of channels occupied by
protonated morpholino-N-acetic acid species. Coor-
dination of Na atoms is different. In NaUSe, [(UO2)2
(SeO4)3(H2O)]2− layers are pillared by {Na2O8(H2O)2(Hmfa)2}
complexes to form a microporous framework. In NaUS,
UO7 and SO4 polyhedra of [(UO2)(SO4)2]2− chains share
common oxygen atoms with Na-centered tetrameric com-
plexes providing a three-dimensional integrity of the
structure. Both of the compounds are characterized by IR
spectroscopy.
Keywords: open-framework materials; selenates; sulfates;
uranium.
Introduction
Uranium(VI) compounds with various organic molecules
are extensively studied for the use in actinide separation
*Corresponding author: Oleg I. Siidra, Department of
Crystallography, St. Petersburg State University, University Emb.
7/9, St. Petersburg 199034, Russia; and Nanomaterials Research
Center, Kola Science Center, Russian Academy of Sciences, Apatity
184200, Murmansk Region, Russia, E-mail: o.siidra@spbu.ru
Evgeny V. Nazarchuk: Department of Crystallography, St. Petersburg
State University, University Emb. 7/9, St. Petersburg 199034, Russia
Dmitry O. Charkin, Alexander Yu. Zakharov, Stepan N. Kalmykov,
Yuriy A. Ikhalaynen and Mikhail I. Sharikov: Department of Chemistry,
Moscow State University, Leninskie Gory 1, Moscow 119991, Russia
Nikita V. Chukanov: Institute of Problems of Chemical Physics,
Chernogolovka, Moscow Region 142432, Russia
Z. Kristallogr. 2019; 234(2): 109–118
[1] and extraction [2] industry. The majority of them are
metal-organic compounds with organic molecules directly
coordinating the (UO2)2+ ion (e.g. [3]). We may designate
them with the general formula [AU], where A is an organic
molecule and U denotes uranyl units. In case of additional
metals (Me) participating in the metal-organic framework,
the formula can be extended to [AUMe]. Another, smaller
family is characterized by the structures consisting of
weakly bonded inorganic and organic substructures and
called “organically templated” [4]. Organically templated
materials offer greater structural diversity. Topological
and geometrical features of organic complexes control
the structure of inorganic structural units, though their
role is yet unclear. In the overwhelming majority, the
organic templates are positively charged (most commonly
these species are protonated amine species) and form
strong hydrogen bonds to the inorganic (anionic) part of
the structure (e.g. [5, 6]); less often they are electroneu-
tral yielding organic-inorganic “composite” structures.
The latter is typical for uranyl compounds templated by
crown ethers [7]. As usual, the organic moieties behave
as guest species |A |, and uranyl-based complexes play
the role of hosts [U]. However, the opposite situation with
|U | playing the role of guests and [A], of hosts, also has
its representatives. The synthesis of new uranyl oxysalt
materials under ambient conditions using amine-based
structure-directing agents and aqueous selenic acid has
been employed to produce a variety of many new materi-
als [4]. Among several thousands of organically templated
uranyl oxysalts, only quite a few are known where organic
molecules form complexes with guest metal cations.
|AMe |[U] and/or |U |[AMe] structural architectures were
described previously in uranyl nitrate and uranyl acetate
templated by sodium-cucurbit[6]uril complexes [8] and in
several uranyl phosphates templated by zinc- and silver-
bipyridyl complexes [9]. In both reported systems, organic
molecules are not protonated.
Recently, the use of polyfunctional species featur-
ing both amine and carboxylic group (N-phenylglycine)
in combination with Na+ cations led us serendipitously
to a particularly complex uranyl-sulfate nanotube-like
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110 O.I. Siidra et al.: Open-framework uranyl compounds

structure; the Na+ ions coordinate the oxygen atoms

from both inorganic backbone and carboxylic groups of
the organic template [10]. To see if the combined effect
of amino acid and sodium cations could provide more
non-trivial structures, we have undertaken a study with
a distantly structurally related non-aromatic compound,
morpholine-N-acetic acid O(CH2CH2)2NCH2COOH (mfa).
This yielded two unique framework compounds incorpo-
rating the protonated ligand O(CH2CH2)2(NH+)CH2COOH
(Hmfa) and sodium cations which are playing quite differ-
ent roles. |Na(Hmfa) |[(UO2)2(SeO4)3(H2O)](H2O)2 (NaUSe)
and [Na2(SO3OH)(Hmfa)] |(UO2)(SO4)2 | (NaUS) were crys-
tallized from aqueous solution by evaporation. Though
the crystals of both compounds were obtained within
identical synthetic procedures, their structure differs dra-
matically and no analogies are observed. Fig. 1: Infrared absorption spectra of NaUS (1) and NaUSe (2). The
assignment of IR bands is given in Tables 1 and 2.

