research papers

(3+1)-Incommensurately modulated crystal struc-

ture of Cs3ScSi6O15
ISSN 2052-5206
Clivia Hejny,a* Volker Kahlenberg,a Daniela Schmidmaira and Predrag Dabićb

a
Institute of Mineralogy and Petrography, University of Innsbruck, Innrain 52, Innsbruck A-6020, Austria, and bLaboratory
of Crystallography, University of Belgrade, Dušina 7, Belgrade 11000, Serbia. *Correspondence e-mail:
[email protected]
Received 15 July 2015
Accepted 18 November 2015
Single-crystal X-ray diffraction of Cs3ScSi6O15 shows the presence of main
reflections and satellite reflections up to the fourth order along the c* direction.
Edited by M. Dusek, Academy of Sciences of the The (3+1)-dimensional incommensurately modulated structure was solved in
Czech Republic, Czech Republic superspace group X 3 m1ð00Þ0s0 [a = 13.861 (1), c = 6.992 (1) Å, V =
1163.4 (2) Å3] with a modulation wavevector q = 0.14153 (2)c*. Refinement of
Keywords: incommensurately modulated crystal
three modulation waves for positional and anisotropic displacement parameter
structure; (3+1)-dimensional refinement; fourth-
order satellite reflections; mixed tetrahedral– values for all atoms converged to Robs values for all, main and satellite
octahedral framework. reflections of first, second and third order of 0.0200, 0.0166, 0.0181, 0.0214 and
0.0303, respectively. Cs3ScSi6O15 forms a mixed tetrahedral–octahedral frame-
CCDC reference: 1437877 work with prominent six-membered rings of [SiO4]-tetrahedra interconnected
by [ScO6]-octahedra. Apart from Sc, all atoms are strongly affected by positional
B-IncStrDB reference: 11472EwF4su
modulation with maximum atomic displacements of up to 0.93 Å causing rigid
polyhedral arrangements to perform tilt and twist movements relative to each
Supporting information: this article has
supporting information at journals.iucr.org/b other, such as a rotation of the Sc-octahedra around the 3 -axis by over 38 . Cs
has an irregular coordination environment; however, considering distances up to
3.5 Å, the bond-valence sum changes by no more than 0.02 as a function of t and
thus overall kept at a level of ca 1.075.

1. Introduction
In the field of applied inorganic chemistry, caesium containing
silicates have been studied for two main reasons: (i) tailoring
of materials that can serve as radioactive waste deposits for
137
Cs and (ii) the search for new luminescent compounds that
may be used for the development of new circuits and devices
for electronic, optoelectronic as well as communications
industries.
Due to its short half-life of about 30 years, 137Cs has high
activity and is still the main source of beta-radiation after the
nuclear disasters related to the accidents in the power plants
of Chernobyl and Fukushima Dai-ichi (Povinec et al., 2013;
Steinhauser et al., 2014). Several phases have been proposed in
the past as potential hosts for the immobilization of radio-
active caesium including porous framework structures such as
pollucite (CsAlSi2O6), CsAlSiO4 or CsAlSi5O12 (Rodriguez et
al., 2013; Gatta et al., 2008; Fisch et al., 2008) or mica-related
compounds such as Cs-annite [CsFe3(AlSi3)O10(OH)2] (Klika
et al., 2006).
On the other hand, quite a number of caesium-bearing
synthetic oxosilicates containing trivalent rare earth element
(REE) cations that can be potentially used as host lattices for
luminescence have been disclosed in the literature. Examples
include Cs3NdSi8O19 and CsNd2Si21O48 (Schäfer & Schleid,
2009), Cs3EuSi6O15 (Huang et al., 2005), Cs3DySi6O15 (Zhao et
# 2016 International Union of Crystallography al., 2010), Cs1.86K1.14DySi6O15 and Cs1.6K1.4SmSi6O15 (Wierz-

Acta Cryst. (2016). B72, 109–116 http://dx.doi.org/10.1107/S2052520615022076 109

research papers
Table 1 characterization of Cs3ScSi6O15 has been complemented by
Data collection and refinement parameters of Cs3ScSi6O15. micro-Raman spectroscopy.
Crystal data
Superspace group X 3 m1ð00Þ0s0


