Article

pubs.acs.org/crystal

Crystal Chemistry of Alkali Thorium Silicates Under Hydrothermal

Conditions
J. Matthew Mann, Colin D. McMillen, and Joseph W. Kolis*
Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University,
Clemson, South Carolina 29634-0973, United States
S Supporting Information
*

ABSTRACT: An investigation into the crystal chemistry of

the alkali thorium silicates resulted in the formation of ve
novel materials by hydrothermal synthesis. Of these,
Rb4Th2Si12O30, and K2ThSi4O10F2 are new structure types
crystallizing in space groups P1 and Pnma, respectively. The
structure of Rb4Th2Si12O30 reveals a silicate sheet structure
with eight-, six-, ve-, and four-membered silicate rings.
Crystals of a related composition, Cs2ThSi6O15, were also
synthesized. They crystallize in space group Cmc21 and have a
silicate sheet containing eight-, six-, and four-membered silicate
rings. The structure of K2ThSi4O10F2 consists of a tubular
silicate column comprised of eight-, six-, and four-membered silicate rings and features chains of uorine-bridged Th atoms. Two
new wadeite analogues Cs2ThSi3O9 and Rb2ThSi3O9 were also discovered and constitute the rst actinide representatives in this
mineral family. All products were crystallized from reactions of ThO2 and silica with alkali uorides or hydroxides in
hydrothermal uids at 575 C. They were all characterized by single crystal X-ray diraction and infrared spectroscopy, and
detailed structural comparisons are provided. The work signicantly expands the eld of synthetic thorium silicates.

I. INTRODUCTION

The two polymorphs of ThSiO4, thorite and huttonite, are

the only examples of thorium orthosilicate minerals.9 When
heated, the thorite phase will transform into the huttonite phase
at approximately 1200 C.10 However, the low temperature
thorite phase is usually found in a metamict state, which results
from an ongoing transformation from a crystalline to
amorphous state in the presence of ssionable nuclides.1114
While this phenomenon allows the age of mineralogical veins
containing thorite to be compared based upon its level of
deterioration, it also introduces challenges in structurally
characterizing natural samples since they are often in poorly
crystalline states.15 The mineralogical formation of other
thorium silicates is quite limited, especially when compared
to the extensive tetravalent titanium and zirconium silicate
families.1618 The thorium silicate minerals generally consist of
poorly characterized or rare minerals in the steenstrupine,19
thornasite,20,21 ekanite,22,23 and coutinhoite families.24 So in
addition to the challenges of poor crystallinity, the descriptive
and structural chemistry of thorium silicates has not garnered
much attention with few natural examples.
Also, a considerable limitation to synthetic studies of thorium
silicate chemistry is the refractory nature of ThO2, having a
melting point of approximately 3377 C and almost complete
insolubility in conventional solvents or uxes.25 This precludes

Despite its potential signicance, the fundamental descriptive

crystal chemistry of thorium with standard building blocks
(silicates, phosphates, etc.) remains surprisingly underdeveloped. In particular, its simple reaction chemistry compared to
uranium is still poorly understood for many classes of
compounds. Although thorium is more prevalent in the Earths
crust than uranium, there are signicantly fewer minerals based
on thorium.1 Much of this is due to the variety of stable
oxidation states of uranium, and the more soluble nature of
uranium in these oxidation states than Th4+.2 In particular, U6+
is quite soluble in many aqueous environments as the uranyl
(UO22+) ion, while U4+ is slightly soluble in carbonate and
chloride containing hydrothermal uids. In contrast thorium
only exists in the tetravalent state, and Th4+ is essentially
completely insoluble in almost anything but high concentrations of uoride.3,4 While thorium does participate as a
substituting element in many minerals, those that utilize
thorium as a primary building block are much fewer. Given the
signicance of thorium in geological processes related to rare
earth ores, as well as growing interest in thorium as a nuclear
fuel source,5,6 its role in modeling long-term waste immobilization,7 and the relatively undeveloped state of exploratory
thorium chemistry, it is useful to expand the descriptive
inorganic crystal chemistry of thorium.8 This paper provides an
initial report on the chemistry of Th4+ with alkali silicate
building blocks.
XXXX American Chemical Society

