Последња измена: 2020-04-16 17:54:38

Polymorphism and photoluminescence properties of K3ErSi2O7

Predrag Dabić, Marko G. Nikolić, Sabina Kovač, Aleksandar Kremenović

Дигитални Репозиторијум Рударско-геолошког факултета Универзитета у Београду

[Др.РГФ]

Predrag Dabić, Marko G. Nikolić, Sabina Kovač, Aleksandar Kremenović | Polymorphism and photoluminescence properties
of K3ErSi2O7 | Acta Crystallographica Section C Structural Chemistry | 2019

DOI: 10.1107/S2053229619011926

URI: dr.rgf.bg.ac.rs/s/repo/item/5268

Дигитални репозиторијум Рударско-геолошког факултета
Универзитета у Београду омогућава приступ издањима
Факултета и радовима запослених доступним у слободном
приступу. Претрага репозиторијума доступна је на
dr.rgf.bg.ac.rs
The Digital repository of The University of Belgrade
Faculty of Mining and Geology archives faculty
publications available in open access, as well as the
employees' publications. The Repository is available at:
dr.rgf.bg.ac.rs
 electronic reprint

ISSN: 2053-2296
journals.iucr.org/c

Polymorphism and photoluminescence properties of

K3ErSi2O7

Predrag Dabić, Marko G. Nikolić, Sabina Kovač and Aleksandar

Kremenović

Acta Cryst. (2019). C75, 1417–1423

IUCr Journals
CRYSTALLOGRAPHY JOURNALS ONLINE
Copyright 
c International Union of Crystallography
Author(s) of this article may load this reprint on their own web site or institutional repository provided that
this cover page is retained. Republication of this article or its storage in electronic databases other than as
specified above is not permitted without prior permission in writing from the IUCr.
For further information see http://journals.iucr.org/services/authorrights.html

Acta Cryst. (2019). C75, 1417–1423 Dabić et al. · Polymorphism of K3 ErSi2 O7


ISSN 2053-2296
Received 15 August 2019
Accepted 28 August 2019
Edited by P. Fanwick, Purdue University, USA
Keywords: alkali rare-earth silicates; lanthanide
silicates; polymorphism; photoluminescence;
crystal structure.
CCDC references: 1950047; 1950046
Supporting information: this article has
supporting information at journals.iucr.org/c
# 2019 International Union of Crystallography
Acta Cryst. (2019). C75, 1417–1423
research papers
Polymorphism and photoluminescence properties
of K3ErSi2O7
Predrag Dabić,a* Marko G. Nikolić,b Sabina Kovača and Aleksandar Kremenovića
a
University of Belgrade, Faculty of Mining and Geology, Ðušina 7, Belgrade 11000, Serbia, and bUniversity of Belgrade,
Institute of Physics, Pregrevica 118, Belgrade 11080, Serbia. *Correspondence e-mail: predrag.dabic@rgf.bg.ac.rs
Two polymorphs of tripotassium erbium disilicate, K3ErSi2O7, were synthesized
by high-temperature flux crystal growth during the exploration of the flux
technique for growing new alkali rare-earth elements (REE) containing
silicates. Their crystal structures were determined by single-crystal X-ray
diffraction analysis. One of them (denoted 1) crystallizes in the space group
P63/mmc and is isostructural with disilicates K3LuSi2O7, K3ScSi2O7 and
K3YSi2O7, while the other (denoted 2) crystallizes in the space group
P63/mcm and is isostructural with disilicates K3NdSi2O7, K3REESi2O7 (REE =
Gd–Yb), K3YSi2O7, K3(Y0.9Dy0.1)Si2O7 and K3SmSi2O7. In the crystal structure
of polymorph 1, the Er cations are in an almost perfect octahedral coordination,
while in the crystal structure of polymorph 2, part of the Er cations are in a
slightly distorted octahedral coordination and the other part are in an ideal
trigonal prismatic coordination environment. Sharing six corners, disilicate
Si2O7 groups in the crystal structure of polymorph 1 link six ErO6 octahedra,
forming a three-dimensional network and nine-coordinated potassium cations
are located in its holes. In the crystal structure of polymorph 2, the disilicate
Si2O7 groups connect four ErO6 octahedra, as well as one ErO6 trigonal prism.
Three differently coordinated potassium cations are situated between them.
Different site symmetries of the erbium cations in the crystal structures of
polymorphs 1 and 2 affect their photoluminescence properties. Only polymorph
2 exhibits luminescence. Intense narrow lines in the emission spectrum are a
result of the 4f–4f transition. The green emission line at 560 nm is the result of
the Er3+ transition 4S3/2!4I15/2, and the luminescence line at 690 nm is the result
of a 4F9/2!4I15/2 transition. The crystal morphologies of the two polymorphs are
similar. Crystals of polymorph 1 are in the form of a hexagonal prism in
combination with a hexagonal base, while crystals of polymorph 2 contain a
dihexagonal prism in combination with a hexagonal base, although poorly
developed faces of the dihexagonal pyramid can also be noticed.
1. Introduction
Silicates form a large number of different phases and exhibit a
broad structural diversity (Liebau, 1985), which leads to their
extensive applications. Among them, silicates containing rare-
earth elements (REE) are the subject of intense research (for
example, Felsche, 1973; Rocha, 2003; Kolitsch & Tillmanns,
2004; Liu et al., 2014; Wierzbicka-Wieczorek et al., 2015b;
Dabić et al., 2016). They possess a highly adaptive framework
that can incorporate almost all REEs. This opens up the
possibility of synthesizing numerous structures and structural
series of REE-containing silicates. A wide range of observed
optical and magnetic properties makes them very interesting
and promising materials for different applications (for
example, Kitai, 2008; Latshaw et al., 2015, 2016b; Figueiredo et
al., 2016). REE-containing compounds have been studied
intensively because their luminescence radiation is emitted
over a large spectral range (Chiang et al., 2007). In recent
https://doi.org/10.1107/S2053229619011926 1417
electronic reprint
research papers
Table 1
Experimental details.
For both determinations, the chemical formula is K3ErSi2O7, Mr = 452.74. Experiments were carried out at 298 K with Mo K radiation using an Agilent Xcalibur
Sapphire3 Gemini diffractometer. An analytical absorption correction was employed (Clark & Reid, 1995).
Crystal data
Crystal system, space group
a, c (Å)
V (Å3)
Z 2
 (mm1)
Crystal size (mm)
Data collection
No. of measured, independent and observed
[I > 2(I)] reflections
Rint
(sin /)max (Å1)
Refinement
R[F 2 > 2(F 2)], wR(F 2), S
No. of reflections
No. of parameters

max,
min (e Å3)
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1994), SHELXL2015 (Sheldrick, 2015), VESTA (Momma & Izumi, 2011), WinGX (Farrugia, 2012) and
publCIF (Westrip, 2010).
decades, many studies were carried out on REE-containing
silicates because of their high thermal stability and interesting
luminescence properties.
Several ternary potassium–REE silicates with the stoichio-
metric composition K3REESi2O7 have been reported in the
literature. The compounds isostructural with polymorph 1, i.e.
K3LuSi2O7 (Vidican et al., 2003), K3ScSi2O7 (Napper et al.,
2004) and K3YSi2O7 (Latshaw et al., 2016a), crystallize in the
space group P63/mmc (No. 194). There are also several
compounds isostructural with polymorph 2, which crystallize
in the space group P63/mcm (No. 193), namely K3EuSi2O7
(Bondar et al., 1965), K3NdSi2O7 (Hwang et al., 1987),
K3REESi2O7 (REE = Gd–Yb) (Vidican et al., 2003), K3YSi2O7
(Latshaw et al., 2016a) and K3SmSi2O7 (Latshaw et al., 2016b).
During our investigations, aimed at an exploration of the
flux technique for growing new potassium–REE silicates, two
polymorphs of K3ErSi2O7 were synthesized. Each of them was
synthesized in a separate batch. The crystal structure of
polymorph 1 is presented for the first time, while the crystal
structure of polymorph 2 has been reported previously
(Vidican et al., 2003), although the photoluminescence prop-
erties of both polymorphs are unknown. The focus of this
article is the determination of the structural characteristics
and photoluminescence properties of both polymorphs in the
single-crystal form.
2. Experimental
Both polymorphs were analyzed by the single-crystal X-ray
diffraction method. Room-temperature intensity data for
polymorphs 1 and 2 were collected and relevant information
on the crystal data and data collection are compiled in Table 1.
The synthesized products were also tested using powder
X-ray diffraction (PXRD). A small amount of material from
1418 Dabić et al.  Polymorphism of K3ErSi2O7
electronic reprint
1 2
Hexagonal, P63/mmc Hexagonal, P63/mcm
5.7513 (1), 13.9960 (3) 9.8338 (2), 14.2843 (4)
400.93 (2) 1196.28 (6)
6
12.32 12.39
0.12  0.06  0.05 0.16  0.11  0.08
2755, 237, 218 5150, 578, 512
0.035 0.023
0.684 0.682
0.015, 0.039, 1.30 0.021, 0.046, 1.23
237 578
20 41
0.56, 0.65 0.59, 0.82
both batches was finely ground and tested on a Rigaku
SmartLab powder X-ray diffractometer at room temperature
using Bragg–Brentano geometry and Cu K radiation. The
diffractometer was operated at 40 kV and 30 mA, while the
scan range was from 3 to 60 2, with a step size of 0.01 and a
scanning speed of 5  min1. PDXL 2 software (Rigaku, 2007)
was used for the powder diffraction data analysis.
Scanning electron microscopy–energy dispersive X-ray
spectroscopy (SEM–EDS) was used for the morphological and
semiquantitative chemical characterization of both poly-
morphs. The analyses were carried out on single crystals using
a JEOL JSM-6610LV instrument equipped with an Oxford
INCA Energy 350 EDS detector. In order to obtain a crystal
surface without impurities, several crystals of polymorphs 1
and 2 were polished. Crystals were mounted on a piece of two-
sided tape. A special plastic ring was used to enclose a zone in
which epoxy resin was poured. After hardening of the epoxy,
the mount was ground with an automatic grinding machine to
produce a flat surface and it was then polished with diamond
paste.
The photoluminescence spectral measurements were
carried out under continuous excitation with light of a 30 mW
diode laser at 405 nm. Photoluminescence spectra were
collected at room temperature on an Avantes 2048-TEC
spectrometer with a cooled CCD in the range 540–720 nm.
2.1. Synthesis and crystallization
2.1.1. Synthesis of 1. The following chemicals were used for
the high-temperature flux synthesis (batch 1) of polymorph 1:
Er2O3 (Sigma–Aldrich, 99.99%), SiO2 (Merck, p.a.) and KF
(Centrohem, 99%). 0.1647 g of a mixture of Er2O3 and SiO2 in
a 1:4 molar ratio was measured and then 2 g KF was added.
The resulting mixture was homogenized in an agate mortar
Acta Cryst. (2019). C75, 1417–1423
 research papers
Table 2 Table 3
Selected bond lengths (Å) for polymorph 1. Selected bond lengths (Å) for polymorph 2.
K1—O1i 2.87943 (14) K2—O1xii 2.797 (3) K1—O1i 2.742 (2) K3—O2iii 2.726 (3)
K1—O1ii 2.87943 (14) K2—O2xiii 3.32050 (5) K1—O1ii 2.742 (2) K3—O2xix 2.726 (3)
K1—O1iii 2.87943 (14) K2—O2 3.32051 (6) K1—O2iii 2.9302 (13) K3—O2xx 2.726 (3)
K1—O1iv 2.87943 (14) K2—O2xiv 3.32054 (6) K1—O2iv 2.9302 (13) Er1—O1xxi 2.236 (2)
K1—O1v 2.87943 (14) Er1—O1xv 2.241 (2) K1—O1v 2.962 (2) Er1—O1ix 2.236 (2)
K1—O1 2.87943 (14) Er1—O1xvi 2.241 (2) K1—O1vi 2.962 (2) Er1—O1xxii 2.236 (2)
K1—O1vi 3.041 (3) Er1—O1iv 2.241 (2) K1—O1vii 3.014 (2) Er1—O1xii 2.236 (2)
K1—O1vii 3.041 (3) Er1—O1vii 2.241 (2) K1—O1viii 3.014 (2) Er1—O1xxiii 2.236 (2)
K1—O1viii 3.041 (3) Er1—O1x 2.241 (2) K2—O1ix 2.899 (2) Er1—O1xiii 2.236 (2)
K2—O1 2.797 (3) Er1—O1 2.241 (2) K2—O1x 2.899 (2) Er2—O2xxiv 2.279 (3)
K2—O1ix 2.797 (3) Si1—O1 1.613 (3) K2—O1xi 2.899 (2) Er2—O2iii 2.279 (3)
K2—O1x 2.797 (3) Si1—O1xvii 1.613 (3) K2—O1xii 2.899 (2) Er2—O2xx 2.279 (3)
K2—O1xi 2.797 (3) Si1—O1v 1.613 (3) K2—O1xiii 2.899 (2) Er2—O2iv 2.279 (3)
K2—O1iv 2.797 (3) Si1—O2 1.6418 (17) K2—O1xiv 2.899 (2) Er2—O2xxv 2.279 (3)
K2—O3xv 2.9830 (14) Er2—O2xxvi 2.279 (3)
Symmetry codes: (i) x + y, x + 1, z; (ii) x, y + 1, z; (iii) y + 1, x  y + 1, z; (iv) y, x  y,
z; (v) x + y + 1, x + 1, z; (vi) y, x + y + 1, z; (vii) x  y, x, z; (viii) x + 1, y + 1,
K2—O3xvi 2.9830 (14) Si1—O1vi 1.609 (2)
z; (ix) x, y, z + 12; (x) x + y, x, z; (xi) y, x  y, z + 12; (xii) x + y, x, z + 12; (xiii) K2—O3iv 2.9830 (14) Si1—O1v 1.609 (2)
x  1, y  1, z; (xiv) x  1, y, z; (xv) x, y, z; (xvi) y, x + y, z; (xvii) y + 1, x  y, K3—O2xvii 2.726 (3) Si1—O2 1.626 (3)
z. K3—O2iv 2.726 (3) Si1—O3 1.663 (2)
K3—O2xviii 2.726 (3)