Experimental section pelletized, and analyzed using an ALPHA FTIR spectrometer (Bruker
Optics) with a resolution of 4 cm−1. 16 Scans were obtained. The IR
Synthesis spectrum of an analogous pellet of pure KBr was used as a reference.
The assignment (Tables 1 and 2) of absorption bands was made in
The sodium N-morpholine acetate (0.2 mmol) was prepared accord-
ing to [11]. Chloroacetic acid (Vekton, Voronezh, Russia; 99.5%)
(4.725 g, 50 mmol) and sodium hydroxide (Vekton, Voronezh, Russia; Tab. 1: IR absorption bands of NaUSe (w, weak band; s, strong
98%) (4.0 g, 100 mmol) were added to 15 mL ethanol and stirred in band; sh, shoulder) and their assignment.
an ice bath. Morpholine (Vekton, Voronezh, Russia; 99.8%) (4.35 mL,
50 mmol) and 10 mL ethanol were added dropwise while vigorous stir- Wavenumbers (cm − 1) Assignment
ring. So obtained solution was stirred for another 1 h at 0 °C and at
3615sh, 3572, 3460, 3398 O–H stretching vibrations of H2O
room temperature for 5 h. Then it was heated under reflux at 50–65 °C
3145w, 2991, 2956w, N–H and C–H stretching
for 3 h and after that evaporated to complete dryness. Recrystalliza-
2918w, 2878, 2860 vibrations
tion was carried out by diluting the crude product in 40 mL methanol–
2778, 2748, 2712, 2690sh, O–H stretching vibrations (acid
acetonitrile (1:3 v/v) mixture and filtering the undissolved particles
2655w, 2613w, 2553w, 2460 groups)
out. Diffusion of ether into the filtrate gave white needle-like crystals
1703 C=O stretching vibrations
which were isolated by filtration and washed with 15 mL acetone. The
1629, 1598 HOH bending vibrations of H2O
purity of the product was confirmed by 1H NMR: (400 MHz, DMSO-
1469, 1457, 1448, 1436, HCH and HNC bending vibrations
d6) δ ppm 2.38 (br. s., 4 H) 2.69 (s, 2 H) 3.53–3.58 (m, 4 H) (Figure S1).
1421, 1402, 1336w, 1355w,
The precursor was dissolved in 2 mL of distilled water. In a separate
1343, 1307w, 1285, 1258
vial, 10 mmol of H2SO4 (taken as 1 M solution) or H2SeO4 (98%) were
1148w, 1124 Stretching vibrations of C–O
added to 2 mL of 0.1 M solution of UO2(NO3)2. The solutions of ura-
bonds
nium and organic template were mixed, poured onto watch glasses
1096, 1069, 1017, 1019w, Mixed modes involving C–O, C–N
and left evaporate in a fume hood. Good quality yellow crystals exhib-
1005w, 960s and C–C stretching vibrations
iting green luminescence were formed and collected after 2 weeks.
924, 904s Asymmetric stretching vibrations
The remaining yellow syrupy residues were discarded. The estimated
of UO22+
yields are ca. 20%. The pH values of the solutions described above are
847s, 830, 820sh Asymmetric ν3(F2) stretching
close to 1. Precipitation of crystals increases acidity.
vibrations of SeO42− and
Qualitative electron microprobe analysis of NaUSe and NaUS
stretching vibrations of C–N
(LINK AN-10000 EDS system) revealed no other elements, except Na,
bonds (overlapping bands and/or
U, Se (in NaUSe) and S (in NaUS) with atomic number greater than
mixed modes)
11 (Na).
740, 712 Pendular vibrations of CH2 groups
667, 634 Mixed bending modes
Infrared spectroscopy 517w, 464, 419 COC, CCO and CCC bending
vibrations
393s, 379 ν4(F2) – bending vibrations of
In order to obtain infrared (IR) absorption spectra (Figure 1), pow-
SeO42−
dered samples of NaUSe and NaUS have been mixed with dried KBr,

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 O.I. Siidra et al.: Open-framework uranyl compounds 111