Received: November 24, 2014

Revised: April 7, 2015

DOI: 10.1021/cg5017164
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Table 1. Crystallographic Data of Alkali Thorium Silicates
chemical formula
F.W. (g/mol)
temperature (K)
crystal system
space group
unit cell dimensions
a ()
b ()
c ()
(deg)
(deg)
(deg)
volume (3)
Z
D (calcd) (g/cm3)
, mm1
F(000)
crystal size (mm3)
2 range,
indices (min)
(max)
rens collected
indep reections
obs rens (I > 2(I))
parameters
nal R (I > 2(I))
R
wR
nal R (all data)
R
wR
goodness of t (S)
extinction coe
Flack parameter

Cs2ThSi6O15

Rb4Th2Si12O30

K2ThSi4O10F2

Cs2ThSi3O9

Rb2ThSi3O9

906.40
293
orthorhombic
Cmc21 (No. 36)

1623.04
293
triclinic
P1 (No. 2)

620.60
293
orthorhombic
Pnma (No. 62)

726.13
293
hexagonal
P63/m (No. 176)

631.25
293
hexagonal
P63/m (No. 176)

7.2813(15)
16.420(3)
13.591(3)
90
90
90
1625.0(6)
4
3.705
14.106
1616
0.24 0.22 0.17
2.4826.40
[8, 20, 16]
[8, 20, 16]
7540
1573, Rint = 0.0726
1381
125

7.3288(15)
12.235(2)
17.510(4)
98.97(3)
90.97(3)
106.44(3)
1484.4(5)
2
3.631
17.124
1472
0.27 0.10 0.10
2.7025.15
[8, 14, 20]
[8, 14, 20]
12302
5228, Rint = 0.0505
3387
433

11.794(2)
8.5762(17)
22.099(4)
90
90
90
2235.3(7)
8
3.688
14.591
2256
0.24 0.18 0.12
3.0825.25
[14, 9, 26]
[14, 9, 26]
16600
2157, Rint = 0.0583
1738
214

7.4738(11)
7.4738(11)
10.674(2)
90
90
120
516.34(15)
2
4.670
21.762
628
0.29 0.21. 0.14
3.1526.32
[9, 8, 13]
[9, 8, 13]
4540
372, Rint = 0.0661
337
28

7.3064(10)
7.3064(10)
10.604(2)
90
90
120
490.22(14)
2
4.276
25.467
556
0.27 0.26 0.11
3.2226.40
[9, 9, 13]
[9, 9, 13]
4335
357, Rint = 0.0865
320
28

0.0391
0.0814

0.0322
0.0590

0.0382
0.0893

0.0251
0.0563

0.0305
0.0649

0.0470
0.0867
1.080
0.00044
0036(14)

0.0614
0.0701
0.750
0.0007

0.0488
0.0954
1.115

0.0294
0.0590
1.183
0.0238

0.0338
0.0664
1.183
0.0164

considerably, and we now exploit it to extend the hydrothermal

chemistry to the thorium silicates. Given the signicance of
thorium geochemistry, the classical problems with the poor
quality of natural thorium compounds due to the metamict
states of many thorium-based minerals,40 and especially the
challenge of understanding the reaction chemistry of refractory
oxides, an expansion of the descriptive hydrothermal chemistry
of the thorium silicates seems timely.

the use of traditional melt-based techniques for synthesis of

new materials. In fact, the only purely synthetic thorium silicate
single crystal known (Cs2ThSi6O15) was synthesized somewhat
fortuitously.26 A second synthetic thorium silicate, RbNaCaThSi8O20 (based on the ekaniteturkestanite system), was only
obtained as a powder from a solid-state reaction of metal
nitrates with silica.27 Thus, the targeted synthesis of thorium
silicate single crystals still remains somewhat of a rarity. In
1957, Frondel and Collette used mixed gel reactants to
synthesize both polymorphs of ThSiO4 hydrothermally
between 150 and 800 C.28 Both thorite and huttonite have
been found to form naturally in the later stages of magmatic
activity and specically thought to crystallize in hydrothermal
veins.29,30 In general, the thorium silicate geochemistry is a
result of natural hydrothermal activity in strongly alkaline
media.31
Recently, we demonstrated that the hydrothermal method
provides a useful route to many new thorium uoride
complexes as high quality single crystals using uoride
mineralizers with ThF4 as a starting material.3236 We also
found that ThO2 can be solubilized using a concentrated
mixture of OH and F as a mineralizer, which can dissolve and
recrystallize ThO2 at relatively low temperatures.3739 The
presence of uoride is especially critical in solubilizing ThO2,
which is consistent with thorium mineral paragenesis.1 This is
allowing us to expand the chemistry of the thorium oxides

