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I. INTRODUCTION
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
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
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
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
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
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
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
Cs2ThSi3O9
Cs2ThSi6O15
Rb4Th2Si12O30
K2ThSi4O10F2
1003
963
932
1024
537
525
529
525
686
686
662, 637
616
598
673
722
636
587
645
604
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
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ASSOCIATED CONTENT
S Supporting Information
*
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
We would like to thank the National Science Foundation
(DMR-0305377, DMR-0907395, and DMR-1410727) for
funding and support.
REFERENCES
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX
Article
DOI: 10.1021/cg5017164
Cryst. Growth Des. XXXX, XXX, XXXXXX