Centring vectors (0,0,0,0) 13 ; 23 ; 23 ; 13 2 1 1 2
3;3;3;3
Modulation wavevector q 0.14153 (2)c*
a, c (Å) 13.861 (1), 6.992 (1)
V (Å3) 1163.4 (2)
2. Experimental
Z 3 2.1. Synthesis
Dx (g m3) 3.65
Radiation type, source X-ray, Mo K Single crystals of Cs3ScSi6O15 were obtained during a series
 (mm1) 7.95 of flux syntheses experiments aiming for the preparation of
Crystal size (mm) 0.13  0.09  0.05
new Cs-REE fluoride silicates. The starting materials (Sc2O3
Data collection (Alfa Aesar, 99.9%), SiO2 (Alfa Aesar, 99.9995%) and CsF
Diffractometer Gemini R Ultra (Alfa Aesar, 99.8%) were dried at 393 K. Because of the
(Oxford Diffraction)
Monochromator Graphite pronounced hygroscopic character of the alkali fluoride,
Data collection temperature (K) 293  2 sample preparation was performed in a glove bag under
Generator settings (kV, mA) 50, 40 nitrogen atmosphere. The nutrient (0.1 g), consisting of a
Detector, distance (mm) CCD, 70
Scan width ( ) 0.5 mixture of Sc2O3:SiO2 in the molar ratio 1:4, was homogenized
Measurement time per frame (s) 80.0 in an agate mortar with 0.1 g CsF. Subsequently, the educts
No. of measured, independent and 17 243, 2193, 1838 were transferred into a platinum tube (20 mm length, 3 mm
observed [I > 3(I] reflections
Rint 0.032 outer diameter) and welded shut. The container was fired in a
max 28.68 resistance heated furnace from 373 K to 1373 K with a ramp of
Range of h, k, l, m h = 18 ! 17, k = 18 ! 18, l = 9 50 K h1. The target temperature was held for 2 h. Subse-
! 9, m = 3 ! 3
Faces for absorption correction 10 quently, the sample was cooled down to 1073 K at a rate of
5 K h1 and, finally, the temperature was reduced to 373 K at a
Refinement rate of 100 K h1. After removal from the platinum tube, the
Criterion for observed reflections I > 3(I)
R (observed / all reflections) R = 0.0200 / 0.0289, solidified melt cake was immediately crushed in an agate
wR = 0.0235/0.0259 mortar and transferred to a glass slide under a polarizing
R (observed / all main reflections) R = 0.0166 / 0.0202, binocular. A first optical inspection revealed the presence of a
wR = 0.0232/0.0240
R (observed / all satellite reflections, R = 0.0181 / 0.0231, polycrystalline matrix of CsF in which a great number of
m =  1) wR = 0.0218/0.0231 transparent, colourless-birefringent, hexagonal-prismatic
R (observed / all satellite reflections, R = 0.0214 / 0.0333, single crystals up to 150 mm in size were embedded. Several
m =  2) wR = 0.0229/0.0263
R (observed / all satellite reflections, R = 0.0303 / 0.0541, crystals that optically appeared to be the same material were
m =  3) wR = 0.0298/0.0357 proven to have the same lattice parameters and an identical
Goodness-of-fit on F (observed / all) 1.16 / 1.16 Raman spectrum (up to 15 individual crystals were checked);
Maximum change/s.u. 0.0423 for x sin2 (Cs)
No. of parameters 130 the Raman spectrum is given in the supporting information in