2. EXPERIMENTAL METHODS
Hydrothermal synthesis was used to prepare single crystals of several
novel thorium silicate species by spontaneously nucleation. Reactions
were performed in welded ampules fashioned from silver tubing
(Leach Garner, 99.99%) 2.5 in. in length, with an outer diameter of 1/
4 in. Powders of ThO2 (Strem, 99.99%) and SiO2 (Alfa Aesar, 99.99%)
were loaded into the silver reaction vessel in a 1:5 molar ratio. A
mineralizer solution consisting of an alkali uoride or a combination of
an alkali uoride and alkali hydroxide was then loaded into the ampule.
Specically, Cs2ThSi6O15 was prepared using 6 M CsF (Alfa Aesar,
99.9%), Rb4Th2Si12O30 using 6 M RbF (Alfa Aesar, 99.9%),
K2ThSi4O10F2 using 6 M KF (Alfa Aesar, 99.99%), Cs2ThSi3O9
using 6 M CsF + 1 M CsOH (Alfa Aesar, 99%), and Rb2ThSi3O9
using 6 M RbF + 1 M RbOH (Alfa Aesar, 99%). The ampules were
welded shut and placed into an Inconel autoclave having 27 mL
internal volume. The remaining volume was lled with deionized water
to counter-pressure the ampules. The autoclave vessel was then heated
to 575 C, which generated pressures of 30 000 psi. After 7 days at
these conditions, the autoclave was allowed to cool to room
B

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Figure 1. Hydrothermal reaction chemistry of thorium silicates at 575 C, 30 kpsi, 7 days.

temperature before the ampules were retrieved. The ampules were
opened and the contents were ushed onto lter paper with deionized
water. The crystalline products were then characterized by single
crystal and powder X-ray diraction.
Full structural analysis of the novel thorium silicates was performed
by single crystal X-ray diraction using a Rigaku AFC8 diractometer
with a sealed tube used to generate graphite monochromated Mo K
( = 0.71073 ) radiation. The diractometer was equipped with a
Mercury CCD detector. Crystals were mounted on glass bers using
epoxy glue, and data were collected at room temperature by omega
scans over 480 diraction images (360 images collected with and
xed at 45 and 0, respectively, and rotated from 90 to 90 in
0.5 increments; 120 images collected with and xed at 45 and
90, respectively, with rotated from 30 to 30 in 0.5 increments).
Data processing, including integration and correction for absorption,
Lorentz and polarization eects, was performed using the Crystal
Clear software package.41 The space groups were determined from the
systematic absences, and the structures were solved by direct methods
and rened by least-squares techniques using the SHELXTL software
suite.42 All atoms were rened anisotropically in all structures.
Crystallographic data from the renements are reported in Table 1.
Selected interatomic distances and angles derived from the renements are reported in the Supporting Information, Tables S1 and S2.
Characterization of additional reaction products was performed by
single crystal unit cell determination or by powder X-ray diraction.
For the latter, Scintag XDS 2000 and Rigaku Ultima IV powder
diractometers were used, both equipped with Cu K ( = 1.54056 )
radiation. These data were collected in 0.2 deg steps from 5 to 65 in
2-theta at a rate of 1 deg/min (Supporting Information, Figures S1
S3). Infrared spectroscopy was performed as further characterization
of the novel silicates. Crystals of the target phases were individually
selected, ground to a powder, mixed with a KBr matrix, and
subsequently pressed into a pellet. Pellets were then oven-dried at
80 C before being transferred to a Nicolet Magna 550 FTIR
spectrometer. The spectrometer was purged with nitrogen, and data
were collected from 400 to 4000 cm1. A blank KBr pellet was used as
a background correction.