and transferred to a platinum crucible which was closed with a
lid. The mixture was transferred to a resistance-heated furnace
which was already heated to a temperature of 413 K. The
reaction mixture was heated to 1173 K at a rate of 200 K h1
and kept for 12 h at the final temperature. The temperature
was lowered to 973 K at a rate of 5 K h1 and then the furnace
was allowed to cool to room temperature. As a result, trans-
parent pale-pink prismatic single crystals up to 0.2 mm in
length (yield about 90%) were obtained and washed with
distilled water and dried in air.
2.1.2. Synthesis of 2. Single crystals of polymorph 2 were
obtained in the synthesis (batch 2) using the same chemicals as
for polymorph 1. A total of 0.2 g of a nutrient made up of a
mixture of Er2O3 and SiO2 in a molar ratio of 1:4 was
measured. 0.8 g of KF was then added and the mixture was
homogenized in an agate mortar. The material thus obtained
was transferred to a platinum crucible, covered with a
platinum lid and placed in a resistance-heated furnace. The
mixture was heated in air to a temperature of 1473 K at a rate
of 100 K h1. The achieved temperature was maintained for
Symmetry codes: (i) x  y, x  1, z + 1; (ii) y + 1, x + 1, z + 1; (iii) y, x  y  1, z;
(iv) x + y + 1, x + 1, z; (v) x, x  y, z + 1; (vi) y, x + y, z + 1; (vii) x + 1, x + y,
z  1; (viii) y + 1, x  y, z  1; (ix) x  y, x, z + 1; (x) y, x + y + 1, z  12; (xi) x  y, x,
z  12; (xii) y, x + y + 1, z + 1; (xiii) x + 1, y + 1, z + 1; (xiv) x + 1, y + 1, z  12;
(xv) y, x  y, z; (xvi) x, y + 1, z; (xvii) x  y  1, x  1, z; (xviii) y, x + y + 1, z; (xix)
x + 1, y, z; (xx) x  1, y, z; (xxi) x + 1, x + y + 1, z  1; (xxii) x  y, y + 1, z  1;
(xxiii) y, x, z  1; (xxiv) x + y + 1, x + 1, z + 12; (xxv) y, x  y  1, z + 12; (xxvi) x  1,
y, z + 12.
4 h and then lowered to 873 K at a rate of 10 K h1. The
furnace was then allowed to cool to room temperature. The
obtained transparent pink prismatic single crystals up to
0.2 mm in length (yield about 30%) were washed with distilled
water and dried in air.
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. The structures were solved
by a combination of direct methods and difference Fourier
syntheses and they were refined by full-matrix least-squares
techniques. The refinements of polymorphs 1 and 2 were
initiated with the atomic coordinates of K3LuSi2O7 and
K3ErSi2O7 (Vidican et al., 2003), respectively. The relevant
information on the refinements is compiled in Table 1.
Selected bond lengths and angles, as well as bond-valence-sum
calculations, obtained using VaList software (Wills, 2010), are
presented in Tables 2–5. All figures were plotted using VESTA
(Momma & Izumi, 2011).

3. Results and discussion

Figure 1
A polyhedral view of the framework in the crystal structure of polymorph
1 along [001]. Colour code: SiO4 tetrahedra are yellow, ErO6 octahedra
are violet and K atoms are presented by blue spheres (K1 is light blue and
K2 is dark blue).
3.1. Single-crystal X-ray diffraction
As a result of high-temperature flux syntheses, two poly-
morphs of K3ErSi2O7 were grown. The crystal structure of 1
corresponds to a novel polymorph of K3ErSi2O7 which crys-
tallizes in the space group P63/mmc, while the crystal structure
of 2, which crystallizes in the space group P63/mcm, has been
described previously (Vidican et al., 2003). Both crystal
structures are related to the sorosilicate structure types
described earlier by Vidican and co-authors.

Acta Cryst. (2019). C75, 1417–1423 Dabić et al.  Polymorphism of K3ErSi2O7 1419
electronic reprint
research papers
Table 4
Bond valences ij (valence units) for polymorph 1.
K1 K2 Er1 Si1
O1 0.133  6 + 0.086  3 0.166  6 0.505  6 1.030  3
O2 – 0.040  3 – 0.953
ij 1.056 (6) 1.116 (12) 3.03 (1) 4.043 (1)
The crystal structure of polymorph 1 is built up from Si2O7
groups and ErO6 polyhedra connected into a three-dimen-
sional (3D) framework. The large potassium ions are located
in the holes of the 3D framework (Fig. 1). All atoms are
situated in special positions. There are two potassium, one
erbium, one silicon and two oxygen unique sites per unit cell.
Erbium cations are octahedrally coordinated and each ErO6
octahedron is connected to six Si2O7 groups sharing corners.
The Er—O distances of 2.241 (2) Å are uniform. The ErO6
octahedra are interconnected via O—Si—O linkages. The
Si2O7 groups are mutually isolated units formed by two
corner-sharing SiO4 tetrahedra and they are parallel to the c
axis (Fig. 2). Each Si2O7 group is connected to six different
erbium cations, adopting an Si—O—Si angle of 180 , which is
not common in sorosilicate structures. Bond distances in the
SiO4 tetrahedra are in the normal range, but it is obvious that
the bond distance from silicon to the bridging oxygen ion
[1.6418 (17) Å in 1] is longer than the remaining nonbridging
Si—O bonds [1.613 (3) Å in 1]. The O—Si—O bond angles
range from 108.35 (11) to 110.57 (11) , which are rather
typical for sorosilicate structures. Both potassium sites are
nine-coordinated, with K—O bond lengths ranging from
2.87943 (14) to 3.041 (3) Å in K1O6+3 polyhedra and from
2.797 (3) to 3.32051 (6) Å in K2O6+3 polyhedra. The coordi-
nation polyhedron of K1 is a nondistorted hexagonal pyramid
with a triple apex, while the coordination polyhedron of K2 is
a nondistorted tricapped trigonal prism.
Figure 2
The Si2O7 groups and ErO6 octahedra in the crystal structure of
polymorph 1 projected along [110] showing their connections. The colour
coding is as in Fig. 1. Potassium cations have been omitted for clarity.
1420 Dabić et al.  Polymorphism of K3ErSi2O7
electronic reprint
Table 5
Bond valences ij (valence units) for polymorph 2.
ij K1 K2 K3 Er1 Er2 Si1 ij
1.967 O1 0.192  2 0.126  6 – 0.512  6 – 1.041  2 2.069
2.026 + 0.106  2
+ 0.092  2
O2 0.116  2 – 0.201  6 – 0.455  6 0.995 1.883
O3 – 0.100  3 – – – 0.900 2.000
ij 1.012 (1) 1.056 (6) 1.206 (21) 3.072 (2) 2.73 (9) 3.977 (1)
The crystal structure of polymorph 2 consists also of Si2O7
groups and ErO6 polyhedra which form a 3D framework with
potassium ions in the holes (Fig. 3). There are two unique
erbium sites, both in sixfold coordination: Er1O6 is an octa-
hedron and Er2O6 is a trigonal prism. Two types of polyhedra
around erbium cations are characterized by a small difference
in the Er—O distances: all Er1—O distances are 2.236 (2) Å,
while all Er2—O bond lengths are 2.279 (3) Å. Each Er1O6
octahedron is connected to six different Si2O7 groups via
corner sharing. Each Er2O6 trigonal prism also shares six
corners, but with only three different Si2O7 groups. Contrary
to polymorph 1, for polymorph 2, each Si2O7 group is
connected to five different cations, i.e. four Er1 and one Er2.
In addition, the Si2O7 groups are bent (Fig. 4), with Si—O—Si
angles of 135.0 (3) . Individual Si—O distances show a greater
dispersion compared to polymorph 1. However, the observed
values are in the normal range for silicate structures. The
bridging Si—O bond [1.663 (2) Å] is expectedly longer than
the nonbridging Si—O bonds [1.609 (2) and 1.626 (3) Å]. The
O—Si—O bond angles range from 106.47 (12) to 111.46 (11) .
Three potassium cations exhibit three different coordination
environments. The coordination spheres of K1, K2 and K3
include eight, nine and six oxygen ions, respectively. The
coordination polyhedron K1O2+4+2 can be described as a
distorted hexagonal pyramid with a split apex [distances range
from 2.742 (2) to 3.014 (2) Å], the coordination polyhedron
K2O6+3 is a regular tricapped trigonal prism [distances are
Figure 3
A polyhedral representation of the framework in the crystal structure of
polymorph 2 along [001]. Colour code: SiO4 tetrahedra are yellow, Er1O6
octahedra are violet, Er2O6 trigonal prisms are purple and K atoms are
presented by blue spheres [K1 is light blue, K2 is dark blue and K3 atoms,
which are located at (0,0,0), have been omitted for clarity].
Acta Cryst. (2019). C75, 1417–1423
 research papers
Table 6
Comparison of the unit-cell parameters for the two known structure types of potassium sorosilicates containing REEs with the general formula
K3REESi2O7.
Compound Space group a (Å) c (Å) V (Å3) Reference

K3NdSi2O7 P63/mcm 10.025 (1) 14.526 (1) 1264.1 (3) Hwang et al. (1987)
K3SmSi2O7 P63/mcm 9.9764 (1) 14.4844 (3) 1248.47 (4) Latshaw et al. (2016b)
K3EuSi2O7 a P63/mcm 9.98 (1) 14.44 (2) 1245.54 (4) Bondar et al. (1965)
K3GdSi2O7 P63/mcm 9.9359 (2) 14.4295 (4) 1233.66 (5) Vidican et al. (2003)
K3TbSi2O7 P63/mcm 9.8873 (1) 14.3856 (3) 1217.91 (3) Vidican et al. (2003)
K3DySi2O7 P63/mcm 9.8673 (2) 14.3572 (4) 1210.59 (5) Vidican et al. (2003)
K3HoSi2O7 P63/mcm 9.8408 (3) 14.3206 (6) 1200.93 (7) Vidican et al. (2003)
K3Y0.9Dy0.1Si2O7 P63/mcm 9.8496 (2) 14.3292 (4) 1203.90 (6) Latshaw et al. (2016a)
K3YSi2O7 P63/mcm 9.8450 (2) 14.3236 (3) 1202.30 (5) Latshaw et al. (2016a)
K3ErSi2O7 P63/mcm 9.8212 (1) 14.2986 (2) 1194.41 (2) Vidican et al. (2003)
K3ErSi2O7 P63/mcm 9.8338 (2) 14.2843 (4) 1196.28 (6) This work
K3TmSi2O7 P63/mcm 9.8020 (1) 14.2863 (4) 1188.72 (4) Vidican et al. (2003)
K3YbSi2O7 P63/mcm 9.7819 (1) 14.2401 (3) 1180.02 (3) Vidican et al. (2003)
K3YSi2O7 P63/mmc 5.7627 (1) 14.0205 (6) 403.22 (2) Latshaw et al. (2016a)
K3ErSi2O7 P63/mmc 5.7513 (1) 13.9960 (3) 400.93 (2) This work
K3LuSi2O7 P63/mmc 5.7116 (1) 13.8883 (6) 392.37 (2) Vidican et al. (2003)
K3ScSi2O7 P63/mmc 5.6065 (1) 13.6420 (4) 371.357 (14) Napper et al. (2004)
Note: (a) only the lengths of the unit-cell axes are reported.