Tab. 2: IR absorption bands of NaUS (w, weak band; s, strong band; Tab. 3: Crystallographic data and refinement parameters for
sh, shoulder) and their assignment. Na(Hmfa)[(UO2)2(SeO4)3(H2O)](H2O)2 and Na2(SO3OH)(Hmfa)[(UO2)
(SO4)2].
Wavenumbers (cm − 1) Assignment
NaUSe NaUS
3488, 3475, 3422 O–H stretching vibrations
(adsorbed water) a (Å) 10.7767(5) 6.860(3)
3040sh, 3022s N–H stretching vibrations b (Å) 12.2679(5) 10.546(4)
2963, 2920, 2883 C–H stretching vibrations c (Å) 17.9043(8) 13.047(5)
2795, 2777, 2760, 2722, O–H stretching vibrations (acid α (°) 85.186(6)
2610, 2512, 2470, 2265w groups) β (°) 92.1260(10) 88.017(5)
1775sh, 1751s, 1725sh C=O stretching vibrations γ (°) 79.752(5)
1636w, 1587w HOH bending vibrations (adsorbed V (Å3) 2365.45(18) 925.4(6)
water) Radiation MoKα MoKα
1484w, 1450, 1417, 1403, HCH and HNC bending vibrations Total reflections 26747 9978
1374, 1325, 1310, 1287s Unique reflections 6761 4236
1246s, 1232s, 1184s, Overlapping bands of asymmetric Unique |Fo | ≥ 4σF 5554 3381
1170sh, 1128, 1107s, ν3(F2) stretching vibrations of SO42− Space group P21/c P1̅
1070s, 1053s, 1034s and stretching vibrations of C–O θ range 1.89–29.79 1.57–27.54
bonds and HSO4− Crystal size (mm) 0.12 × 0.11 × 0.05 0.14 × 0.14 × 0.10
1007s Symmetric stretching vibrations of μ (cm−1) 18.408 9.245
distorted SO42− Dcalc (g/cm3) 3.336 2.697
981 Stretching vibrations of HSO4− GoF 1.019 0.990
(nondegenerate mode) R1 0.034 0.055
930s Asymmetric stretching vibrations R1 (all data) 0.047 0.074
of UO22+, possibly mixed with
stretching vibrations of C–N bonds
888, 865s, 852, 840sh Stretching vibrations of C–N bonds,
V = 2365.45(18) Å3, whereas NaUS is triclinic, P1,̅ a = 6.860(3)
possibly mixed with asymmetric
Å, b = 10.546(4) Å, c = 13.047(5) Å, α = 85.186(6)°, β = 88.017(5)°,
stretching vibrations of UO22+
γ = 79.752(5)° V = 925.4(6) Å3 (Table 1). Both structures were success-
740 Bending vibrations of CH2 groups
fully refined with the use of SHELX software package [19]. The final
672, 652, 635sh, 603s, ν4(F2) – bending vibrations of SO42−
model for NaUSe included anisotropic displacement parameters for
591, 578s and bending vibrations of HSO4−
all atoms excluding C and O in mfa and one water molecule (OW3) in
(nondegenerate mode)
a structural cavity. For NaUS, all non-hydrogen atoms were refined
515, 473w, 455, 431, ν2(E) bending mode of SO42−
anisotropically. The hydrogen atoms were added to their ideal posi-
384w anions, COC, CCO and CCC bending
tions using HFIX command. Hydrogen atoms on OW3 molecule in
vibrations (overlapping bands)
NaUSe could not be localized. Further details of the data collection
The acid groups are HSO4− and –COOH−. and refinement are given in Table 3, atomic coordinates and displace-
ment parameters are in Tables 4 and 5 and selected bond lengths in
Tables 6 and 7.
accordance with Smith [12], Hoekstra [13], Čejka [14], Nakamoto [15, The bond-valence sums for all cation and anion sites in inor-
16], and Chukanov and Chervonnyi [17]. ganic units for both compounds are listed in Tables 4 and 5, and
were calculated using the parameters derived by Burns et al. [21] for
U6+, and by Brown and Altermatt [20] for Na+, Se6+ and S6+. The bond-
X-ray experiment valence sums are in good agreement with expected formal oxidation
states for all elements.
The crystals of NaUSe and NaUS selected for data collection were
examined under an optical microscope and mounted on glass fibers.
The single crystal X-ray analysis of NaUSe and NaUS was carried out
using a Bruker SMART diffractometer equipped with an APEX II CCD Results
detector operating with MoKα radiation at 50 kV and 40 mA. A single
yellow translucent prismatic crystal of NaUSe with dimensions of
0.12 × 0.11 × 0.05 mm3 and a one of NaUS with similar habit measur- Cation coordination
ing 0.14 × 0.14 × 0.10 mm3 were chosen. For each crystal more than a
hemisphere of data was collected with a frame width of 0.5° in ω, and Na(Hmfa)[(UO2)2(SeO4)3(H2O)](H2O)2
20 s counting time spent for each frame. The data were integrated
and corrected for absorption using a multi-scan type model using
the Bruker programs APEX and SADABS [18]. The structures were The structure of NaUSe contains (Table 2) two sym-
solved by direct methods. NaUSe is monoclinic, space group P21/c, metrically unique U6+ cations, each strongly bonded
a = 10.7767(5) Å, b = 12.2679(5) Å, c = 17.9043(8) Å, β = 92.1260(10)°, to two oxygen atoms thus forming nearly linear uranyl