product along with small crystals of huttonite-type ThSiO4 as a

minor product. The formation of huttonite was somewhat
unexpected, since it is the high temperature phase of ThSiO4
(forming above 1200 C).10 The analogous reaction with 6 M
RbF resulted in the formation of large crystals of Rb4Th2Si12O30
and again a minor amount of small crystals of huttonite. Both
the Cs- and Rb-containing products are based on single layer
silicate sheet structures, but their structures are quite dierent
(vida inf ra), and it is useful to denote the rubidium compound
as Rb4Th2Si12O30 (rather than Rb2ThSi6O15) based on its more
complex structure. Changing the mineralizer to 6 M KF did not
produce an analogous potassium phase, but rather resulted in
the formation of K2ThSi4O10F2 again accompanied by trace
amounts of huttonite. In this case the uoride from the
mineralizer solution now becomes a part of the lattice, rather
than solely serving to solubilize the feedstocks. The silicate
sheet structures observed in the cesium and rubidium
compounds are not observed in K2ThSi4O10F2, which features
a columnar silicate arrangement instead. Extension of these
reactions to sodium and lithium uoride mineralizer solutions
did not yield any other novel silicates. Rather, both reactions
produced phase pure microcrystalline powders, which powder
X-ray diraction revealed to be the low temperature thorite
phase of ThSiO4. This is in contrast to the huttonite phase
formed in small yields from the larger alkali uoride
mineralizers. The reason for selective formation of the
huttonite and thorite phases in varying alkali uoride solutions
is not known at present.
Pure hydroxide solutions, which are commonly used as
mineralizers in hydrothermal synthesis of most metal oxides,
were not suitable for these systems because of the insoluble
nature of ThO2 in these mineralizers.37 We do nd, however,
that mixtures of hydroxides and uorides alter the chemistry
considerably. When using a solution of 6 M MF and 1 M MOH
with the same 1:5 molar ratio of ThO2 to SiO2, the resultant
product is the M2ThSi3O9 phase (M = Rb, Cs) and an
additional unidentied phase. This M2ThSi3O9 phase is
isostructural with the mineral wadeite, K2ZrSi3O9.43 Attempts
to isolate the potassium analogue using 1 M KOH and 6 M KF
as the mineralizer system were not successful. The wadeite
structure type already has an extensive array of analogues,4346
but this is the rst report of this structure type having an
actinide as the tetravalent metal center. These reactions were
phase-pure for the wadeite analogues and no huttonite or
thorite was observed.
3.2. Comparison of Cs2ThSi6O15 and Rb4Th2Si12O30
Structures. At rst glance, it would seem that Cs2ThSi6O15
and Rb4Th2Si12O30, having the same empirical formula
A2ThSi6O15, should possess similar crystal structures, based in
some way on the [Si6O15] repeat unit.47 We nd these
compounds to have noticeably dierent silicate networks
however. For Cs2ThSi6O15, the [Si6O15] formula unit is
achieved by condensation of two dreier chains (each made up

3. RESULTS AND DISCUSSION

3.1. Reaction Chemistry of the Alkali Thorium
Silicates. The hydrothermal synthesis of ThO2 single crystals
in concentrated uoride solutions was reported recently by our
group.37 The ability to mineralize refractory thorium oxide
using the hydrothermal uoride uids suggests it would also
solubilize the thorium oxide suciently to make it a suitable
reagent in new reaction chemistry. Our investigations of
thorium silicates were conducted in alkali uoride mineralizer
solutions and are summarized in Figure 1. Preliminary reactions
indicated a 1:5 ratio of ThO2 to SiO2 may be a fruitful region of
new phase space at 575 C, and in this way a 5-fold excess of
alkali metal ions relative to Th was supplied by the mineralizer.
Interestingly, the novel products obtained all had identical 2:1
ratios of the alkali metal with thorium, but varied greatly in the
nature and stoichiometry of the silicate building blocks.
The use of 6 M CsF both as a mineralizer and reactant with
ThO2 resulted in the formation of Cs2ThSi6O15 as the major
C

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of three repeating silicate tetrahedra),48 which is repeated to
form a single-layer sheet. The dierent orientations of the
[SiO4] tetrahedra in the two chains cause the silicate sheet to
be corrugated, which allows the monovalent and tetravalent
metals to be accommodated. This sheet contains four-, six-, and
eight-membered silicate rings and is a common arrangement for
[Si6O15] innite sheets. Similar corrugated sheets are observed
in dalyite-type (K 1.7 Na 0.3 ZrSi 6 O 15 ), 49,50 sazhinite-type
(Na3LaSi6O15(H2O)2, for example),51 and K3NdSi6O15-type
(and its hydrates)5254 structures. In Cs2ThSi6O15, parallel
sheets extend throughout the ac plane and are connected to
one another along [010] by distorted [ThO6] octahedra
(Figure 2). The thorium ion is coordintated by four oxygen

four unique dreier chains, accounting for the 12 unique silicon

atoms in the structure. Condensation of these chains into the
sheet structure is more complex (Figure 3). After direct

Figure 2. Extended structure of Cs2ThSi6O15.