max,
min (e Å3) 0.38, 0.35 Fig. S1. Additional crystals of less frequent occurrence and
distinctly different platy form have been identified as
Computer programs used: CrysAlisPRO (Agilent, 2012) and JANA2006 (Petřı́ček et al.,
2014). Cs3ScSi8O19 (Kolitsch & Tillmanns, 2004) on the basis of
determining their lattice parameters and a search for the
lattice parameters in the ICSD database (Belsky et al., 2002).
bicka-Wieczorek et al., 2015), Cs3YSi8O19 (Kolitsch et al.,
2009) as well as Cs3ScSi8O19 (Kolitsch & Tillmanns,
2004).
In the course of a long-term project on the crystal chemistry 2.2. Scanning electron microscopy
of REE-containing silicates and fluoride silicates, we used a Spot analyses of selected crystals were performed with a
flux technique to obtain single crystals of a previously Jeol JSM-6010LV scanning electron microscope using an
unknown phase with a composition of Cs3ScSi6O15. The energy-dispersive system equipped with an Xflash 410-M
compound is structurally related to the corresponding detector (Bruker) for element identification and semi-quan-
dysprosium silicates mentioned above. However, in contrast to titative chemical analysis. Two crystal specimens were directly
Cs3DySi6O15 and Cs1.86K1.14DySi6O15, the Sc-phase adopts a mounted on double-sided sticky carbon tape. Operating
(3+1)-dimensional incommensurately modulated structure. conditions were a low vacuum setting of 30 Pa, a 15 kV
The present contribution reports a description of the crystal acceleration voltage and an incoming counting rate of 2334
structure using the superspace approach and a detailed c.p.s. Using a counting period of 60 s, elemental signals were
crystallochemical comparison with similar materials. Further- recorded for Cs, Sc, Si and O. The following cation ratios were
more, special emphasis was placed on a topological description observed: Cs:Sc:Si = 3.03:1.13:5.90, leading us to the conclu-
as a mixed tetrahedral–octahedral framework offering an sion that the chemical composition of the crystals is
alternative way to rationalize the crystal structure. Finally, the Cs3ScSi6O15.

110 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 Acta Cryst. (2016). B72, 109–116
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2.3. Single-crystal diffraction
An optically homogeneous crystal, showing sharp and clear
extinction under crossed polarizers with dimensions 51  94 
134 mm was selected and mounted for X-ray diffraction data
collection on an Oxford Diffraction Gemini four-circle
diffractometer, equipped with a Ruby CCD detector and using
graphite-monochromated Mo K radiation (50 kV, 40 mA).
Data collection was performed at room temperature. Data
reduction included intensity integration, background and
Lorentz–polarization correction performed with the Crys-
AlisPro software package (Agilent, 2012). The morphology of
the fragment was approximated by ten external faces and an
analytical absorption correction based on these indexed faces
was applied. Experimental details of data collection and
structure refinement are summarized in Table 1.
According to the analysis of a quick pre-experiment, full
intensity data collection of a half-sphere in reciprocal space
with an exposure time of 80 s per frame and an !-step size of
0.5 was chosen. Initial attempts to find a unit cell gave
unrealistically large values. Therefore, only reflections with
the strongest intensity were used to find a hexagonal cell of a =
13.861 (1), c = 6.992 (1) Å. Inspection of the distribution
histograms of the remaining unindexed reflections clearly
showed them to be satellite reflections of up to third order in
the c* direction. The modulation wavevector was subse-
quently refined to q = 0.14153 (2)c*. This is close to but
distinctly different from 1/7. In consideration of the high
intensity of the satellite reflections and the fact that the pairs
of satellite reflections with m = +3/4 and m = 3/+4 have
very close positions along c*, the data were subject to another
thorough re-examination that revealed the presence also of
fourth-order satellite reflections. However, it was not possible
to integrate and use these fourth-order satellite reflections for
the structure refinement.

3. Structure solution and refinement

Visual inspection of precession-type reconstructions of reci-
procal space cuts revealed R0 -centring according to the
reflection condition h – k – l + m = 3n (see Fig. 1 and Fig. S2 in
the supporting information). The Laue class was determined
to be 3 m1 and thus allowed for the superspace groups X 3 m1,
X3m1 or X321, of which the highest symmetry was chosen.
For X 3 m1 two superspace groups, X 3 m1ð00Þ000 or
X 3 m1ð00Þ0s0 that differ in the intrinsic part of the non-
lattice translation, are possible. The structure was solved in

X 3 m1ð00Þ0s0
with the centring vectors (0,0,0,0), 13 ; 23 ; 23 ; 13
and 23 ; 13 ; 13 ; 23 by charge flipping with the program SUPER-
FLIP (Palatinus & Chapuis, 2007) after 71 iterations. A
transformation of the chosen superspace group to standard
setting would lead to the superspace group R3 m1ð00Þ0s, No.
166.1.22.2 (Stokes et al., 2011). The built-in feature of Figure 1
SUPERFLIP to test the reconstructed density for the Sections through reciprocal space with (a) main reflections (m = 0) in the
hk0 layer, (b) first-order satellite reflections (m = 1) in a cut through
symmetry operations of the chosen superspace group
hk0.14, (c) second-order satellite reflections (m = 2) in a cut through
confirmed the choice. Automatic atom assignment by the hk0.28, and (d) third-order satellite reflections (m = 3) in a cut through
program JANA2006 (Petřı́ček et al., 2014) gave atomic posi- hk0.42.