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112 O.I. Siidra et al.: Open-framework uranyl compounds

Tab. 4: Coordinates and isotropic displacement parameters (Å2) of atoms and bond-valence sumsa (B.V.S.) in Na(Hmfa)[(UO2)2(SeO4)3(H2O)]
(H2O)2.

Atom B.V.S.a x y z Ueq

U1 5.98 0.93457(2) 0.049995(16) 0.239679(13) 0.01372(7)

U2 6.01 0.47398(2) −0.171945(17) 0.241847(13) 0.01462(7)
Se1 6.14 0.13950(5) −0.18274(4) 0.17801(4) 0.01549(13)
Se2 6.04 0.63228(5) 0.06229(4) 0.33715(4) 0.01544(13)
Se3 6.07 0.81737(5) −0.23450(4) 0.28040(4) 0.01446(13)
Na1 1.15 0.0833(3) −0.3944(2) 0.04500(18) 0.0347(7)
O1 1.90 0.5203(4) 0.1522(3) 0.3208(3) 0.0187(9)
O2 1.99 0.2905(4) −0.1849(3) 0.1661(3) 0.0191(9)
O3 1.99 0.5653(4) −0.0580(3) 0.3369(3) 0.0225(10)
O4 1.95 0.8563(4) −0.1343(3) 0.2250(3) 0.0184(9)
O5 1.94 0.9643(4) 0.0259(3) 0.3356(3) 0.0198(9)
O6 1.73 0.9024(5) 0.0746(4) 0.1437(3) 0.0266(11)
O7 2.03 0.1082(4) −0.2601(3) 0.2492(3) 0.0233(10)
O8 2.01 0.1073(4) −0.0575(3) 0.2016(3) 0.0242(11)
O9 1.77 0.5461(4) −0.1112(4) 0.1662(3) 0.0272(11)
O10 1.76 0.4010(4) −0.2340(4) 0.3170(3) 0.0244(10)
O11 2.02 0.6662(4) −0.2526(3) 0.2746(3) 0.0255(11)
O12 2.05 0.7245(4) 0.0656(3) 0.2665(3) 0.0257(11)
O13 1.82 0.7029(4) 0.0848(4) 0.4164(3) 0.0284(11)
O14 1.61 0.8625(5) −0.2128(4) 0.3660(3) 0.0328(12)
O15 1.86 0.0679(5) −0.2221(4) 0.1026(3) 0.0319(12)
O16 1.98 0.8735(4) −0.3493(3) 0.2496(3) 0.0281(12)
OW1 0.44 0.3510(4) −0.0046(4) 0.2533(3) 0.0262(11)
H13 0.3631 0.0575 0.2181 0.050
H14 0.2887 0.0015 0.2932 0.050
OW2 0.12 0.1256(8) −0.3274(5) −0.0764(4) 0.060(2)
O18 0.8663(5) −0.4261(4) 0.0152(3) 0.0333(12)
O19 0.7277(7) −0.5062(6) 0.0872(4) 0.0612(19)
H1 0.7654 −0.5778 0.0739 0.050
O20 0.7298(8) −0.0160(7) −0.0217(5) 0.075(2)
OW3 0.3074(8) −0.2039(6) −0.0117(5) 0.074(2)
N1 0.7106(5) −0.2482(5) −0.0097(4) 0.0288(14)
H2 0.7584 −0.2701 −0.0541 0.050
C1 0.7935(8) −0.1808(7) 0.0404(5) 0.041(2)
H3 0.8677 −0.2248 0.0570 0.050
H4 0.7480 −0.1592 0.0858 0.050
C3 0.6650(9) −0.3471(7) 0.0257(5) 0.045(2)
H5 0.5995 −0.3810 −0.0079 0.050
H6 0.6257 −0.3270 0.0736 0.050
C4 0.6031(9) −0.1780(8) −0.0365(6) 0.049(2)
H7 0.5511 −0.2190 −0.0745 0.050
H8 0.5500 −0.1602 0.0065 0.050
C5 0.7672(8) −0.4299(6) 0.0419(5) 0.0362(18)
C6 0.8351(11) −0.0811(9) 0.0007(7) 0.063(3)
H9 0.8922 −0.0377 0.0346 0.050
H10 0.8818 −0.1025 −0.0443 0.050
C7 0.6483(11) −0.0755(9) −0.0702(7) 0.067(3)
H11 0.6922 −0.0935 −0.1169 0.050
H12 0.5752 −0.0286 −0.0845 0.050
a
Expressed in valence units (vu) and calculated using the parameters from Brown and Altermatt [20] for Na+–O, Se6+–O bonds and from
Burns et al. [21] for U6+–O bonds.