2.899 (2) and 2.9830 (14) Å] and K3O6 is an undistorted yttrium analogue crystallizes in two polymorphic modifica-
trigonal antiprism [K—O = 2.726 (3) Å]. tions, i.e. one K3YSi2O7 in the space group P63/mcm and the
Bond-valence calculations (Tables 4 and 5) show that the other K3YSi2O7 in the space group P63/mmc, similar to
bond valences are well balanced and the K—O, Er—O and K3ErSi2O7 polymorphs 1 and 2 presented here.
Si—O bond lengths are consistent with the presence of K+,
Er3+, Si4+ and O2 in both structures. Only in polymorph 2 are
the bond-valence sums for Er2 and O2 slightly undersaturated 3.2. Powder X-ray diffraction (PXRD)
(ij are 2.73 and 1.88 v.u. for Er2 and O2, respectively) and Collected PXRD data for two batches are shown in Figs. S1
that for K3 oversaturated (1.21 v.u.). This means that a slightly and S2 (see supporting information). The CIF files obtained
shorter K3—O2 and slightly longer Er2—O2 and Si1—O2 from the single-crystal data (see supplementary files) of
bonds are formed in order to satisfy the local valence polymorphs 1 and 2 were used to calculate their diffraction
disagreement due to structural disorder. patterns. In both powder samples, only polymorphs 1 and 2
As already mentioned, polymorph 1 is isostructural with were identified unambiguously.
K3LuSi2O7 (Vidican et al., 2003), K3ScSi2O7 (Napper et al.,
2004) and K3YSi2O7 (Latshaw et al., 2016a), while polymorph 2
is isostructural with K3NdSi2O7 (Hwang et al., 1987),
K3REESi2O7 (REE = Gd–Yb) (Vidican et al., 2003),
K3YSi2O7, K3Y0.9Dy0.1Si2O7 (Latshaw et al., 2016a) and
K3SmSi2O7 (Latshaw et al., 2016b). Table 6 shows how the
unit-cell parameters vary as the chemical composition changes
in two known structure types of disilicates incorporating
REEs. Felsche (1973) was among the first to extensively
discuss the relationship between structure type and REE ionic
radii in silicate compounds. Vidican and co-authors concluded
that the size of the REE ionic radii is responsible for whether
the crystals of K3REESi2O7 will crystallize in the space group
P63/mmc or P63/mcm. They supposed that the scandium
analogue, not known at that time, will be isostructural with
K3LuSi2O7 (the ‘effective’ ionic radii of VILu3+ and VISc3+ are
0.861 and 0.745 Å, respectively; Shannon, 1976). After the
successful synthesis of K3ScSi2O7, Napper and co-authors
confirmed their prediction. Vidican and co-authors also
predicted that the yttrium analogue should be isostructural
with the K3REESi2O7 (REE = Gd–Yb) crystal structures since Figure 4
The polyhedra of the Si2O7 groups, Er1O6 octahedra and Er2O6 trigonal
the ionic radius of Y falls between the radii of Er and Ho (the
prisms in the crystal structure of polymorph 2 projected along [120]. The
‘effective’ ionic radii of VIEr3+, VIY3+ and VIHo3+ are 0.89, 0.90 colour coding is as in Fig. 3. Potassium cations have been omitted for
and 0.901 Å, respectively; Shannon, 1976). However, the clarity.

Acta Cryst. (2019). C75, 1417–1423 Dabić et al.  Polymorphism of K3ErSi2O7 1421
electronic reprint
research papers
Figure 5
Scanning electron microscope (SEM) photography of the crystals of (a)
polymorph 1 and (b) polymorph 2.
3.3. Scanning electron microscopy–energy dispersive X-ray
spectroscopy (SEM–EDS)
The crystal morphology of polymorphs 1 and 2 obtained
using a SEM is shown in Fig. 5. A hexagonal prism in
combination with a hexagonal base characterize the crystals of
polymorph 1 (Fig. 5a). A dihexagonal prism in combination
with a hexagonal base characterize the crystals of polymorph 2
(Fig. 5b), although poorly developed faces of the dihexagonal
pyramid can also be noticed. A crystal morphology similar to
polymorph 2 was reported also by Bondar et al. (1965). Both
crystals look homogeneous, but small cracks are observed on a
surface of the crystal representing polymorph 2. Semiquanti-
tative chemical analysis confirmed the presence of potassium,
erbium and silicon elements. However, the results showed an
unexpected K:Er:Si ratio and a significant fluorine content,
which differed from the chemical composition obtained by
single-crystal X-ray structure analysis. In this method of
synthesis, it is not rare that an impurity could be situated on a
crystal surface. Therefore, selected crystals of polymorphs 1
and 2 were polished in order to remove any impurity on the
crystal surface and to obtain the chemical composition of a
pure single crystal. After crystal polishing, the semiquanti-
tative chemical analysis shows a K:Er:Si ratio of 3.05:1.04:1.91
Figure 6
Luminescence spectra of polymorph 1 (black line) and polymorph 2 (red
line).
1422 Dabić et al.  Polymorphism of K3ErSi2O7
electronic reprint
for polymorph 1, and the same ratio for polymorph 2 is
3.01:1.05:1.94, what is in good agreement with the results of
the single-crystal X-ray structure analysis.
3.4. Photoluminescence spectroscopy
Even a small change in the local symmetry of the rare earth
ions REE3+ is visible in their luminescence spectra (Blasse &
Grabmaier, 1994). The photoluminescence properties of the
crystals of polymorphs 1 and 2 were investigated and are
presented in Fig. 6. Single crystals with no impurities
(detectable by SEM) were selected for the recording of
photoluminescence spectra.
The spectra clearly show that only polymorph 2 exhibits
luminescence. Intense narrow lines in the emission spectrum
are the result of a 4f–4f transition. The green emission line at
560 nm results from the Er3+ transition 4S3/2!4I15/2, and the
luminescence line at 690 nm results from the 4F9/2!4I15/2
transition. There was no evident difference in the photo-
luminescence spectra whether the laser beam was aligned
parallel to the c axis of the crystal or perpendicular to it.
Luminescence is determined by the probability of electric-
dipole transitions between certain orbitals in elements which
contain 4f n orbitals (REEs). Although f–f electric-dipole
transitions in REE ions are strictly forbidden due to the parity
selection rule, they can become partially allowed due to the
mixing of orbitals of opposite parity. This happens in struc-
tures in which a REE ion occupies a site without an inversion
centre (Blasse & Grabmaier, 1994). In polymorph 1, there is
only one unique erbium site 2a (site symmetry 3m.) or D3d,
while in polymorph 2, there are two unique erbium sites, i.e.
Er1 (4d, site symmetry 3.2) and Er2 (2a, site symmetry 62m) or
D3 and D3h, respectively. The sites of the Er1 and Er2 ions in
polymorph 2 have no centre of symmetry. Therefore, only
polymorph 2 is luminescence active.
4. Conclusion
Single crystals of two polymorphs of tripotassium erbium
disilicate, K3ErSi2O7, were prepared by high-temperature flux
crystal growth and were characterized by single-crystal X-ray
diffraction, powder X-ray diffraction, SEM–EDS analysis and
photoluminescence spectroscopy. One polymorph (i.e. 1) of
the title compound crystallizes like K3LuSi2O7, K3ScSi2O7 and
K3YSi2O7, sorosilicates which contain the smallest REEs,
lutetium and scandium (the ‘effective’ ionic radii are VILu3+ =
0.861 Å and VISc3+ = 0.745 Å; Shannon, 1976) and the yttrium
ion, which is slightly larger than erbium (the ‘effective’ ionic
radii are VIEr3+ = 0.890 Å and VIY3+ = 0.900 Å; Shannon,
1976). The other polymorph (i.e. 2) crystallizes like disilicates
containing the larger REEs, i.e. Nd, Sm, Eu, Gd, Tb, Dy, Ho,
Er, Tm and Yb. Their ‘effective’ ionic radii range from 0.983 Å
for VINd3+ to 0.868 Å for VIYb3+ (Shannon, 1976). Different
site symmetries of the erbium cations in the crystal structures
of polymorphs 1 (site symmetry m. or D3d) and 2 (site
symmetry 3.2 and 2m or D3 and D3h) cause different photo-
luminescence properties. The erbium sites in polymorph 2
Acta Cryst. (2019). C75, 1417–1423