atoms of one sheet and two oxygen atoms of a parallel sheet,

with ThO bond distances ranging from 2.266(16) to 2.294(9)
. The cesium atoms lie in the voids formed by the silicate
sheets and the [ThO6] polyhedron. It should be noted that the
structures of Cs2ThSi6O15 and Cs2USi6O15 determined in
previous reports crystallize in space groups Pna21 and Cmc21,
respectively, but otherwise exhibit nearly identical structures.26,55 A very subtle dierence is observed in the transOMO bonds of the [MO6] polyhedra in the various
structures. Woodward and co-workers26 observed bent
equatorial OThO bonds (173.8(2) and 173.5(3); those
bonds that connect neighboring sheets) and a more linear axial
OThO bond (177.0(2); connecting oxygen atoms of the
same sheet along [001]), whereas our C-centered structure
exhibits more bent axial OThO bonds (172.5(5)) and
more linear equatorial OThO bonds (175.2(4)). Likewise,
Cs2USi6O15 in space group Cmc21 also features bent axial O
UO bonds (173.2(3)) and more linear equatorial OUO
bonds (176.2(2)). Our crystals of Cs2ThSi6O15 were grown in
a similar fashion to Cs2USi6O15, and our data are likewise best
rened in space group Cmc21, suggesting that synthetic
conditions may facilitate this subtle dierence.
Crystals of Rb4Th2Si12O30 were synthesized from hydrothermal reactions analogous to those that produced
Cs2ThSi6O15, where RbF was the mineralizer instead of CsF.
The physical morphology of the crystals provided the rst
indicator that the two species may have dierent structures, as
Cs2ThSi6O15 formed as rectangular plates and Rb4Th2Si12O30
were columnar in shape. Indeed, the structure of Rb4Th2Si12O30
was determined in space group P1 and has a dierent silicate
sheet structure from Cs2ThSi6O15 despite their formulaic
similarity. The silicate sheets in Rb4Th2Si12O30 are built of

Figure 3. Comparison of the single layer silicate sheets in (a)

Cs2ThSi6O15 and (b) Rb4Th2Si12O30.

condensation of two unique dreier chains (Si1Si2Si3 and

Si4Si5Si6 chains in Figure 3b, for example) and their
inversion symmetry equivalents, a group of four-, six-, and
eight-membered silicate rings is formed, as was observed in
Cs2ThSi6O15. However, the next two condensed unique chains
(Si7Si8Si9 and Si10Si11Si12) and their symmetry
equivalents are sheared (to use the term of Haile and
Wuensch47) from this pattern. This causes a distortion of the
sheet structure at the shear interface (Si4Si5Si6 with Si7
Si8Si9) since these chains must reorient themselves relative to
the original pattern in order to condense with one another and
continue propagation of the sheet. In doing so, ve-membered
silicate rings are formed within the sheet at these interfaces of
the sheared chains. The sheared oset is repeated after every
four condensed chains (two unique chains and their symmetry
equivalents) in the long-range structure creating the observed
pattern of rows of rings in the sheet (584/68584/6
85, denoting the ring type in each row of the sheet). This rare
pattern was previously observed in the structures of Na3Nd(Si6O15)2H2O56 and NaNdSi6O13(OH)22H2O57 (though
D

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exhibited larger anisotropic displacement parameters for three

of the uorine sites and one of the potassium sites, and the
dierence electron density map featured four signicant areas
of residual electron density near these atoms. The disordered
model resulted in improvement of the anisotropic displacement
parameters and accounts for this electron density, having a nal
R1 value of 0.0384. The occupancy values of the disordered
atoms were determined empirically to be 50% for K2 and K2A,
65% for F4, F5, and F6, and 35% for F2, F3, and F7, producing
a chemically reasonable model. The resulting composition
K2ThSi4O10F2 was veried semiquantitatively by EDX, notably
indicating the presence of uorine and corresponding ratios of
K, Th, and Si (in atom %: 10.1(0.9)% K, 5.4(0.4)% Th,
20.3(1.3)% Si, 55.5(1.7)% O, 9.7(0.8)% F).
The structure features an unusual tubular silicate column
built by two unique vierer unbranched silicate chains that
propagate along the b-axis. The column is formed by four
condensed chains and is comprised of one four-, two six-, and
one eight-membered silicate rings around the sheath of the
column (Figure 5). The column also exhibits a cross section

Haile and co-workers conclude that these two structures are

most likely the same material), as well as several other rare
earth analogues of this structure type, crystallizing in space
group Cmm2.58,59 Thus, the present study reveals a new
structure type containing these sheets. The lower symmetry of
Rb4Th2Si12O30 is apparent in the distortion of the ring pattern
in the silicate sheet. This in fact results in two distinct vemembered rings (Si4Si5Si6Si7Si9 and Si5Si6Si7
Si8Si9), a rather unique feature given the rarity of such rings
among the silicates.48 The compounds Cs2ZrSi6O1560 and
M2TiSi6O15 (M = K, Rb, Cs)61,62 also feature ve-membered
rings due to similar shearing interactions; however, in these
structures there is no direct condensation of dreier chains, and
only ve- and eight-membered silicate rings comprise the
sheets.
In Rb4Th2Si12O30 the dreier chains propagate approximately
along [012] and condense along the a-axis to form the
corrugated sheets. Parallel sheets are again connected by
[ThO6] distorted pseudo-octahedra (Figure 4), but in this case