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Tab. 5: Selected interatomic distances (Å) in Na(Hmfa) There are three distinct S6+ sites tetrahedrally coor-
[(UO2)2(SeO4)3(H2O)](H2O)2. dinated by four O atoms each (Table 5). The average S–O
bond-lengths, 1.46–1.47 Å, are consistent with the average
U1–O5 1.760(5) U2–O9 1.754(5) Na1–O15 2.361(6)
value of 1.475 Å given for sulfates in general [22]. The
U1–O6 1.766(5) U2–O10 1.757(5) Na1–OW2 2.384(8)
U1–O12 2.340(5) U2–O11 2.350(4) Na1–O13 2.395(5) S3–OH1 bond is essentially longer (1.566 Å) than the three
U1–O7 2.385(4) U2–O2 2.362(4) Na1–O18 2.411(6) other S–O bonds (1.402–1.444 Å), indicating a hydrosulfate
U1–O8 2.401(4) U2–O3 2.386(4) Na1–O5 2.423(6) monoanion [23]. The bond-valence sum for the OH1 site is
U1–O16 2.411(4) U2–O1 2.434(4) Na1–O18 2.520(6) 1.18 valence units (v.u.), which is in agreement with the
U1–O4 2.424(4) U2–OW1 2.457(4)
assignment of this site to a hydroxyl group.
Se1–O15 1.604(5) Se2–O13 1.610(5) Se3–O14 1.612(5) Coordination of Na1 and Na2 atoms in NaUS is differ-
Se1–O7 1.634(5) Se2–O12 1.637(5) Se3–O16 1.637(4)
ent from Na1 in NaUSe. Coordination number (CN) of Na1
Se1–O8 1.634(4) Se2–O3 1.643(4) Se3–O4 1.644(4)
Se1–O2 1.649(4) Se2–O1 1.653(4) Se3–O11 1.644(4) is five and typical for sodium atoms in oxysalt structures in
<Se1–O> 1.630 <Se2–O> 1.636 <Se3–O> 1.634 general, whereas CN is equal to eight for Na2 (Figure 3b).
NaO5 and NaO8 polyhedra share common edges thus
forming Na4O19 tetramers. Protonated S3O3OH tetrahe-
(UO2)2+ ions (Ur). Each uranyl ion is coordinated by five dra are bridged to these complexes via two common
additional O atoms located at the equatorial vertices of edges. The (Hmfa)+ moieties bridge these Na tetrameric
pentagonal bipyramids (Figure 2), the apical vertices of ­complexes (Figure 3b).
which are the OUr atoms. Bond lengths within the uranyl
ions range from 1.754 to 1.766 Å, whereas the U–O bond
lengths corresponding to the equatorial ligands range Structure description
from 2.340 to 2.457 Å, which is typical for UrO5 polyhe-
dra in uranyl oxysalts [4]. The equatorial plane of uranyl Na(Hmfa)[(UO2)2(SeO4)3(H2O)](H2O)2
group U(2) is defined by four Oeq atoms and one H2O
molecule (OW1) and form UrO4(H2O) pentagonal bipy- The UrO5, UrO4(H2O) and SeO4 coordination polyhedra
ramids. The U(2)–OW(1) bond is somewhat longer than share corners to produce [(UO2)2(SeO4)3(H2O)]2− layers with
other U–Oeq bonds. a relatively common topology. Each SeO4 tetrahedron
The coordination environments of three symmetri- shares three corners with adjacent uranyl polyhedra. The
cally independent selenate tetrahedra in NaUSe are prac- [(UO2)2(SeO4)3(H2O)]2− layers are parallel to the ab plane
tically undistorted. The average <Se–O> bond lengths are (Figure 2a). The structure of NaUSe contains two [(UO2)2
1.63 Å in all tetrahedra. (SeO4)3(H2O)]2− layers per unit cell. [(UO2)2(T6+O4)3(H2O)]2−
The sodium atom is in octahedral environment (T = S6+, Cr6+, Se6+) layers were previously described for a
(Figure 3a), where one vertex is occupied by an oxygen number of uranyl compounds [5, 6, 24–27]. What makes the
atom from the carboxylate group of the organic template structure of NaUSe unique is that the {Na2O8(H2O)2(Hmfa)2}
(Hmfa)+. The Na–O18 bond length is 2.520(6) Å. The other complexes interconnect the [(UO2)2(SeO4)3(H2O)]2− layers
vertex of Na-centered octahedron is occupied by a water into a microporous framework (Figure 4a and b) with a
molecule (OW2). NaO5(H2O) octahedra share common two-dimensional system of channels. There is an “addi-
edges resulting in Na2O8(H2O)2 dimers with Na–Na dis- tional” water molecule (OW3) not bonded to any metal
tance of 3.509(4) Å. Two molecules of the protonated cations; it fills the cavities of the framework.
organic template decorate these species to form isolated
{Na2O8(H2O)2(Hmfa)2} complexes.
Na2(SO3OH)(Hmfa)[(UO2)(SO4)2]