have no centre of symmetry and therefore only polymorph 2 is
luminescence active. The results presented here, as well as the
literature data, show that a critical REE ion size, where two
polymorphs/structure types are possible, is extended and
besides yttrium, includes also erbium (the range is from 0.900
to 0.890 Å). This information should be taken into consid-
eration when a luminescence-active tripotassium REE disili-
cate crystal is to be synthesized.
Acknowledgements
The authors thank the Laboratory for Scanning Electron
Microscopy at the Department of Mineralogy, Crystal-
lography, Petrology and Geochemistry, University of
Belgrade, Faculty of Mining and Geology, the Laboratory of
X-ray diffraction at the Department of Physics, University of
Novi Sad, Faculty of Sciences, and Ljiljana Karanović,
Professor Emeritus since 2016, University of Belgrade, Faculty
of Mining and Geology, Laboratory of Crystallography, for
help and advice.
Funding information
Funding for this research was provided by: Ministry of
Education, Science and Technological Development of the
Republic of Serbia (contract Nos. III45007 and III45015);
Ministry of Education, Science and Technological Develop-
ment of the Republic of Serbia & Austria Federal Ministry of
Education, Science and Research (project No. 451-03-02141/
2017-09/14; WTZ project No. SRB 14/2018).
References
Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton,
Oxfordshire, England.
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla,
M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
Blasse, G. & Grabmaier, B. C. (1994). In Luminescent Materials.
Berlin: Springer-Verlag.
Acta Cryst. (2019). C75, 1417–1423
electronic reprint
research papers
Bondar, I. A., Tenisheva, T. F., Shepelev, Y. F. & Toropov, N. A.
(1965). Dokl. Akad. Nauk SSSR, 160, 1069–1071.
Chiang, P.-Y., Lin, T.-W., Dai, J.-H., Chang, B.-C. & Lii, K.-H. (2007).
Inorg. Chem. 46, 3619–3622.
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
Dabić, P., Kahlenberg, V., Schmidmair, D., Kremenović, A. & Vulić, P.
(2016). Z. Kristallogr. 231, 195–207.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Felsche, J. (1973). In The Crystal Chemistry of the Rare-Earth
Silicates. Rare Earths. Structure and Bonding, Vol. 13. Berlin,
Heidelberg: Springer.
Figueiredo, B. R., Valente, A. A., Lin, Z. & Silva, C. M. (2016).
Microporous Mesoporous Mater. 234, 73–97.
Hwang, M. S., Hong, H. Y.-P., Cheng, M. C. & Wang, Y. (1987). Acta
Cryst. C43, 1241–1243.
Kitai, A. (2008). In Luminescent Materials and Applications.
Chichester: John Wiley & Sons Ltd.
Kolitsch, U. & Tillmanns, E. (2004). Miner. Mag. 68, 677–686.
Latshaw, A. M., Morrison, G., Loye, K. D., Myers, A. R., Smith, M. D.
& zur Loye, H.-C. (2016a). CrystEngComm, 18, 2294–2302.
Latshaw, A. M., Wilkins, B. O., Hughey, K. D., Yeon, J., Williams, D. E.,
Tran, T. T., Halasyamani, P. S. & zur Loye, H.-C. (2015).
CrystEngComm, 17, 4654–4661.
Latshaw, A. M., Yeon, J., Smith, M. D. & zur Loye, H.-C. (2016b). J.
Solid State Chem. 235, 100–106.
Liebau, F. (1985). Structural Chemistry of Silicates: Structure, Bonding
and Classification, p. 347. Berlin, Heidelberg: Springer–Verlag.
Liu, W., Ji, Y., Bao, X., Wang, Y., Li, B., Wang, X., Zhao, X., Liu, X. &
Feng, S. (2014). Dalton Trans. 43, 13892–13898.
Momma, K. & Izumi, F. (2011). J. Appl. Cryst. 44, 1272–1276.
Napper, J. D., Layland, R. C., Smith, M. D. & Loye, H. (2004). J.
Chem. Crystallogr. 34, 347–351.
Rigaku (2007). PDXL 2: Integrated powder X-ray diffraction
software. Version 2.8.3.0. Rigaku Corporation, Tokyo, Japan.
https://www.rigaku.com/en/service/software/pdxl.
Rocha, J. (2003). Curr. Opin. Solid State Mater. Sci. 7, 199–205.
Shannon, R. D. (1976). Acta Cryst. A32, 751–767.
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Vidican, I., Smith, M. & zur Loye, H.-C. (2003). J. Solid State Chem.
170, 203–210.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Wierzbicka-Wieczorek, M., Kolitsch, U., Lenz, C. & Giester, G.
(2015b). J. Lumin. 168, 207–217.
Wills, A. S. (2010). VaList. Available from www.CCP14.ac.uk.
Dabić et al.  Polymorphism of K3ErSi2O7 1423
 supporting information

supporting information

Acta Cryst. (2019). C75, 1417-1423 [https://doi.org/10.1107/S2053229619011926]

Polymorphism and photoluminescence properties of K3ErSi2O7

Predrag Dabić, Marko G. Nikolić, Sabina Kovač and Aleksandar Kremenović

Computing details
For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data
reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s)
used to refine structure: SHELXL2015 (Sheldrick, 2015); molecular graphics: VESTA (Momma & Izumi, 2011); software
used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

Tripotassium erbium disilicate (shelx)

Crystal data
K3ErSi2O7 Dx = 3.750 Mg m−3
Mr = 452.74 Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mmc Cell parameters from 1775 reflections
a = 5.7513 (1) Å θ = 4.1–28.7°
c = 13.9960 (3) Å µ = 12.32 mm−1
V = 400.93 (2) Å3 T = 298 K
Z=2 Prismatic, pale-pink
F(000) = 418 0.12 × 0.06 × 0.05 mm

Data collection
Agilent Xcalibur Sapphire3 Gemini 237 independent reflections
diffractometer 218 reflections with I > 2σ(I)
ω scans Rint = 0.035
Absorption correction: analytical θmax = 29.1°, θmin = 2.9°
(Clark & Reid, 1995) h = −7→7
k = −7→7
2755 measured reflections l = −18→18

Refinement
Refinement on F2 w = 1/[σ2(Fo2) + (0.0164P)2 + 0.5447P]
Least-squares matrix: full where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.015 (Δ/σ)max < 0.001
wR(F2) = 0.039 Δρmax = 0.56 e Å−3
S = 1.30 Δρmin = −0.65 e Å−3
237 reflections Extinction correction: SHELXL2015
20 parameters (Sheldrick, 2015),
0 restraints Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.048 (2)

Acta Cryst. (2019). C75, 1417-1423 sup-1

electronic reprint
 supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
K1 0.3333 0.6667 0.09128 (11) 0.0138 (3)
K2 0.0000 0.0000 0.2500 0.0188 (5)
ER1 0.0000 0.0000 0.0000 0.0058 (2)
SI1 0.6667 0.3333 0.13270 (12) 0.0054 (3)
O1 0.3592 (5) 0.1796 (3) 0.09641 (18) 0.0131 (6)
O2 0.6667 0.3333 0.2500 0.0207 (16)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

K1 0.0121 (4) 0.0121 (4) 0.0173 (7) 0.0060 (2) 0.000 0.000
K2 0.0239 (8) 0.0239 (8) 0.0085 (9) 0.0119 (4) 0.000 0.000
ER1 0.0053 (2) 0.0053 (2) 0.0068 (3) 0.00267 (11) 0.000 0.000
SI1 0.0055 (5) 0.0055 (5) 0.0051 (7) 0.0028 (2) 0.000 0.000
O1 0.0086 (12) 0.0130 (10) 0.0163 (12) 0.0043 (6) −0.0051 (12) −0.0026 (6)
O2 0.029 (3) 0.029 (3) 0.005 (3) 0.0143 (13) 0.000 0.000

Geometric parameters (Å, º)

K1—O1i 2.8794 (1) ER1—O1xvi 2.241 (2)

K1—O1ii 2.8794 (1) ER1—O1xvii 2.241 (2)
K1—O1iii 2.8794 (1) ER1—O1iv 2.241 (2)
K1—O1iv 2.8794 (1) ER1—O1vii 2.241 (2)
K1—O1v 2.8794 (1) ER1—O1x 2.241 (2)
K1—O1 2.8794 (1) ER1—O1 2.241 (2)
K1—O1vi 3.041 (3) ER1—K2xvi 3.4990 (1)
K1—O1vii 3.041 (3) ER1—K1xvi 3.5578 (6)
K1—O1viii 3.041 (3) ER1—K1xiii 3.5578 (6)
K1—SI1viii 3.135 (2) ER1—K1viii 3.5578 (6)
K1—SI1 3.3707 (4) SI1—O1 1.613 (3)
K1—SI1ii 3.3708 (4) SI1—O1xviii 1.613 (3)
K2—O1 2.797 (3) SI1—O1v 1.613 (3)
K2—O1ix 2.797 (3) SI1—O2 1.6418 (17)
K2—O1x 2.797 (3) SI1—K1viii 3.135 (2)
K2—O1xi 2.797 (3) SI1—K1xix 3.3708 (4)
K2—O1iv 2.797 (3) SI1—K1xx 3.3708 (4)
K2—O1xii 2.797 (3) SI1—K2xx 3.7042 (7)
K2—O2xiii 3.3205 (1) SI1—K2xxi 3.7042 (7)
K2—O2 3.3205 (1) O1—K1xix 2.8795 (1)

Acta Cryst. (2019). C75, 1417-1423 sup-2

electronic reprint
 supporting information
K2—O2xiv 3.3205 (1) O1—K1viii 3.041 (3)
K2—ER1 3.4990 (1) O2—SI1ix 1.6418 (17)
K2—ER1xv 3.4990 (1) O2—K2xx 3.3205 (1)
K2—SI1xiii 3.7042 (7) O2—K2xxi 3.3205 (1)

O1i—K1—O1ii 65.11 (10) O1xvii—ER1—O1x 92.51 (10)

O1i—K1—O1iii 119.938 (6) O1iv—ER1—O1x 87.49 (10)
O1ii—K1—O1iii 54.85 (10) O1vii—ER1—O1x 180.00 (14)
O1i—K1—O1iv 54.85 (10) O1xvi—ER1—O1 180.0
O1ii—K1—O1iv 119.938 (6) O1xvii—ER1—O1 92.51 (10)
O1iii—K1—O1iv 174.13 (10) O1iv—ER1—O1 87.49 (10)
O1i—K1—O1v 174.13 (10) O1vii—ER1—O1 92.51 (10)
O1ii—K1—O1v 119.938 (6) O1x—ER1—O1 87.49 (10)
O1iii—K1—O1v 65.11 (10) O1xvi—ER1—K2 127.02 (7)
O1iv—K1—O1v 119.938 (6) O1xvii—ER1—K2 127.02 (7)
O1i—K1—O1 119.938 (6) O1iv—ER1—K2 52.98 (7)
O1ii—K1—O1 174.13 (10) O1vii—ER1—K2 127.02 (7)
O1iii—K1—O1 119.939 (6) O1x—ER1—K2 52.98 (7)
O1iv—K1—O1 65.11 (10) O1—ER1—K2 52.98 (7)
O1v—K1—O1 54.85 (10) O1xvi—ER1—K2xvi 52.98 (7)
O1i—K1—O1vi 66.25 (8) O1xvii—ER1—K2xvi 52.98 (7)
O1ii—K1—O1vi 66.25 (8) O1iv—ER1—K2xvi 127.02 (7)
O1iii—K1—O1vi 89.94 (6) O1vii—ER1—K2xvi 52.98 (7)
O1iv—K1—O1vi 89.94 (6) O1x—ER1—K2xvi 127.02 (7)
O1v—K1—O1vi 117.93 (6) O1—ER1—K2xvi 127.02 (7)
O1—K1—O1vi 117.93 (6) K2—ER1—K2xvi 180.0
O1i—K1—O1vii 89.94 (6) O1xvi—ER1—K1xvi 53.928 (12)
O1ii—K1—O1vii 117.93 (6) O1xvii—ER1—K1xvi 53.929 (12)
O1iii—K1—O1vii 117.93 (6) O1iv—ER1—K1xvi 126.071 (12)
O1iv—K1—O1vii 66.25 (8) O1vii—ER1—K1xvi 121.93 (7)
O1v—K1—O1vii 89.94 (6) O1x—ER1—K1xvi 58.07 (7)
O1—K1—O1vii 66.25 (8) O1—ER1—K1xvi 126.071 (12)
O1vi—K1—O1vii 51.72 (8) K2—ER1—K1xvi 111.04 (2)
O1i—K1—O1viii 117.93 (6) K2xvi—ER1—K1xvi 68.96 (2)
O1ii—K1—O1viii 89.94 (6) O1xvi—ER1—K1xiii 58.07 (7)
O1iii—K1—O1viii 66.25 (8) O1xvii—ER1—K1xiii 126.071 (12)
O1iv—K1—O1viii 117.93 (6) O1iv—ER1—K1xiii 53.929 (12)
O1v—K1—O1viii 66.25 (8) O1vii—ER1—K1xiii 126.071 (12)
O1—K1—O1viii 89.94 (6) O1x—ER1—K1xiii 53.929 (12)
O1vi—K1—O1viii 51.72 (8) O1—ER1—K1xiii 121.93 (7)
O1vii—K1—O1viii 51.72 (8) K2—ER1—K1xiii 68.96 (2)
O1i—K1—SI1viii 91.43 (6) K2xvi—ER1—K1xiii 111.04 (2)
O1ii—K1—SI1viii 91.43 (6) K1xvi—ER1—K1xiii 72.15 (2)
O1iii—K1—SI1viii 91.43 (6) O1xvi—ER1—K1viii 121.93 (7)
O1iv—K1—SI1viii 91.43 (6) O1xvii—ER1—K1viii 53.929 (12)
O1v—K1—SI1viii 91.43 (6) O1iv—ER1—K1viii 126.071 (12)
O1—K1—SI1viii 91.43 (6) O1vii—ER1—K1viii 53.929 (12)
O1vi—K1—SI1viii 30.24 (5) O1x—ER1—K1viii 126.071 (12)