Figure 4. Extended structure of Rb4Th2Si12O30.

thorium atoms are coordinated by three oxygen atoms of each

sheet rather than four from one and two from the next as in
Cs2ThSi6O15. Compared to those in Cs2ThSi6O15, these
[ThO6] polyhedra are noticeably more distorted. For example,
the transOThO bonds (which all connect neighboring
sheets) of Rb4Th2Si12O30 range from 156.2(3) to 169.8(3)
for Th1 and 162.6(3) to 175.6(3) for Th2. There is a long
contact of Th1O4 at a distance of 2.905(7) that, if
considered, creates a face-capped octahedral coordination (6 +
1), accounting for the extreme deviation from 180 of the trans
bond angles about Th1. All other ThO bond distances
(2.276(7)2.354(8) ) are within the normal range.
Ultimately, the smaller size of the Rb cations creates a smaller
coordination sphere about Rb (RbO interactions of
2.805(8)3.598(8) compared to CsO interactions of
3.219(10)3.748(3) ) that probably alters the thorium
silicate framework to accommodate in this dierence.
3.3. Structure of K2ThSi4O10F2. Crystals of K2ThSi4O10F2
resulting from hydrothermal synthesis in aqueous KF are based
on an entirely dierent silicate structural unit. In this case,
uorine atoms from the mineralizer solution are also
incorporated into the lattice to form this new structure type.
The structure was determined in space group Pnma, and the
asymmetric unit consists of three unique ordered potassium
atoms, two disordered potassium atoms (K2 and K2A, each
half-occupied), four unique silicon atoms, 12 unique oxygen
atoms, one fully occupied uorine atom (F1), and six
disordered uorine atoms (F2F7). The structure was initially
rened as an ordered model with fully occupied sites (four K
sites and four F sites) with R1 = 0.0503. This preliminary model

Figure 5. Silicate column in K2ThSi4O10F2 viewed slightly o [100].

Representative four-, six-, and eight-membered silicate rings are
identied by polyhedra. A second unique six-membered ring occurs
approximately normal to [001], but for clarity is not denoted here.

perpendicular to the b-axis that is an eight-membered silicate

ring (Figure 6). Siliconoxygen bond distances of 1.544(10)
1.653(7) are observed, with SiO bonds bridging to thorium
atoms (O1, O5, O12, O8) always corresponding to the shortest
end of this range. Neighboring columns are connected by
chains of [ThO4F4] polyhedra to form channels extending
along [010] that contain potassium cations, in addition to those
potassium atoms that reside within the tubular silicate column.
In this way, K3 atoms are located in the tubular column, while
E

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equatorial bonds to oxygen atoms of the silicate columns. In

this case it is demonstrated that additional uoride anions can
be accommodated in the new pattern of chain propagation to
properly balance the charge of the tetravalent thorium cations.
We also note dierences in the column orientation in this new
structure type compared to those structures with P21/m space
group symmetry. In K2ThSi4O10F2, the columns exhibit two
dierent orientations in the ac plane, each rotated 90 deg with
respect to one another (Figure 6). In the previously reported
structures having this silicate column, the column maintains
only one orientation in the ac plane in the long-range structure.
Correspondingly, the c-axis of K2ThSi4O10F2 is signicantly
longer than the a- and c-axes in those structures (22.099(4)
vs 11.065(3)11.8165(3) ).
3.4. Wadeite-Type Cs2ThSi3O9 and Rb2ThSi3O9. The
compounds Cs2ThSi3O9 and Rb2ThSi3O9 form analogues of
the wadeite (K2ZrSi3O9) structure type.43 The formation of this
structure type based on a thorium building block is rather
interesting since reports of this structure type in the literature
previously appear conned to the tetravalent cations Ti4+, Sn4+,
Si4+, and Zr4+.4346 The present compounds signicantly
extend the known versatility of this structure type to larger
tetravalent metals six-coordinate Shannon crystal radius of 1.08
for Th4+ vs 0.86 for Zr4+).67 The unit cell volume of
Cs2ThSi3O9 is about 11% larger than that of the previous
largest silicate wadeite, Cs2ZrSi3O9, with a volume of 465.11 3.
Furthermore, the unit cell volume of Cs2ThSi3O9 is 43% larger
than that of the smallest silicate wadeite, K2SiSi3O9 (360.11 3),
indicating a wide range of exibility for this structure type.
The wadeite structure type is well-known, consisting of
isolated [Si3O9] cyclosilicate groups that are linked together
through [MO6] octahedra to form a three-dimensional metal
silicate framework. The alkali metal cations occupy voids in the
framework (Figure 8). Since this is the rst example of an
actinide wadeite analogue, it is useful to examine the behavior
of Th in this structure. Thorium coordinates with oxygen to
form a nearly ideal octahedron (ThO = 2.302(5) ), only