Na2(SO3OH)(Hmfa)[(UO2)(SO4)2] The structure of NaUS is based upon uranyl sulfate chains

The triclinic structure of NaUS contains one symmetri-
cally independent U6+ cation also forming linear Ur uranyl
ion which is coordinated by five oxygen atoms at the equa-
torial vertices of pentagonal bipyramids similar to those
observed in NaUSe. Water molecules are absent in the
coordination sphere of uranium atom in NaUS.
with the composition [(UO2)(SO4)2]2− (Figure 2b). Similar
chains were described before in several organically tem-
plated uranyl sulfate compounds [28, 29]. Within the
chain, two adjacent UrO5 pentagonal bipyramids share
three equatorial O atoms and O–O edge with S1O4 and S1O4
tetrahedra. Thus S1O4 tetrahedra are interconnected with
UrO5 in a monodentate fashion, whereas S2O4 tetrahedra

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114 O.I. Siidra et al.: Open-framework uranyl compounds

Tab. 6: Coordinates and isotropic displacement parameters (Å2) of atoms and bond-valence sumsa (B.V.S.) in Na2(SO3OH)(Hmfa)[(UO2)(SO4)2].

Atom B.V.S.a x y z Ueq

U1 6.08 −0.26295(5) 0.47052(4) 0.16431(3) 0.01870(14)

S1 6.12 0.2274(3) 0.5407(3) 0.11019(18) 0.0194(5)
S2 6.06 −0.2815(4) 0.5298(3) 0.39316(19) 0.0237(6)
S3 6.32 −0.0594(5) 0.9068(3) 0.3738(3) 0.0430(8)
Na1 1.10 0.2013(7) 0.5983(5) 0.3535(3) 0.0342(11)
Na2 0.97 0.1199(8) 0.7938(5) 0.5860(4) 0.0438(13)
O1 1.78 −0.3163(12) 0.6339(8) 0.1196(6) 0.0329(18)
O2 1.79 −0.2150(11) 0.3064(8) 0.2115(6) 0.0311(18)
O3 2.09 0.2408(11) 0.5956(8) 0.0042(6) 0.0279(17)
O4 2.03 0.0684(10) 0.4611(8) 0.1186(6) 0.0268(17)
O5 2.04 −0.1097(11) 0.5242(8) 0.3196(6) 0.0301(18)
O6 1.98 0.1941(13) 0.6402(8) 0.1798(6) 0.0312(18)
O7 2.00 0.4146(10) 0.4479(8) 0.1346(6) 0.0279(17)
O8 2.03 −0.4478(10) 0.5156(8) 0.3263(6) 0.0279(17)
O9 2.05 −0.2468(12) 0.4241(8) 0.4722(6) 0.0337(19)
O10 1.83 −0.0380(13) 0.0227(8) 0.3107(7) 0.039(2)
O11 1.59 −0.3196(13) 0.6544(9) 0.4367(7) 0.041(2)
O12 2.01 0.1262(16) 0.8214(10) 0.3890(9) 0.056(3)
O13 1.18 −0.1893(18) 0.8392(10) 0.3071(9) 0.061(3)
H1 −0.1537 0.7432 0.3214 0.050
O14 1.95 −0.1626(18) 0.9340(11) 0.4663(8) 0.061(3)
N1 0.3215(15) 0.0556(10) 0.2105(8) 0.031(2)
H2 0.175(15) 0.052(9) 0.237(7) 0.005
C1 0.6306(18) 0.8090(12) 0.6487(9) 0.030(3)
O15 −0.2387(14) 0.9899(9) −0.0053(6) 0.039(2)
C2 0.391(2) 0.9252(12) 0.1685(9) 0.035(3)
H3 0.3914 0.8545 0.2247 0.050
H4 0.5293 0.9200 0.1395 0.050
C3 0.303(2) 0.1596(13) 0.1238(10) 0.039(3)
H5 0.4358 0.1635 0.0909 0.050
H6 0.2498 0.2455 0.1506 0.050
C4 0.456(2) 0.0777(14) 0.2929(11) 0.045(3)
H7 0.4830 0.9985 0.3417 0.050
H8 0.5858 0.0925 0.2607 0.050
C5 −0.161(2) 0.8705(14) −0.0442(11) 0.044(3)
H9 −0.1449 0.8006 0.0133 0.050
H10 −0.0282 0.8739 −0.0771 0.050
C6 −0.251(2) 0.0899(12) −0.0847(10) 0.042(3)
H11 −0.1154 0.0908 −0.1158 0.050
H12 −0.2964 0.1748 −0.0548 0.050
O16 0.4951(13) 0.7819(9) 0.5887(7) 0.039(2)
H13 0.5309 0.6896 0.5718 0.050
O17 0.7973(13) 0.7545(10) 0.6547(7) 0.045(2)
a
Expressed in valence units (vu) and calculated using the parameters from Brown and Altermatt [20] for Na+–O, S6+–O bonds and from Burns
et al. [21] for U6+–O bonds.