Acta Cryst. (2016). B72, 109–116 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 111
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tions for Cs, Sc, Si and three O atoms. Structure refinement
with JANA2006 of these six atomic positions each with one
positional and an anisotropic displacement parameter (ADP)
modulation wave quickly converged to a Robs value for all
reflections of below 0.1. Subsequent refinement of three
modulation waves for positional and ADP values smoothly
converged to Robs values for all, main, and satellite reflections
of first, second and third order of 0.02, 0.0166, 0.0181, 0.0214
and 0.0303, respectively. The refined positional parameters
and the anisotropic displacement parameters including their
modulations can be found as supporting information in CIF
format. A graphical presentation of electron density sections
are given in Figs. S3–S8.

Figure 3
(a) The 3d-average structure of Cs3ScSi6O18 in a view along the c-axis. (b)
Approximant structure of (3+1)-incommensurately modulated
Cs3ScSi6O18 for seven unit cells along the c-axis.

4. The crystal structure of Cs3ScSi6O15

4.1. The basic structural motifs
[SiO4]-tetrahedra form six-membered rings (see Fig. 2)
around the 3 -axis with the O1 atoms functioning as bridging
atoms to connect the tetrahedra. In the average structure
modelled from main reflections only O1 atoms are located on
a central plane of the six-membered ring. Tetrahedra adjacent
in the six-membered ring are rotated around the O1—O1 line
in an alternating way up and down from the ring plane
(‘alternating up–down six-membered ring conformation’). In
the unmodulated average structure the angle between the
normal to the ring plane (defined by the six bridging atoms
O1) and the connecting line O2—O3 is  63.8 . O2 atoms
function as a bridge to the next six-membered ring; O3 atoms
connect to octahedrally coordinated Sc atoms [Sc—O3 6
2.068 (1) Å] above and below the six-membered ring and thus
forming an infinite column of strictly alternating [ScO6]-
[Si6O18]-units along the 3 -axis. In this way, a three-dimensional
network of [SiO4]-tetrahedra and [ScO6]-octahedra is formed
(see Fig. 3). Cs atoms occupy large open channels along the
[11 2] direction within the Sc–Si network. The contributions
from six O atoms in the coordination sphere of Cs up to
3.3 Å (see Table 2) add up to give a bond-valence sum of
Figure 2
Six-membered ring of [SiO4]-tetrahedra in the unmodulated 3d-average only 0.650 (1) v.u. for Cs. Six further caesium–oxygen
structure in a view along the c-axis (a) and ca along the a-axis (b). distances up to 3.5 Å have to be considered as bonding

112 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 Acta Cryst. (2016). B72, 109–116
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Table 2
Interatomic distances (Å) and angles ( ) of Cs3ScSi6O15.
(3+1) average: average distance in the (3+1)-incommensurately modulated
structure. 3d average: distance in the average structure calculated from only
main reflections without the contribution of the satellite reflections.
(3+1) (3+1) (3+1) 3d
min–max range average average

Cs—O1 (4) 3.187 (5)–3.405 (5) 0.218 3.274 (4) 3.212 (1)
Cs—O3 (2) 3.256 (2)–3.360 (2) 0.104 3.309 (2) 3.300 (2)
Cs—O3 (4) 3.204 (6)–3.829 (6) * 3.505 (6) 3.480 (2)
Cs—O2 (2) 3.319 (7)–5.022 (7) * 4.193 (5) 3.495 (1)
Cs—O1 (2) 3.262 (7)–5.661 (7) * 4.415 (6) > 4.4
Sc—O3 (6) 2.100 (2)–2.122 (2) 0.022 2.111 (2) 2.068 (1)
Si—O1 (2) 1.614 (5)–1.653 (5) 0.039 1.622 (5) 1.596 (1)
Si—O2 (1) 1.611 (3)–1.638 (3) 0.027 1.628 (2) 1.568 (1)
Si—O3 (1) 1.567 (2)–1.571 (2) 0.004 1.569 (2) 1.562 (1)
O1—Si—O1 105.0 (2)–107.2 (2) 2.2 106.0 (2) 104.6 (1)
O1—Si—O2 101.8 (2)–107.1 (2) 5.4 104.6 (2) 104.4 (1)
O1—Si—O3 114.0 (2)–115.7 (2) 1.7 114.8 (2) 115.8 (1)
O2—Si—O3 110.6 (1)–111.6 (1) 1.0 111.1 (1) 110.8 (1)
Si—O1—Si 124.7 (2)–177.8 (3) 53.1 149.7 (2) 150.7 (1)
Si—O2—Si 144.8 (4)–179.9 (2) 35.1 154.9 (3) 180.0
Si—O3—Sc 147.0 (2)–154.2 (1) 7.2 150.5 (2) 154.2 (1)