Figure 6. Extended structure of K2ThSi4O10F2 viewed along [010].

K1, disordered K2/K2A, and K4 atoms are located in sixmembered channels bound by two Th and four Si atoms.
Similar columns have been observed in K2CuSi4O10,63
K2InSi4O10(OH),64 K2LuSi4O10(OH),65 and Rb2LuSi4O10F.66
Those compounds all have comparable lattice parameters and
crystallize in space group P21/m. Of particular interest,
however, is the nature and coordination of the linking metals
(Figure 7). In K2CuSi4O10, Cu is divalent and adopts a square
planar geometry with oxygen. The trivalent metals in the
hydroxide and uoride species are all six-coordinate as
[MO4(X)2] and form chains that propagate along the b-axis
by corner sharing of the hydroxide or uoride groups. The
coordination of tetravalent Th in K2ThSi4O10F2 is dierent still
(eight coordinate ThO4F4) and results in a new higher
symmetry structure type in space group Pnma. Because of the
uorine disorder, two types of [ThO4F4] coordination and
connectivity are observed (Figure 7). When the majorityoccupied (65%) uorine atoms F4, F5, and F6 are considered,
the resulting coordination is an intermediate between a cube
and a square antiprism about Th, with chain propagation
through shared uorine edges. When the minority-occupied
(35%) uorine atoms F2, F3, and F7 are considered, the chain
propagation alternates between corner-shared F7 atoms and
shared F1F2F3 faces. Clearly there is a lot of exibility in
the nature of the metal chains, provided they maintain four

Figure 7. Comparison of metal center bridging and b-axis chain propagation in related silicates. Note the two means of [ThO4F4] chain propagation
in K2ThSi4O10F2 occurring through majority-occupied (65%) and minority-occupied (35%) uorine atoms.
F

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Crystal Growth & Design

ward. The rarity of ve- and eight-membered silicate rings has

also made their assignment less absolute in the literature.
We observe three-, four-, ve-, six-, and eight-membered
silicate rings in the thorium silicates of this study. Table 2
denotes the type of rings present by identifying N as the
number of silicate members in each ring, and the observed Si
OSi stretching ring vibrations for each. We note the bands
from the three-, four-, and six-membered ring vibrations for
each compound all fall within the expected ranges. The
vibrational spectrum of Rb4Th2Si12O30 is the only compound in
this study that contains ve-membered rings and contains
additional bands at 662 and 637 cm1, intermediate to the fourand six- membered ring vibrations in those structures
(Supporting Information, Figure S4). This appears to be a
reasonable range for the ve-membered ring vibration and has
been tentatively assigned as such. The presence of two distinct
bands in this region may be consistent with two unique vemembered rings in the crystal structure which are serendipitously free of signicant deformation, permitting their
observation. By extrapolation of the trend observed for the
vibrational frequencies of three-, four-, and six-membered rings,
the additional IR bands from 580 to 605 cm1 observed in
Cs2ThSi6O15, Rb4Th2Si12O30, and K2ThSi4O10F2 can be
tentatively assigned to the eight-membered rings (Supporting
Information, Figure S5). Because of the severe deformation of
the eight-membered ring around the sheath of the silicate
column in K2ThSi4O10F2, it seems likely that the weak band at
604 cm1 in that spectrum results from the eight-membered
ring of the columns cross section. It should also be noted that
the vibrational spectrum of K2ThSi4O10F2 is free of signicant
features from 3000 to 3500 cm1, suggesting the absence of
OH in that structure and consistent with the structure
renement of bridging uorine atoms (Supporting Information,
Figure S6; other infrared spectra are included as Figures S7
S10).