are bidentatly bridged. [(UO2)(SO4)2]2− chains extend along
the a axis. Note that S3O3OH tetrahedron does not share
common oxygen atoms with UrO5 bipyramids in the uranyl
sulfate chains. The Na-centered tetrameric complexes
share common oxygen atoms with uranyl and sulfate poly-
hedra of the [(UO2)(SO4)2]2− chains. Similar to NaUSe, the
resulting framework (Figure 4d and e) also exhibits a 2D
system of channels occupied by organic molecules.
In both structures, the C–C, C–N and C–O bond
lengths as well as the bond angles in Hmfa are within the
limits typically observed for this molecule. Additional
linkage between Hmfa and uranyl selenate (in NaUSe)

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 O.I. Siidra et al.: Open-framework uranyl compounds 115

Tab. 7: Selected interatomic distances (Å) in Na2(SO3OH)(Hmfa) 1.763, 1.751 Å, respectively, which is in a good agreement
[(UO2)(SO4)2]. with the values determined from X-ray structural data
(1.760 + 1.766 and 1.754 + 1.757 Å). A worse agreement
U1–O1 1.751(8) Na1–O6 2.273(9) Na2–O10 2.425(11)
between these values in the case of NaUS (1.767 Å calcu-
U1–O2 1.765(8) Na1–O9 2.293(9) Na2–O17 2.449(11)
U1–O7 2.316(7) Na1–O12 2.398(1) Na2–O9 2.480(10) lated for the IR band at 930 cm−1 and the values of 1.754
U1–O4 2.317(7) Na1–O8 2.435(8) Na2–O16 2.556(10) and 1.765 Å determined from structural data) may be due
U1–O3 2.353(7) Na1–O5 2.465(8) Na2–O12 2.561(12) to resonance between U–O and C–N stretching vibrations
U1–O8 2.463(7) Na2–O14 2.679(14) resulting in some band shifts.
U1–O5 2.466(7) Na2–O2 2.816(10)
Na2–O14 2.958(13)
S1–O6
S1–O3
1.428(8)
1.461(8)
S2–O9
S2–O11
1.446(8)
1.452(9)
S3–O14
S3–O12
1.402(11)
1.432(10)
Discussion
S1–O4 1.486(8) S2–O5 1.490(8) S3–O10 1.442(9)
S1–O7 1.495(7) S2–O8 1.496(7) S3–O13 1.563(11) The novel compounds, uranyl selenate |Na(Hmfa) |[(UO2)2
<S1–O> 1.468 <S2–O> 1.471 <S3–O> 1.460 (SeO4)3(H2O)](H2O)2 (NaUSe) and uranyl sulfate [Na2(HSO4)
(Hmfa)] | (UO2)(SO4)2 | (NaUS) were obtained and their
crystal structures solved. 2∞ [(UO2 )2 (SeO4 )3 (H2O)]2 − and
or uranyl sulfate units in NaUS is provided via N–H · · · O 1
∞
[(UO2 )(SO4 )2 ]2− units were reported previously in a
hydrogen bonds. number of uranyl oxysalts. Topology of both structural
According to the correlation dU−O (Å) = 81.2ν3−2/3 + 0.895 units is very different. 2∞ [(UO2 )2 (SeO4 )3 (H2O)]2 − have only
for uranyl groups [13], the ν3 bands at 904, and 924 cm−1 monodentate bridging (Figure 2a) between uranyl poly-
in NaUSe correspond to the mean U–O bond lengths of hedra and SeO4 tetrahedra, whereas 1∞ [(UO2 )(SO4 )2 ]2−