For interatomic distances exceeding 3.5 Å in some parts of the modulated structure the
value for the range of the respective distance has been omitted (*), because such large
interatomic distances are not considered bonding distances any more and a value for the
range would therefore be misleading.

distances as well, thus resulting in a bond-valence sum of

0.985 (1) v.u. for Cs.

4.2. Modulated structure

Apart from Sc, all atoms show a large positional modula-
tion: the largest amplitudes in the positional modulation Figure 4
function is found for the x coordinates of O2 and Cs followed Interatomic distances within the [SiO4]-tetrahedron (a) and [ScO6]-
by O3, Si and O1 with maximum displacements of 0.93 Å (x of octahedron (b) as a function of t.
O2), 0.74 Å (x of Cs), 0.62 Å (x of O3), 0.53 Å (x of Si) and
0.51 Å (x of O1), respectively. In contrast to this, the maximum O2–O3, to take one example, ranges from 62.8 to 66.2 .
atomic displacement of the Sc atom is only 0.02 Å (see Another example is the very strong variation of the Si—O1—
graphical representation of the displacive modulation function Si angle taking values between 124.7 (2) and 177.8 (3) . The
in Figs. S9–S14 in the supporting information). The polyhedral
coordination of scandium and silicon is rigid with only minor
variation of the atomic bond distances (see Table 2 and Fig. 4).
In the modulated structure, Sc—O3 distances vary from
2.100 (2) to 2.122 (2) Å. The position of the Sc atom is only
slightly modulated; however, due to the pronounced posi-
tional modulation of O3 coordinating Sc, [ScO6]-octahedra
rotate around the 3 -axis by over 38 (see Figs. 5 and S15). As is
expected for [SiO4]-tetrahedra, the atomic distances from Si to
the bridging atoms O1 and O2 are larger [average values in the
modulated structure of 1.622 (5) and 1.628 (2) Å, respectively]
than to the terminal O3 atom [average value of 1.569 (2) Å].
Likewise, the larger Si—O1 and Si—O2 distances show a
larger range from minimum to maximum atomic distances of
up to 0.039 Å in comparison with the shorter Si—O3 distance,
which varies by only 0.004 Å. Comparable to the rotation of
the [ScO6]-octahedron the [Si6O18]-ring rotates around the 3 -
axis. Furthermore, the tetrahedra perform several twist
Figure 5
movements affecting inter-tetrahedral angles. The angle Rotation of the [ScO6]-octahedron around the 3 -axis expressed by the
between the normal to the ring plane and the connecting line torsion angle O3—Sc—Sc—O3 as a function of t.

Acta Cryst. (2016). B72, 109–116 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 113
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Table 3
Coordination sequences {Nk} of the Si and Sc atoms as well as the extended point symbols in Cs3ScSi6O15.
Coordination sequences {Nk} (k = 1–14)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 Extended point symbol