Acta Cryst. (2019). C75, 1417-1423 sup-3

electronic reprint
 supporting information
O1vii—K1—SI1viii 30.24 (5) O1—ER1—K1viii 58.07 (7)
O1viii—K1—SI1viii 30.24 (5) K2—ER1—K1viii 111.04 (2)
O1i—K1—SI1 145.66 (5) K2xvi—ER1—K1viii 68.96 (2)
O1ii—K1—SI1 145.66 (5) K1xvi—ER1—K1viii 107.85 (2)
O1iii—K1—SI1 92.28 (5) K1xiii—ER1—K1viii 180.00 (5)
O1iv—K1—SI1 92.28 (5) O1xvi—ER1—K1 126.071 (12)
O1v—K1—SI1 28.56 (5) O1xvii—ER1—K1 126.071 (12)
O1—K1—SI1 28.56 (5) O1iv—ER1—K1 53.929 (12)
O1vi—K1—SI1 130.14 (7) O1vii—ER1—K1 58.07 (7)
O1vii—K1—SI1 84.29 (4) O1x—ER1—K1 121.93 (7)
O1viii—K1—SI1 84.29 (4) O1—ER1—K1 53.929 (12)
SI1viii—K1—SI1 99.90 (4) K2—ER1—K1 68.96 (2)
O1i—K1—SI1ii 92.28 (5) K2xvi—ER1—K1 111.04 (2)
O1ii—K1—SI1ii 28.56 (5) K1xvi—ER1—K1 180.0
O1iii—K1—SI1ii 28.56 (5) K1xiii—ER1—K1 107.85 (3)
O1iv—K1—SI1ii 145.66 (5) K1viii—ER1—K1 72.15 (3)
O1v—K1—SI1ii 92.28 (5) O1—SI1—O1xviii 110.57 (11)
O1—K1—SI1ii 145.66 (5) O1—SI1—O1v 110.57 (11)
O1vi—K1—SI1ii 84.29 (4) O1xviii—SI1—O1v 110.57 (11)
O1vii—K1—SI1ii 130.14 (7) O1—SI1—O2 108.35 (11)
O1viii—K1—SI1ii 84.29 (4) O1xviii—SI1—O2 108.35 (11)
SI1viii—K1—SI1ii 99.90 (4) O1v—SI1—O2 108.35 (11)
SI1—K1—SI1ii 117.11 (2) O1—SI1—K1viii 71.65 (11)
O1—K2—O1ix 100.46 (10) O1xviii—SI1—K1viii 71.65 (11)
O1—K2—O1x 67.28 (8) O1v—SI1—K1viii 71.65 (11)
O1ix—K2—O1x 142.69 (4) O2—SI1—K1viii 180.0
O1—K2—O1xi 142.69 (4) O1—SI1—K1 58.557 (11)
O1ix—K2—O1xi 67.28 (8) O1xviii—SI1—K1 151.75 (13)
O1x—K2—O1xi 142.69 (4) O1v—SI1—K1 58.557 (11)
O1—K2—O1iv 67.28 (8) O2—SI1—K1 99.90 (4)
O1ix—K2—O1iv 142.69 (4) K1viii—SI1—K1 80.10 (4)
O1x—K2—O1iv 67.28 (8) O1—SI1—K1xix 58.558 (11)
O1xi—K2—O1iv 100.46 (10) O1xviii—SI1—K1xix 58.557 (11)
O1—K2—O1xii 142.69 (4) O1v—SI1—K1xix 151.75 (13)
O1ix—K2—O1xii 67.28 (8) O2—SI1—K1xix 99.90 (4)
O1x—K2—O1xii 100.46 (10) K1viii—SI1—K1xix 80.10 (4)
O1xi—K2—O1xii 67.28 (8) K1—SI1—K1xix 117.11 (2)
O1iv—K2—O1xii 142.69 (4) O1—SI1—K1xx 151.75 (13)
O1—K2—O2xiii 108.65 (2) O1xviii—SI1—K1xx 58.557 (11)
O1ix—K2—O2xiii 108.65 (2) O1v—SI1—K1xx 58.557 (11)
O1x—K2—O2xiii 50.23 (5) O2—SI1—K1xx 99.90 (4)
O1xi—K2—O2xiii 108.65 (2) K1viii—SI1—K1xx 80.10 (4)
O1iv—K2—O2xiii 108.65 (2) K1—SI1—K1xx 117.11 (2)
O1xii—K2—O2xiii 50.23 (5) K1xix—SI1—K1xx 117.10 (2)
O1—K2—O2 50.23 (5) O1—SI1—K2xx 124.40 (4)
O1ix—K2—O2 50.23 (5) O1xviii—SI1—K2xx 44.66 (10)
O1x—K2—O2 108.65 (2) O1v—SI1—K2xx 124.40 (4)
O1xi—K2—O2 108.65 (2) O2—SI1—K2xx 63.69 (2)

Acta Cryst. (2019). C75, 1417-1423 sup-4

electronic reprint
 supporting information
O1iv—K2—O2 108.65 (2) K1viii—SI1—K2xx 116.31 (2)
O1xii—K2—O2 108.65 (2) K1—SI1—K2xx 163.59 (6)
O2xiii—K2—O2 120.0 K1xix—SI1—K2xx 68.573 (16)
O1—K2—O2xiv 108.65 (2) K1xx—SI1—K2xx 68.573 (16)
O1ix—K2—O2xiv 108.65 (2) O1—SI1—K2xxi 124.40 (4)
O1x—K2—O2xiv 108.65 (2) O1xviii—SI1—K2xxi 124.40 (4)
O1xi—K2—O2xiv 50.23 (5) O1v—SI1—K2xxi 44.66 (10)
O1iv—K2—O2xiv 50.23 (5) O2—SI1—K2xxi 63.69 (2)
O1xii—K2—O2xiv 108.65 (2) K1viii—SI1—K2xxi 116.31 (2)
O2xiii—K2—O2xiv 120.0 K1—SI1—K2xxi 68.574 (16)
O2—K2—O2xiv 120.0 K1xix—SI1—K2xxi 163.59 (6)
O1—K2—ER1 39.77 (5) K1xx—SI1—K2xxi 68.574 (16)
O1ix—K2—ER1 140.23 (5) K2xx—SI1—K2xxi 101.85 (3)
O1x—K2—ER1 39.77 (5) O1—SI1—K2 44.66 (10)
O1xi—K2—ER1 140.23 (5) O1xviii—SI1—K2 124.40 (4)
O1iv—K2—ER1 39.77 (5) O1v—SI1—K2 124.40 (4)
O1xii—K2—ER1 140.23 (5) O2—SI1—K2 63.69 (2)
O2xiii—K2—ER1 90.0 K1viii—SI1—K2 116.31 (2)
O2—K2—ER1 90.0 K1—SI1—K2 68.574 (16)
O2xiv—K2—ER1 90.0 K1xix—SI1—K2 68.574 (16)
O1—K2—ER1xv 140.23 (5) K1xx—SI1—K2 163.59 (6)
O1ix—K2—ER1xv 39.77 (5) K2xx—SI1—K2 101.85 (3)
O1x—K2—ER1xv 140.23 (5) K2xxi—SI1—K2 101.85 (3)
O1xi—K2—ER1xv 39.77 (5) SI1—O1—ER1 161.33 (17)
O1iv—K2—ER1xv 140.23 (5) SI1—O1—K2 111.42 (13)
O1xii—K2—ER1xv 39.77 (5) ER1—O1—K2 87.25 (8)
O2xiii—K2—ER1xv 90.0 SI1—O1—K1 92.88 (5)
O2—K2—ER1xv 90.0 ER1—O1—K1 87.09 (5)
O2xiv—K2—ER1xv 90.0 K2—O1—K1 89.46 (6)
ER1—K2—ER1xv 180.0 SI1—O1—K1xix 92.88 (5)
O1—K2—SI1xiii 86.91 (4) ER1—O1—K1xix 87.09 (5)
O1ix—K2—SI1xiii 128.858 (17) K2—O1—K1xix 89.46 (6)
O1x—K2—SI1xiii 23.92 (6) K1—O1—K1xix 174.13 (10)
O1xi—K2—SI1xiii 128.857 (17) SI1—O1—K1viii 78.11 (12)
O1iv—K2—SI1xiii 86.91 (4) ER1—O1—K1viii 83.22 (7)
O1xii—K2—SI1xiii 76.54 (6) K2—O1—K1viii 170.47 (10)
O2xiii—K2—SI1xiii 26.31 (2) K1—O1—K1viii 90.06 (6)
O2—K2—SI1xiii 116.629 (6) K1xix—O1—K1viii 90.06 (6)
O2xiv—K2—SI1xiii 116.628 (6) SI1ix—O2—SI1 180.0
ER1—K2—SI1xiii 63.69 (2) SI1ix—O2—K2xx 90.0
ER1xv—K2—SI1xiii 116.31 (2) SI1—O2—K2xx 90.0
O1xvi—ER1—O1xvii 87.49 (10) SI1ix—O2—K2xxi 90.0
O1xvi—ER1—O1iv 92.51 (10) SI1—O2—K2xxi 90.0
O1xvii—ER1—O1iv 180.00 (10) K2xx—O2—K2xxi 120.0
O1xvi—ER1—O1vii 87.49 (10) SI1ix—O2—K2 90.0
O1xvii—ER1—O1vii 87.49 (10) SI1—O2—K2 90.0

Acta Cryst. (2019). C75, 1417-1423 sup-5

electronic reprint
 supporting information
O1iv—ER1—O1vii 92.51 (10) K2xx—O2—K2 120.0
O1xvi—ER1—O1x 92.51 (10) K2xxi—O2—K2 120.0
Symmetry codes: (i) −x+y, −x+1, z; (ii) x, y+1, z; (iii) −y+1, x−y+1, z; (iv) −y, x−y, z; (v) −x+y+1, −x+1, z; (vi) y, −x+y+1, −z; (vii) x−y, x, −z; (viii) −x+1,
−y+1, −z; (ix) x, y, −z+1/2; (x) −x+y, −x, z; (xi) −y, x−y, −z+1/2; (xii) −x+y, −x, −z+1/2; (xiii) x−1, y−1, z; (xiv) x−1, y, z; (xv) −x, −y, z+1/2; (xvi) −x, −y,
−z; (xvii) y, −x+y, −z; (xviii) −y+1, x−y, z; (xix) x, y−1, z; (xx) x+1, y, z; (xxi) x+1, y+1, z.