Fig. 2: UO7 pentagonal pyramids share common corners and edges with SeO4 or SO4 tetrahedra thus forming units of different
dimensionality. Polyhedral and balls-and-sticks representation of [(UO2)2(SeO4)3 (H2O)]2− layers in NaUSe and [(UO2)(SO4)2]2− in NaUS.

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116 O.I. Siidra et al.: Open-framework uranyl compounds
Fig. 3: Na2O10 dimers coordinated by Hmfa in the structure of NaUSe (a). Na4O19 tetramers and SO3OH tetrahedra in the structure of NaUS (b).
Coordination of Na atoms by Hmfa in NaUS (c).
combine monodentate and bidentate coordination
modes (Figure 2b). Bidentate bridging is impossible for
uranyl polyhedra and SeO4 tetrahedra because of the
relatively large size of Se6+ and high repulsive forces.
Thus the topology of 1∞ [(UO2 )(SO4 )2 ]2− cannot be realized
in selenate compounds. NaUSe and NaUS structures are
interesting representatives of uranyl compounds with
tetrahedral oxyanions, where 2∞ [(UO2 )2 (SeO4 )3 (H2O)]2 −
and 1∞ [(UO2 )(SO4 )2 ]2− participate in the formation of open-
frameworks. Guest Na complexes with (Hmfa)+ cations link
the host 2∞ [(UO2 )2 (SeO4 )3 (H2O)]2 − layers (Figure 4c) into the
framework in NaUSe. The reverse structural architecture
(Figure 4f) is observed in NaUS, where 1∞ [(UO2 )(SO4 )2 ]2−
chains (guests) are inserted between the complex Na
tetrameric units (hosts) (Figure 4b). The striking structural
differences between the selenate and sulfate synthesized
under identical conditions are the result of the higher
more than an order of magnitude reduction potential of
H2SeO4 compared to H2SO4 [30].
In both structures, protonated form of morpholino-
N-acetic acid (CH2)4O(NH)+(CH2)COOH together with
Na+ cations, compensates the negative charge of
uranyl selenate and uranyl sulfate complexes, overall
electroneutrality of the structure. Usually in oxysalt struc-
tures with various metals, aminoacids are present in the
form of anion or a zwitterion [31]. Note, in NaUS (Hmfa)+
associates with hydrosulfate HSO4− group. Protonated
aminoacids were previously reported in sulfate com-
pounds [32].
NaUSe and NaUS differ from the most of previously
reported organically templated uranyl oxysalts with tet-
rahedral anions in the dimensionality of their structures.
Na atoms play an important role in the formation of
open-frameworks in both studied compounds. Two dif-
ferent host-guest architectures corresponding to |AMe |[U]
(in NaUSe) and |U |[AMe] (in NaUS) types are observed.
Recently, nanotubular complexes were reported in Na
uranyl sulfate templated by protonated N-phenylglycine
[10]. Understanding the structural principles of the forma-
tion of host-guest uranyl based compounds with various
organic templating agents might contribute to the design
of open-framework arrangements. Amino acids seem to
be underexplored for this purpose. Protonated amino
acids might be taken applied in synthetic strategies for
designing of uranyl compounds with microporous and
mesoporous structural architectures.
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Fig. 4: General projection of the open-frameworks of NaUSe (designations: (UO2)O5, orange; SeO4, green; NaO6, blue) along the b (a) and a
axis (b) and NaUS (designations: (UO2)O5, orange; SO4, yellow; Na tetramers, blue) along the a (d) and c axis (e). Schematic representations
of the frameworks in NaUSe (c) and NaUS (f) (designations: [(UO2)2(SeO4)3(H2O)]2−, [(UO2)(SO4)2]2−, orange; sodium polyhedra, blue).
Acknowledgements: This work was financially supported
by the Russian Science Foundation through the grant
16-17-10085. Technical support by the SPbSU X-ray Diffrac-
tion and Microscopy and Microanalysis Resource Centers
is gratefully acknowledged.
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Supplementary Material: The online version of this article offers
supplementary material (https://doi.org/10.1515/zkri-2018-2103).
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