Si 4 4 14 11 34 26 70 44 116 71 182 103 252 133 4.72.4.72.4.72

Sc 6 6 18 12 30 26 84 54 138 66 150 98 270 156 4.4.4.4.4.4.7.7.7.7.7.7.94.94.94

coordination environment of Cs in the modulated structure is (Si, Sc) and the anions (O). Each node of this sub-structure
irregular because all Cs—O interatomic distances vary as a can be classified by its coordination sequence {Nk} (Brunner &
function of t (see Table 2, Fig. S16 in the supporting infor- Laves, 1971). It has to be emphasized that two crystal-
mation). The six O atoms closest to Cs, O1 and O3 remain lographically independent nodes can be topologically
within a distance of < 3.4 Å. However, O atoms at further equivalent and expressed in equal values of {Nk}. The coor-
distance from Cs move in and out of the coordination sphere dination sequences as well as the corresponding extended
as a function of t. Even atoms that are certainly not being point symbols [listing all shortest circuits for each angle for
considered as bonding to Cs in the average structure move any non-equivalent atom; Blatov et al. (2010)] have been
into the bonding distance, such as Cs—O1 with an atomic calculated using the TOPOS program suite (Blatov et al., 2014)
distance of over 4.4 Å in the average structure in comparison (see Table 3). For the determination of the extended point
with a distance of 3.262 (7) Å at t = 0.18 and t = 0.68 in the symbols the O atoms have been excluded. Subsequently, so-
modulated structure. Considering the coordination sphere of called polyhedral microensembles (PMEs) were constructed.
Cs up to 3.5 Å the coordination of Cs is nine- to 11-fold with a On the lowest sub-level they are formed for each octahedron
bond-valence sum of 1.066–1.087 as a function of t. The and tetrahedron in the asymmetric unit by considering all
average bond-valence sum of 1.071 (1) of Cs in the modulated directly bonded [MX6]- and [TX4]-groups. They can be
structure is slightly increased in comparison to the value of considered as above-polyhedral invariants of the crystal
0.985 (1) in the 3d-average structure (see Fig. 6). structure and represent a geometrical interpretation of the
coordination sequences up to k = 3. The PMEs of the first sub-
level observed for the M nodes can be described as follows:
5. Topological analysis of the average structure each [ScO6]-octahedron is immediately linked to six [SiO4]-
The crystal structure of Cs3ScSi6O15 can be described as a tetrahedra (see Fig. S17 in the supporting information), i.e. the
mixed tetrahedral–octahedral or MT framework, which is PME of a single M node contains six T nodes. According to the
formed from vertex sharing of [TX4]-tetrahedra and [MX6]- classification given by Ilyushin & Blatov (2002) based on the
octahedra. In their review on the crystal chemistry of zircon calculation of the coordination sequences up to k = 3 the
silicates, which are a prominent family of compounds PMEs can be denoted as {6,6,18} or, alternatively, this has also
belonging to this class of materials, Ilyushin & Blatov (2002) been classified as PME type A-1. The PMEs for the tetra-
suggested a classification based on a combination of topolo- hedral T nodes contain three tetrahedra and one octahedron,
gical and geometrical aspects. For the present study we and can be allocated to the {4,4,14} class (see Fig. S17).
focused on the sub-structure of the framework forming cations

6. Comparison to related structures and discussion

The only other CsSc silicate known to date, Cs3ScSi8O19
(Kolitsch & Tillmanns, 2004), has a unique microporous
framework structure. Although the coordination environment
of Sc and of the fully occupied Cs positions is very similar in
Cs3ScSi8O19 and Cs3ScSi6O15, the connectivity of the [SiO4]-
tetrahedra and [ScO6]-octahedra is very different, resulting in
four-, six- and eight-membered rings within the framework of
Cs3ScSi8O19, that is characterized by an unusual high
[TO4]:[MO6] ratio of > 6:1.
However, similar topological features as found in
Cs3ScSi6O15 have also been reported for Cs3EuSi6O15 (Huang
et al., 2005), Cs3DySi6O15 (Zhao et al., 2010) and
Cs1.86K1.14DySi6O15 (Wierzbicka-Wieczorek et al., 2015). All
four structures contain A-1-type PMEs for the octahedra and
topologically identical six-membered [Si6O18]-rings with the
Figure 6
Bond-valence sum of Cs as a function of t calculated up to a distance of same alternating up–down conformation of the tetrahedra.
3.5 Å. The [Si6O18]-rings are connected by A-1-type octahedra to