Figure 8. Extended structure of Cs2ThSi3O9, a wadeite analogue.

departing in the cisOThO angles (89.51(18) and

90.49(18) for the Cs analogue and 88.70(17) and
91.30(17) for the Rb analogue), similar to other wadeite
analogues. The silicate group is not appreciably changed by the
presence of the larger Th4+ cation, having comparable SiO
bond distances as well as comparable OSiO, SiOSi, and
ThOSi bond angles to those based on other tetravalent
metals in the wadeite series. It has been noted that the presence
of larger alkali metals results in increased SiOSi and MO
Si angles in structures based on the same M4+ cations,46 and
that is consistent in these Rb- and Cs-containing Th4+ wadeites.
Interestingly, the SiOSi and MOSi angles in Cs2ThSi3O9
(134.3(4) and 147.5(3), respectively) are not quite as large as
those in Cs2ZrSi3O9 (137.5(5) and 149.6(4)), suggesting that
the larger Th4+ cation is probably the most suited to
accommodate larger alkali metals in a wadeite structure by
minimizing the silicate distortion. This may also explain why
K2ThSi3O9 was not encountered during this study.
3.5. Infrared Analysis of Thorium Silicates. Infrared
spectroscopy was used to verify certain structural features of the
above compounds. In all structures vibrational frequencies
within the typical ranges of 9001100 cm1 and 500550 cm1
were observed for SiO stretching vibrations (both bridging
and terminal) and OSiO bending vibrations, respectively
(Table 2). Since the above compounds all contain silicate rings

4. CONCLUSIONS
In this study, ve new alkali thorium silicates were synthesized
and characterized by single crystal X-ray diraction. In all cases
the starting materials included ThO2 and SiO2. The reactions
required the presence of uoride in the hydrothermal solution
to solubilize the thoria. Hydroxide was not sucient in this
regard even in high concentrations and high reaction
temperatures. When growth conditions were limited to alkali
uoride mineralizers, the new crystalline products isolated were
Cs2ThSi6O15, Rb4Th2Si12O30, and K2ThSi4O10F2. Both polymorphs of ThSiO4, thorite and huttonite were also stable in this
region of phase space depending on the choice of alkali ion.
Upon the addition of hydroxides to the uoride mineralizer two
new wadeite crystals, Cs2ThSi3O9 and Rb2ThSi3O9, were
isolated in good yield. These represent the rst analogues of
this structure to contain an actinide metal. Overall, the
hydrothermal descriptive chemistry of the alkali thorium
silicates has resulted in two novel structure types and a great
variety of silicate arrangements, including two dierent types of
single layer silicate sheets, tubular silicate columns, and isolated
cyclosilicate groups. These polysilicates were further comprised
of a variety of three-, four-, ve-, six-, and eight-membered
rings, and their characteristic infrared spectra were studied. This
exploratory work represents the rst step into a relatively
untouched thorium silicate family. The hydrothermal method
appears to provide a route to a very rich descriptive chemistry

Table 2. Infrared Analysis of Thorium Silicates (values in

cm1)
SiO
stretching
OSiO
bending
N=3
N=4
N=5
N=6
N=8

Cs2ThSi3O9

Cs2ThSi6O15

Rb4Th2Si12O30

K2ThSi4O10F2

1003

963

932

1024

537

525

529

525

686

686
662, 637
616
598

673

722

636
587

645
604

of some form, our emphasis was on correlating the infrared

spectra with the rings observed in the crystallographic models.
The technique has been shown to be a useful tool for such
correlations, by probing stretching vibrations from SiOSi
bridging bonds within the cyclosilicates (sometimes called ring
vibrations).68 Highly symmetrical rings have been shown to
have well-dened vibrational frequency ranges in the cases of
three- (700760 cm1), four- (650690 cm1), and six(615630 cm1) membered rings.6870 Highly deformed
rings tend to exhibit a weaker signal with a larger number of
low intensity bands, making their assignment less straightforG

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Article

Crystal Growth & Design

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of the thorium silicates and suggests that many other building

blocks may also be suitable reagents in this chemistry.

ASSOCIATED CONTENT

S Supporting Information
*

Tables of selected interatomic distances and angles, infrared

spectra, crystal structure data in CIF format. The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/cg5017164.

AUTHOR INFORMATION

Corresponding Author

*Address: Department of Chemistry, Clemson University, 485

H. L. Hunter Laboratories, Clemson, SC 29634. Phone: (864)
656-4739; fax: (864) 656-6613; e-mail: kjoseph@clemson.edu.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We would like to thank the National Science Foundation
(DMR-0305377, DMR-0907395, and DMR-1410727) for
funding and support.

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