Tripotassium erbium disilicate (shelx_1)

Crystal data
K3ErSi2O7 Dx = 3.771 Mg m−3
Mr = 452.74 Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mcm Cell parameters from 2298 reflections
a = 9.8338 (2) Å θ = 3.7–28.9°
c = 14.2843 (4) Å µ = 12.39 mm−1
V = 1196.28 (6) Å3 T = 298 K
Z=6 Prismatic, pink
F(000) = 1254 0.16 × 0.11 × 0.08 mm

Data collection
Agilent Xcalibur Sapphire3 Gemini 578 independent reflections
diffractometer 512 reflections with I > 2σ(I)
ω scans Rint = 0.023
Absorption correction: analytical θmax = 29.0°, θmin = 3.7°
(Clark & Reid, 1995) h = −13→11
k = −13→12
5150 measured reflections l = −18→19

Refinement
Refinement on F2 w = 1/[σ2(Fo2) + (0.0156P)2 + 2.7206P]
Least-squares matrix: full where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.021 (Δ/σ)max < 0.001
wR(F2) = 0.046 Δρmax = 0.59 e Å−3
S = 1.23 Δρmin = −0.82 e Å−3
578 reflections Extinction correction: SHELXL2015
41 parameters (Sheldrick, 2015),
0 restraints Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.00223 (11)

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
K1 0.33132 (11) 0.0000 0.09214 (9) 0.0170 (2)
K2 0.3333 0.6667 0.2500 0.0148 (4)
K3 0.0000 0.0000 0.0000 0.0178 (6)
ER1 0.3333 0.6667 0.0000 0.00505 (13)
ER2 0.0000 0.0000 0.2500 0.00584 (15)
SI1 0.65794 (12) 0.0000 0.14248 (9) 0.0050 (2)

Acta Cryst. (2019). C75, 1417-1423 sup-6

electronic reprint
 supporting information
O1 0.6785 (3) 0.5233 (3) 0.90838 (16) 0.0115 (5)
O2 0.8232 (3) 0.0000 0.1469 (2) 0.0103 (7)
O3 0.5932 (4) 0.0000 0.2500 0.0117 (10)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

K1 0.0147 (4) 0.0102 (5) 0.0245 (6) 0.0051 (2) 0.0045 (4) 0.000
K2 0.0169 (6) 0.0169 (6) 0.0107 (10) 0.0084 (3) 0.000 0.000
K3 0.0195 (9) 0.0195 (9) 0.0145 (15) 0.0097 (4) 0.000 0.000
ER1 0.00503 (14) 0.00503 (14) 0.0051 (2) 0.00252 (7) 0.000 0.000
ER2 0.00548 (17) 0.00548 (17) 0.0066 (3) 0.00274 (9) 0.000 0.000
SI1 0.0047 (4) 0.0054 (6) 0.0053 (5) 0.0027 (3) −0.0001 (5) 0.000
O1 0.0133 (11) 0.0092 (11) 0.0130 (12) 0.0064 (9) −0.0001 (10) 0.0024 (10)
O2 0.0079 (11) 0.0136 (16) 0.0113 (17) 0.0068 (8) −0.0003 (13) 0.000
O3 0.0107 (16) 0.020 (3) 0.007 (2) 0.0102 (13) 0.000 0.000

Geometric parameters (Å, º)

K1—O1i 2.742 (2) ER1—K1xx 3.5416 (7)

K1—O1ii 2.742 (2) ER1—K1xvii 3.5416 (7)
K1—O2iii 2.9302 (13) ER1—K1xvi 3.5416 (7)
K1—O2iv 2.9302 (13) ER1—K1xxix 3.5416 (7)
K1—O1v 2.962 (2) ER1—K1xxiv 3.5416 (7)
K1—O1vi 2.962 (2) ER1—K1iv 3.5416 (7)
K1—O1vii 3.014 (2) ER2—O2xxx 2.279 (3)
K1—O1viii 3.014 (2) ER2—O2iii 2.279 (3)
K1—SI1 3.2915 (15) ER2—O2xxi 2.279 (3)
K1—SI1ix 3.3529 (15) ER2—O2iv 2.279 (3)
K1—SI1iii 3.3893 (9) ER2—O2xxxi 2.279 (3)
K1—SI1iv 3.3893 (9) ER2—O2xxxii 2.279 (3)
K2—O1x 2.899 (2) ER2—K3xxxiii 3.5711 (1)
K2—O1xi 2.899 (2) ER2—K1xxv 3.9623 (11)
K2—O1xii 2.899 (2) ER2—K1xxxiv 3.9623 (11)
K2—O1xiii 2.899 (2) ER2—K1xviii 3.9623 (11)
K2—O1xiv 2.899 (2) ER2—K1xxxv 3.9623 (11)
K2—O1xv 2.899 (2) SI1—O1vi 1.609 (2)
K2—O3xvi 2.9830 (14) SI1—O1v 1.609 (2)
K2—O3xvii 2.9830 (14) SI1—O2 1.626 (3)
K2—O3iv 2.9830 (14) SI1—O3 1.663 (2)
K2—ER1xviii 3.5711 (1) SI1—K1ix 3.3530 (15)
K2—ER1 3.5711 (1) SI1—K1xxxvi 3.3893 (9)
K2—SI1xvi 3.5819 (7) SI1—K1xxxvii 3.3893 (9)
K3—O2xix 2.726 (3) SI1—K2xxxviii 3.5819 (7)
K3—O2iv 2.726 (3) SI1—K2xxxix 3.5819 (7)
K3—O2xx 2.726 (3) SI1—K3xl 3.9315 (12)
K3—O2iii 2.726 (3) O1—SI1x 1.609 (2)
K3—O2ix 2.726 (3) O1—ER1xiv 2.236 (2)

Acta Cryst. (2019). C75, 1417-1423 sup-7

electronic reprint
 supporting information
K3—O2xxi 2.726 (3) O1—K1xli 2.742 (2)
K3—K1xxii 3.5139 (11) O1—K2xiv 2.899 (2)
K3—K1xvi 3.5139 (11) O1—K1x 2.962 (2)
K3—K1xxiii 3.5139 (11) O1—K1xlii 3.014 (2)
K3—K1xxiv 3.5139 (11) O2—ER2xl 2.279 (3)
K3—K1xxv 3.5139 (11) O2—K3xl 2.726 (3)
ER1—O1xxvi 2.236 (2) O2—K1xxxvii 2.9302 (13)
ER1—O1x 2.236 (2) O2—K1xxxvi 2.9302 (13)
ER1—O1xxvii 2.236 (2) O3—SI1xviii 1.663 (2)
ER1—O1xiii 2.236 (2) O3—K2xxxviii 2.9830 (14)
ER1—O1xxviii 2.236 (2) O3—K2xxxix 2.9830 (14)
ER1—O1xiv 2.236 (2) O3—K1xviii 3.423 (4)

O1i—K1—O1ii 173.67 (10) O1xxvi—ER1—K1xx 50.74 (6)

O1i—K1—O2iii 56.12 (8) O1x—ER1—K1xx 57.71 (6)
O1ii—K1—O2iii 117.97 (8) O1xxvii—ER1—K1xx 56.39 (6)
O1i—K1—O2iv 117.97 (8) O1xiii—ER1—K1xx 128.78 (6)
O1ii—K1—O2iv 56.12 (8) O1xxviii—ER1—K1xx 122.26 (6)
O2iii—K1—O2iv 61.86 (12) O1xiv—ER1—K1xx 124.09 (6)
O1i—K1—O1v 119.66 (3) O1xxvi—ER1—K1xvii 57.71 (6)
O1ii—K1—O1v 66.66 (9) O1x—ER1—K1xvii 50.74 (6)
O2iii—K1—O1v 163.64 (9) O1xxvii—ER1—K1xvii 128.78 (6)
O2iv—K1—O1v 120.06 (7) O1xiii—ER1—K1xvii 56.39 (6)
O1i—K1—O1vi 66.66 (9) O1xxviii—ER1—K1xvii 124.09 (6)
O1ii—K1—O1vi 119.66 (3) O1xiv—ER1—K1xvii 122.26 (6)
O2iii—K1—O1vi 120.06 (7) K1xx—ER1—K1xvii 72.51 (4)
O2iv—K1—O1vi 163.64 (9) O1xxvi—ER1—K1xvi 124.09 (6)
O1v—K1—O1vi 53.00 (8) O1x—ER1—K1xvi 56.39 (6)
O1i—K1—O1vii 64.65 (8) O1xxvii—ER1—K1xvi 57.71 (6)
O1ii—K1—O1vii 116.60 (6) O1xiii—ER1—K1xvi 122.26 (6)
O2iii—K1—O1vii 100.81 (8) O1xxviii—ER1—K1xvi 128.78 (6)
O2iv—K1—O1vii 129.67 (9) O1xiv—ER1—K1xvi 50.74 (6)
O1v—K1—O1vii 89.75 (7) K1xx—ER1—K1xvi 73.44 (3)
O1vi—K1—O1vii 66.68 (8) K1xvii—ER1—K1xvi 107.03 (2)
O1i—K1—O1viii 116.60 (6) O1xxvi—ER1—K1xxix 56.39 (6)
O1ii—K1—O1viii 64.65 (8) O1x—ER1—K1xxix 124.09 (6)
O2iii—K1—O1viii 129.67 (9) O1xxvii—ER1—K1xxix 122.26 (6)
O2iv—K1—O1viii 100.81 (8) O1xiii—ER1—K1xxix 57.71 (6)
O1v—K1—O1viii 66.68 (8) O1xxviii—ER1—K1xxix 50.74 (6)
O1vi—K1—O1viii 89.75 (7) O1xiv—ER1—K1xxix 128.78 (6)
O1vii—K1—O1viii 52.03 (9) K1xx—ER1—K1xxix 107.03 (2)
O1i—K1—SI1 93.12 (5) K1xvii—ER1—K1xxix 73.44 (3)
O1ii—K1—SI1 93.12 (5) K1xvi—ER1—K1xxix 179.44 (3)
O2iii—K1—SI1 137.49 (7) O1xxvi—ER1—K1xxiv 122.26 (6)
O2iv—K1—SI1 137.49 (7) O1x—ER1—K1xxiv 128.78 (6)
O1v—K1—SI1 29.22 (4) O1xxvii—ER1—K1xxiv 50.74 (6)
O1vi—K1—SI1 29.22 (4) O1xiii—ER1—K1xxiv 124.09 (6)
O1vii—K1—SI1 88.54 (6) O1xxviii—ER1—K1xxiv 56.39 (6)

Acta Cryst. (2019). C75, 1417-1423 sup-8

electronic reprint
 supporting information
O1viii—K1—SI1 88.54 (6) O1xiv—ER1—K1xxiv 57.71 (6)
O1i—K1—SI1ix 89.95 (6) K1xx—ER1—K1xxiv 107.03 (2)
O1ii—K1—SI1ix 89.95 (6) K1xvii—ER1—K1xxiv 179.44 (3)
O2iii—K1—SI1ix 107.02 (7) K1xvi—ER1—K1xxiv 72.51 (4)
O2iv—K1—SI1ix 107.02 (7) K1xxix—ER1—K1xxiv 107.03 (2)
O1v—K1—SI1ix 88.24 (6) O1xxvi—ER1—K1iv 128.78 (6)
O1vi—K1—SI1ix 88.24 (6) O1x—ER1—K1iv 122.26 (6)
O1vii—K1—SI1ix 28.65 (4) O1xxvii—ER1—K1iv 124.09 (6)
O1viii—K1—SI1ix 28.65 (4) O1xiii—ER1—K1iv 50.74 (6)
SI1—K1—SI1ix 100.81 (4) O1xxviii—ER1—K1iv 57.71 (6)
O1i—K1—SI1iii 27.96 (5) O1xiv—ER1—K1iv 56.39 (6)
O1ii—K1—SI1iii 146.42 (6) K1xx—ER1—K1iv 179.44 (3)
O2iii—K1—SI1iii 28.66 (6) K1xvii—ER1—K1iv 107.03 (2)
O2iv—K1—SI1iii 90.34 (7) K1xvi—ER1—K1iv 107.03 (2)
O1v—K1—SI1iii 143.15 (5) K1xxix—ER1—K1iv 72.51 (4)
O1vi—K1—SI1iii 91.90 (5) K1xxiv—ER1—K1iv 73.44 (3)
O1vii—K1—SI1iii 84.87 (5) O2xxx—ER2—O2iii 135.13 (6)
O1viii—K1—SI1iii 131.65 (6) O2xxx—ER2—O2xxi 135.13 (6)
SI1—K1—SI1iii 114.05 (3) O2iii—ER2—O2xxi 82.75 (12)
SI1ix—K1—SI1iii 103.10 (4) O2xxx—ER2—O2iv 80.51 (16)
O1i—K1—SI1iv 146.42 (6) O2iii—ER2—O2iv 82.75 (12)
O1ii—K1—SI1iv 27.96 (5) O2xxi—ER2—O2iv 82.75 (12)
O2iii—K1—SI1iv 90.34 (7) O2xxx—ER2—O2xxxi 82.75 (12)
O2iv—K1—SI1iv 28.66 (6) O2iii—ER2—O2xxxi 80.51 (16)
O1v—K1—SI1iv 91.90 (5) O2xxi—ER2—O2xxxi 135.13 (6)
O1vi—K1—SI1iv 143.15 (5) O2iv—ER2—O2xxxi 135.13 (6)
O1vii—K1—SI1iv 131.65 (6) O2xxx—ER2—O2xxxii 82.75 (12)
O1viii—K1—SI1iv 84.87 (5) O2iii—ER2—O2xxxii 135.13 (6)
SI1—K1—SI1iv 114.05 (3) O2xxi—ER2—O2xxxii 80.51 (16)
SI1ix—K1—SI1iv 103.10 (4) O2iv—ER2—O2xxxii 135.13 (6)
SI1iii—K1—SI1iv 118.52 (5) O2xxxi—ER2—O2xxxii 82.75 (12)
O1x—K2—O1xi 143.56 (4) O2xxx—ER2—K3 130.25 (8)
O1x—K2—O1xii 102.59 (9) O2iii—ER2—K3 49.75 (8)
O1xi—K2—O1xii 65.58 (7) O2xxi—ER2—K3 49.75 (8)
O1x—K2—O1xiii 65.58 (7) O2iv—ER2—K3 49.75 (8)
O1xi—K2—O1xiii 102.59 (9) O2xxxi—ER2—K3 130.25 (8)
O1xii—K2—O1xiii 143.56 (4) O2xxxii—ER2—K3 130.25 (8)
O1x—K2—O1xiv 65.58 (7) O2xxx—ER2—K3xxxiii 49.75 (8)
O1xi—K2—O1xiv 143.56 (4) O2iii—ER2—K3xxxiii 130.25 (8)
O1xii—K2—O1xiv 143.56 (4) O2xxi—ER2—K3xxxiii 130.25 (8)
O1xiii—K2—O1xiv 65.58 (7) O2iv—ER2—K3xxxiii 130.25 (8)
O1x—K2—O1xv 143.56 (4) O2xxxi—ER2—K3xxxiii 49.75 (8)
O1xi—K2—O1xv 65.58 (7) O2xxxii—ER2—K3xxxiii 49.75 (8)
O1xii—K2—O1xv 65.58 (7) K3—ER2—K3xxxiii 180.0
O1xiii—K2—O1xv 143.56 (4) O2xxx—ER2—K1xxv 174.43 (8)
O1xiv—K2—O1xv 102.59 (9) O2iii—ER2—K1xxv 47.04 (2)
O1x—K2—O3xvi 52.90 (5) O2xxi—ER2—K1xxv 47.04 (2)
O1xi—K2—O3xvi 116.39 (6) O2iv—ER2—K1xxv 105.06 (8)