114 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 Acta Cryst. (2016). B72, 109–116
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form chains of alternating [ScO6]-[Si6O18]-units. In monoclinic 7. Conclusion
Cs3EuSi6O18, the symmetry of the [Si6O18]-ring is not The structure of Cs3ScSi6O15 forms a mixed tetrahedral–
constrained: the bridging atoms are situated almost within the octahedral framework with very large positional modulation
ring plane [maximum distance of 0.055(4) Å of individual O of the constituting atoms and thus giving rise to a diffraction
atoms from ring plane] and the angles between the normal to pattern composed of main and satellite reflections of
the ring plane and the connecting line between the terminal O remarkable intensity and high order. Structurally related
atoms range from 45.9 (1) to 80.0 (1) . The [ScO6]-[Si6O18]- compounds with very similar chains of alternating [MO6]-
chains run along the a-axis and are interconnected to form a [Si6O18]-units and large alkali cations have been reported:
tetrahedral silicate framework structure consisting of loop- Cs3EuSi6O15 has a different topological connectivity of the
branched vierer double chains with four-, six- and eight- [MO6]-[Si6O18]-chains in comparison to Cs3ScSiO15. The
membered rings. This is different from Cs3ScSi6O15, in which structures of Cs3DySi6O15 and Cs1.86K1.14DySi6O15 have the
tetrahedra within the framework form six-membered rings same topology with identical connections in between the
and ring-shaped formations with other numbers can only be [MO6]-[Si6O18]-chains as found for Cs3ScSiO15. A more thor-
found for rings composed of tetrahedra and octahedra. ough comparison of Cs3ScSi6O15, Cs3DySi6O15 and
In the crystal structure of Cs3DySi6O15 [a = 13.996 (1), c = Cs1.86K1.14DySi6O15 would be facilitated by the description of
7.1775 (6) Å, R3 m1 (Zhao et al., 2010)], the [ScO6]-[Si6O18]- all structures with the same basic structure and their positional
chains are arranged and connected in a very similar way as in modulations, either incommensurate as suspected for
Cs3ScSi6O15. However, the published structure has positional Cs3DySi6O15, or commensurate with a wavevector q = 1/5c*
disorder for Si, O and Cs atoms without further specification for Cs1.86K1.14DySi6O15. It seems likely that the ratio of the
or discussion of the disorder. This leads to the suggestion that ionic radii of Sc, Dy and Eu on the octahedral position to the
Cs3DySi6O15 may have a modulated structure similar to ionic radii of Cs and K is responsible for the presence of a
Cs3ScSi6O15. Another indicator for the possible modulated modulated or an unmodulated structure. However, from the
character of Cs3DySi6O15 is the conspicuously large displace- scarce data available any conclusion about the formation of a
ment ellipsoids with prolate form for some and oblate form for modulated structure, a topologically identical but unmodu-
other atoms. Such unusually large atomic displacement para- lated structure or a structure with different topology is highly
meters are typical for the refinement from only main reflec- speculative and deserves the synthesis of further members in
tions of a modulated structure and hence resulting in atomic this structural family and leaves room for further studies.
parameters averaged over the true atomic positions in the
modulated structure.
Cs1.86K1.14DySi6O15 (hereafter denoted CsKDy) [a =
8. Related literature
13.896 (2), c = 35.623 (7) Å, R32 (Wierzbicka-Wieczorek et al.,
2015)] has recently been published with the same basic References cited in the supporting information include: Chang
topology as Cs3ScSi6O15. In CsKDy, Cs is partially (38%) et al. (2013); Hejny et al. (2012); Sitarz et al. (1998).
exchanged by K. Although Cs/K in CsKDy has a 10- to 11-fold
coordination comparable to the coordination environment of Acknowledgements
Cs in Cs3ScSi6O15, the calculated bond-valence sums of the Cs/
This work was supported by the CEEPUS network (CIII-R0-
K site is 0.74–0.83 and thus indicates an underbonded char-
0038-10-1415) and the Serbian Ministry of Education, Science
acter. This is in contrast to the balanced coordination envir-
and Technological Development (under contract No.
onment of Cs in the (3+1) modulated structure of the title
III45007). The help, advice and quick response to all questions
compound. The main difference between Cs3ScSi6O15 and
concerning the JANA2006 program from M. Dusek and V.
CsKDy is the translational periodicity along the c direction,
Petřı́ček is highly appreciated. The authors express their
which is five times as large in CsKDy in comparison to
gratitude to two anonymous referees.
Cs3ScSi6O15. As in Cs3ScSi6O15, octahedra in CsKDy are
rotated around the 3 -axis. The octahedra in CsKDy occur in
five different rotational positions ( 13.5,  16.2,  19.5 and References
 20.7 relative to the octahedra in the origin) along the c Agilent (2012). CrysAlisPRO. Agilent Technologies, Yarnton,
translational period and each sixth DyO6-octahedron is Oxfordshire, UK.
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116 Clivia Hejny et al.  (3+1)-Incommensurately modulated structure of Cs3ScSi6O15 Acta Cryst. (2016). B72, 109–116