Acta Cryst. (2019). C75, 1417-1423 sup-9

electronic reprint
 supporting information
O1xii—K2—O3xvi 52.91 (5) O2xxxi—ER2—K1xxv 93.09 (6)
O1xiii—K2—O3xvi 116.39 (6) O2xxxii—ER2—K1xxv 93.09 (6)
O1xiv—K2—O3xvi 99.13 (7) K3—ER2—K1xxv 55.313 (18)
O1xv—K2—O3xvi 99.13 (7) K3xxxiii—ER2—K1xxv 124.687 (18)
O1x—K2—O3xvii 99.13 (7) O2xxx—ER2—K1xxxiv 47.04 (2)
O1xi—K2—O3xvii 52.90 (5) O2iii—ER2—K1xxxiv 174.43 (8)
O1xii—K2—O3xvii 99.13 (7) O2xxi—ER2—K1xxxiv 93.09 (6)
O1xiii—K2—O3xvii 52.91 (5) O2iv—ER2—K1xxxiv 93.09 (6)
O1xiv—K2—O3xvii 116.39 (6) O2xxxi—ER2—K1xxxiv 105.06 (8)
O1xv—K2—O3xvii 116.39 (6) O2xxxii—ER2—K1xxxiv 47.04 (2)
O3xvi—K2—O3xvii 120.0 K3—ER2—K1xxxiv 124.687 (18)
O1x—K2—O3iv 116.39 (6) K3xxxiii—ER2—K1xxxiv 55.313 (18)
O1xi—K2—O3iv 99.13 (7) K1xxv—ER2—K1xxxiv 131.448 (11)
O1xii—K2—O3iv 116.39 (6) O2xxx—ER2—K1xviii 47.04 (2)
O1xiii—K2—O3iv 99.13 (7) O2iii—ER2—K1xviii 93.09 (6)
O1xiv—K2—O3iv 52.90 (5) O2xxi—ER2—K1xviii 174.43 (8)
O1xv—K2—O3iv 52.90 (5) O2iv—ER2—K1xviii 93.09 (6)
O3xvi—K2—O3iv 120.000 (1) O2xxxi—ER2—K1xviii 47.04 (2)
O3xvii—K2—O3iv 120.000 (1) O2xxxii—ER2—K1xviii 105.06 (8)
O1x—K2—ER1xviii 141.30 (4) K3—ER2—K1xviii 124.687 (18)
O1xi—K2—ER1xviii 38.70 (4) K3xxxiii—ER2—K1xviii 55.313 (18)
O1xii—K2—ER1xviii 38.70 (4) K1xxv—ER2—K1xviii 131.448 (11)
O1xiii—K2—ER1xviii 141.30 (4) K1xxxiv—ER2—K1xviii 90.81 (2)
O1xiv—K2—ER1xviii 141.30 (4) O2xxx—ER2—K1xxxv 105.06 (8)
O1xv—K2—ER1xviii 38.70 (4) O2iii—ER2—K1xxxv 93.09 (6)
O3xvi—K2—ER1xviii 90.0 O2xxi—ER2—K1xxxv 93.09 (6)
O3xvii—K2—ER1xviii 90.0 O2iv—ER2—K1xxxv 174.43 (8)
O3iv—K2—ER1xviii 90.0 O2xxxi—ER2—K1xxxv 47.04 (2)
O1x—K2—ER1 38.70 (4) O2xxxii—ER2—K1xxxv 47.04 (2)
O1xi—K2—ER1 141.30 (4) K3—ER2—K1xxxv 124.687 (18)
O1xii—K2—ER1 141.30 (4) K3xxxiii—ER2—K1xxxv 55.313 (18)
O1xiii—K2—ER1 38.70 (4) K1xxv—ER2—K1xxxv 69.37 (4)
O1xiv—K2—ER1 38.70 (4) K1xxxiv—ER2—K1xxxv 90.81 (2)
O1xv—K2—ER1 141.30 (4) K1xviii—ER2—K1xxxv 90.81 (2)
O3xvi—K2—ER1 90.0 O1vi—SI1—O1v 110.45 (17)
O3xvii—K2—ER1 90.0 O1vi—SI1—O2 111.46 (11)
O3iv—K2—ER1 90.0 O1v—SI1—O2 111.46 (11)
ER1xviii—K2—ER1 180.0 O1vi—SI1—O3 106.47 (12)
O1x—K2—SI1xvi 26.13 (5) O1v—SI1—O3 106.47 (12)
O1xi—K2—SI1xvi 130.89 (5) O2—SI1—O3 110.3 (2)
O1xii—K2—SI1xvi 76.79 (5) O1vi—SI1—K1 63.98 (9)
O1xiii—K2—SI1xvi 89.16 (5) O1v—SI1—K1 63.98 (9)
O1xiv—K2—SI1xvi 84.75 (5) O2—SI1—K1 169.62 (14)
O1xv—K2—SI1xvi 125.29 (5) O3—SI1—K1 80.10 (15)
O3xvi—K2—SI1xvi 27.45 (3) O1vi—SI1—K1ix 63.88 (9)
O3xvii—K2—SI1xvi 107.29 (7) O1v—SI1—K1ix 63.88 (9)
O3iv—K2—SI1xvi 126.17 (7) O2—SI1—K1ix 90.43 (13)
ER1xviii—K2—SI1xvi 115.393 (18) O3—SI1—K1ix 159.29 (15)

Acta Cryst. (2019). C75, 1417-1423 sup-10

electronic reprint
 supporting information
ER1—K2—SI1xvi 64.608 (18) K1—SI1—K1ix 79.19 (4)
O2xix—K3—O2iv 180.00 (15) O1vi—SI1—K1xxxvi 140.04 (10)
O2xix—K3—O2xx 67.08 (10) O1v—SI1—K1xxxvi 53.04 (9)
O2iv—K3—O2xx 112.92 (10) O2—SI1—K1xxxvi 59.79 (4)
O2xix—K3—O2iii 112.92 (10) O3—SI1—K1xxxvi 113.08 (7)
O2iv—K3—O2iii 67.08 (10) K1—SI1—K1xxxvi 116.94 (3)
O2xx—K3—O2iii 180.00 (13) K1ix—SI1—K1xxxvi 76.81 (4)
O2xix—K3—O2ix 67.08 (11) O1vi—SI1—K1xxxvii 53.04 (9)
O2iv—K3—O2ix 112.92 (11) O1v—SI1—K1xxxvii 140.04 (10)
O2xx—K3—O2ix 67.08 (11) O2—SI1—K1xxxvii 59.79 (4)
O2iii—K3—O2ix 112.92 (10) O3—SI1—K1xxxvii 113.08 (7)
O2xix—K3—O2xxi 112.92 (11) K1—SI1—K1xxxvii 116.94 (3)
O2iv—K3—O2xxi 67.08 (11) K1ix—SI1—K1xxxvii 76.81 (4)
O2xx—K3—O2xxi 112.92 (10) K1xxxvi—SI1—K1xxxvii 112.71 (5)
O2iii—K3—O2xxi 67.08 (11) O1vi—SI1—K2xxxviii 52.51 (8)
O2ix—K3—O2xxi 180.00 (13) O1v—SI1—K2xxxviii 133.90 (9)
O2xix—K3—K1xxii 54.253 (17) O2—SI1—K2xxxviii 114.61 (7)
O2iv—K3—K1xxii 125.747 (17) O3—SI1—K2xxxviii 55.79 (4)
O2xx—K3—K1xxii 54.253 (17) K1—SI1—K2xxxviii 70.76 (2)
O2iii—K3—K1xxii 125.747 (17) K1ix—SI1—K2xxxviii 116.25 (2)
O2ix—K3—K1xxii 107.65 (7) K1xxxvi—SI1—K2xxxviii 166.57 (5)
O2xxi—K3—K1xxii 72.35 (7) K1xxxvii—SI1—K2xxxviii 69.70 (2)
O2xix—K3—K1xvi 125.747 (17) O1vi—SI1—K2xxxix 133.90 (9)
O2iv—K3—K1xvi 54.253 (17) O1v—SI1—K2xxxix 52.51 (8)
O2xx—K3—K1xvi 72.35 (7) O2—SI1—K2xxxix 114.62 (7)
O2iii—K3—K1xvi 107.65 (7) O3—SI1—K2xxxix 55.79 (4)
O2ix—K3—K1xvi 125.747 (17) K1—SI1—K2xxxix 70.76 (2)
O2xxi—K3—K1xvi 54.253 (17) K1ix—SI1—K2xxxix 116.25 (2)
K1xxii—K3—K1xvi 73.17 (2) K1xxxvi—SI1—K2xxxix 69.70 (2)
O2xix—K3—K1xxiii 54.253 (17) K1xxxvii—SI1—K2xxxix 166.57 (5)
O2iv—K3—K1xxiii 125.747 (17) K2xxxviii—SI1—K2xxxix 104.85 (3)
O2xx—K3—K1xxiii 107.65 (7) O1vi—SI1—K3xl 93.70 (9)
O2iii—K3—K1xxiii 72.35 (7) O1v—SI1—K3xl 93.70 (9)
O2ix—K3—K1xxiii 54.253 (17) O2—SI1—K3xl 33.42 (12)
O2xxi—K3—K1xxiii 125.747 (17) O3—SI1—K3xl 143.69 (15)
K1xxii—K3—K1xxiii 106.83 (2) K1—SI1—K3xl 136.21 (5)
K1xvi—K3—K1xxiii 180.00 (4) K1ix—SI1—K3xl 57.02 (3)
O2xix—K3—K1xxiv 107.65 (7) K1xxxvi—SI1—K3xl 56.79 (3)
O2iv—K3—K1xxiv 72.35 (7) K1xxxvii—SI1—K3xl 56.79 (3)
O2xx—K3—K1xxiv 54.253 (17) K2xxxviii—SI1—K3xl 126.367 (16)
O2iii—K3—K1xxiv 125.747 (17) K2xxxix—SI1—K3xl 126.368 (16)
O2ix—K3—K1xxiv 54.253 (17) SI1x—O1—ER1xiv 167.49 (14)
O2xxi—K3—K1xxiv 125.747 (17) SI1x—O1—K1xli 98.99 (11)
K1xxii—K3—K1xxiv 106.83 (2) ER1xiv—O1—K1xli 90.12 (8)
K1xvi—K3—K1xxiv 73.17 (2) SI1x—O1—K2xiv 101.35 (11)
K1xxiii—K3—K1xxiv 106.83 (2) ER1xiv—O1—K2xiv 87.12 (7)
O2xix—K3—K1xxv 72.35 (7) K1xli—O1—K2xiv 89.90 (7)
O2iv—K3—K1xxv 107.65 (7) SI1x—O1—K1x 86.81 (10)

Acta Cryst. (2019). C75, 1417-1423 sup-11

electronic reprint
 supporting information
O2xx—K3—K1xxv 125.747 (17) ER1xiv—O1—K1x 84.66 (7)
O2iii—K3—K1xxv 54.253 (17) K1xli—O1—K1x 173.33 (9)
O2ix—K3—K1xxv 125.747 (17) K2xiv—O1—K1x 85.71 (6)
O2xxi—K3—K1xxv 54.253 (17) SI1x—O1—K1xlii 87.47 (10)
K1xxii—K3—K1xxv 73.17 (2) ER1xiv—O1—K1xlii 83.45 (7)
K1xvi—K3—K1xxv 106.83 (2) K1xli—O1—K1xlii 93.27 (8)
K1xxiii—K3—K1xxv 73.17 (2) K2xiv—O1—K1xlii 170.05 (9)
K1xxiv—K3—K1xxv 180.00 (3) K1x—O1—K1xlii 90.25 (7)
O2xix—K3—K1 125.747 (17) SI1—O2—ER2xl 142.0 (2)
O2iv—K3—K1 54.253 (17) SI1—O2—K3xl 127.41 (18)
O2xx—K3—K1 125.746 (17) ER2xl—O2—K3xl 90.61 (10)
O2iii—K3—K1 54.254 (17) SI1—O2—K1xxxvii 91.55 (7)
O2ix—K3—K1 72.35 (7) ER2xl—O2—K1xxxvii 98.27 (6)
O2xxi—K3—K1 107.65 (7) K3xl—O2—K1xxxvii 76.73 (7)
K1xxii—K3—K1 180.0 SI1—O2—K1xxxvi 91.55 (7)
K1xvi—K3—K1 106.83 (2) ER2xl—O2—K1xxxvi 98.27 (6)
K1xxiii—K3—K1 73.17 (2) K3xl—O2—K1xxxvi 76.73 (7)
K1xxiv—K3—K1 73.17 (2) K1xxxvii—O2—K1xxxvi 148.71 (13)
K1xxv—K3—K1 106.83 (2) SI1—O3—SI1xviii 135.0 (3)
O1xxvi—ER1—O1x 87.29 (12) SI1—O3—K2xxxviii 96.756 (16)
O1xxvi—ER1—O1xxvii 89.20 (8) SI1xviii—O3—K2xxxviii 96.756 (15)
O1x—ER1—O1xxvii 94.55 (12) SI1—O3—K2xxxix 96.757 (15)
O1xxvi—ER1—O1xiii 94.55 (12) SI1xviii—O3—K2xxxix 96.757 (15)
O1x—ER1—O1xiii 89.20 (8) K2xxxviii—O3—K2xxxix 144.22 (16)
O1xxvii—ER1—O1xiii 174.83 (12) SI1—O3—K1 71.31 (10)
O1xxvi—ER1—O1xxviii 89.20 (8) SI1xviii—O3—K1 153.73 (19)
O1x—ER1—O1xxviii 174.83 (12) K2xxxviii—O3—K1 76.64 (7)
O1xxvii—ER1—O1xxviii 89.20 (8) K2xxxix—O3—K1 76.64 (7)
O1xiii—ER1—O1xxviii 87.29 (12) SI1—O3—K1xviii 153.73 (19)
O1xxvi—ER1—O1xiv 174.83 (12) SI1xviii—O3—K1xviii 71.31 (10)
O1x—ER1—O1xiv 89.20 (8) K2xxxviii—O3—K1xviii 76.64 (7)
O1xxvii—ER1—O1xiv 87.29 (12) K2xxxix—O3—K1xviii 76.64 (7)
O1xiii—ER1—O1xiv 89.20 (8) K1—O3—K1xviii 82.41 (11)
O1xxviii—ER1—O1xiv 94.55 (12)

O1vi—SI1—O2—ER2xl −118.04 (11) K1xxxvi—SI1—O3—SI1xviii −64.81 (7)

O1v—SI1—O2—ER2xl 118.04 (11) K1xxxvii—SI1—O3—SI1xviii 64.81 (7)
O3—SI1—O2—ER2xl 0.000 (1) K2xxxviii—SI1—O3—SI1xviii 106.60 (9)
K1—SI1—O2—ER2xl 180.000 (1) K2xxxix—SI1—O3—SI1xviii −106.60 (9)
K1ix—SI1—O2—ER2xl 180.0 K3xl—SI1—O3—SI1xviii 0.000 (1)
K1xxxvi—SI1—O2—ER2xl 105.57 (7) O1vi—SI1—O3—K2xxxviii 14.46 (16)
K1xxxvii—SI1—O2—ER2xl −105.57 (7) O1v—SI1—O3—K2xxxviii 132.33 (11)
K2xxxviii—SI1—O2—ER2xl −60.66 (6) O2—SI1—O3—K2xxxviii −106.60 (9)
K2xxxix—SI1—O2—ER2xl 60.66 (6) K1—SI1—O3—K2xxxviii 73.40 (9)
K3xl—SI1—O2—ER2xl 180.000 (1) K1ix—SI1—O3—K2xxxviii 73.40 (9)
O1vi—SI1—O2—K3xl 61.96 (11) K1xxxvi—SI1—O3—K2xxxviii −171.41 (5)
O1v—SI1—O2—K3xl −61.96 (11) K1xxxvii—SI1—O3—K2xxxviii −41.79 (15)
O3—SI1—O2—K3xl 180.000 (1) K2xxxix—SI1—O3—K2xxxviii 146.79 (18)

Acta Cryst. (2019). C75, 1417-1423 sup-12

electronic reprint
 supporting information
K1—SI1—O2—K3xl 0.000 (1) K3xl—SI1—O3—K2xxxviii −106.60 (9)
K1ix—SI1—O2—K3xl 0.000 (1) O1vi—SI1—O3—K2xxxix −132.33 (11)
K1xxxvi—SI1—O2—K3xl −74.43 (7) O1v—SI1—O3—K2xxxix −14.46 (16)
K1xxxvii—SI1—O2—K3xl 74.43 (7) O2—SI1—O3—K2xxxix 106.60 (9)
K2xxxviii—SI1—O2—K3xl 119.34 (6) K1—SI1—O3—K2xxxix −73.40 (9)
K2xxxix—SI1—O2—K3xl −119.34 (6) K1ix—SI1—O3—K2xxxix −73.40 (9)
O1vi—SI1—O2—K1xxxvii −12.47 (15) K1xxxvi—SI1—O3—K2xxxix 41.79 (15)
O1v—SI1—O2—K1xxxvii −136.39 (11) K1xxxvii—SI1—O3—K2xxxix 171.42 (5)
O3—SI1—O2—K1xxxvii 105.57 (7) K2xxxviii—SI1—O3—K2xxxix −146.79 (18)
K1—SI1—O2—K1xxxvii −74.43 (7) K3xl—SI1—O3—K2xxxix 106.60 (9)
K1ix—SI1—O2—K1xxxvii −74.43 (7) O1vi—SI1—O3—K1 −58.93 (10)
K1xxxvi—SI1—O2—K1xxxvii −148.86 (14) O1v—SI1—O3—K1 58.93 (10)
K2xxxviii—SI1—O2—K1xxxvii 44.91 (12) O2—SI1—O3—K1 180.000 (1)
K2xxxix—SI1—O2—K1xxxvii 166.23 (5) K1ix—SI1—O3—K1 0.000 (1)
K3xl—SI1—O2—K1xxxvii −74.43 (7) K1xxxvi—SI1—O3—K1 115.19 (7)
O1vi—SI1—O2—K1xxxvi 136.39 (11) K1xxxvii—SI1—O3—K1 −115.19 (7)
O1v—SI1—O2—K1xxxvi 12.47 (15) K2xxxviii—SI1—O3—K1 −73.40 (9)
O3—SI1—O2—K1xxxvi −105.57 (7) K2xxxix—SI1—O3—K1 73.40 (9)
K1—SI1—O2—K1xxxvi 74.43 (7) K3xl—SI1—O3—K1 180.000 (1)
K1ix—SI1—O2—K1xxxvi 74.43 (7) O1vi—SI1—O3—K1xviii −58.93 (10)
K1xxxvii—SI1—O2—K1xxxvi 148.86 (14) O1v—SI1—O3—K1xviii 58.93 (10)
K2xxxviii—SI1—O2—K1xxxvi −166.23 (5) O2—SI1—O3—K1xviii 180.000 (1)
K2xxxix—SI1—O2—K1xxxvi −44.91 (12) K1—SI1—O3—K1xviii 0.000 (1)
K3xl—SI1—O2—K1xxxvi 74.43 (7) K1ix—SI1—O3—K1xviii 0.000 (1)
O1vi—SI1—O3—SI1xviii 121.07 (10) K1xxxvi—SI1—O3—K1xviii 115.19 (7)
O1v—SI1—O3—SI1xviii −121.07 (10) K1xxxvii—SI1—O3—K1xviii −115.19 (7)
O2—SI1—O3—SI1xviii 0.000 (1) K2xxxviii—SI1—O3—K1xviii −73.40 (9)
K1—SI1—O3—SI1xviii 180.000 (1) K2xxxix—SI1—O3—K1xviii 73.40 (9)
K1ix—SI1—O3—SI1xviii 180.000 (1) K3xl—SI1—O3—K1xviii 180.000 (1)

Symmetry codes: (i) x−y, x−1, −z+1; (ii) −y+1, −x+1, −z+1; (iii) −y, x−y−1, z; (iv) −x+y+1, −x+1, z; (v) x, x−y, −z+1; (vi) y, −x+y, −z+1; (vii) −x+1, −x+y,
z−1; (viii) −y+1, x−y, z−1; (ix) −x+1, −y, −z; (x) x−y, x, −z+1; (xi) y, −x+y+1, z−1/2; (xii) x−y, x, z−1/2; (xiii) y, −x+y+1, −z+1; (xiv) −x+1, −y+1, −z+1;
(xv) −x+1, −y+1, z−1/2; (xvi) −y, x−y, z; (xvii) x, y+1, z; (xviii) x, y, −z+1/2; (xix) x−y−1, x−1, −z; (xx) y, −x+y+1, −z; (xxi) x−1, y, z; (xxii) −x, −y, −z;
(xxiii) y, −x+y, −z; (xxiv) x−y, x, −z; (xxv) −x+y, −x, z; (xxvi) −x+1, −x+y+1, z−1; (xxvii) x−y, −y+1, z−1; (xxviii) y, x, z−1; (xxix) −x+1, −y+1, −z; (xxx)
−x+y+1, −x+1, −z+1/2; (xxxi) −y, x−y−1, −z+1/2; (xxxii) x−1, y, −z+1/2; (xxxiii) −x, −y, z+1/2; (xxxiv) −y, x−y, −z+1/2; (xxxv) −x+y, −x, −z+1/2; (xxxvi)
−y+1, x−y, z; (xxxvii) −x+y+1, −x, z; (xxxviii) x, y−1, z; (xxxix) x−y+1, −y+1, −z+1/2; (xl) x+1, y, z; (xli) y+1, −x+y+1, −z+1; (xlii) −x+y+1, −x+1, z+1.

Acta Cryst. (2019). C75, 1417-1423 sup-13

electronic reprint