Journal of Solid State Chemistry 243 (2016) 215–220

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Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Porous layered and open-framework mixed-valence copper tellurites

Mishel R. Markovski, Oleg I. Siidra n, Roman A. Kayukov, Evgeni W. Nazarchuk
Department of Crystallography, St. Petersburg State University, Universitetskaya Nab 7/9, 199034 St.Petersburg, Russia

art ic l e i nf o a b s t r a c t

Article history: |Cu þ Cl3|[Cu22 þ (TeO3)] (1), |Сu1.7

þ
Cl3.8|[Cu24 þ O(TeO3)2] (2) and Tl2þ [Cu22 þ Te6 þ Te46 þ O18] (3) were obtained by
Received 18 July 2016 CVT and hydrothermal methods in CuCl-CuCl2-TeO2 and Tl2CO3-CuO-TeO2 systems. 1 demonstrates
Received in revised form layered topology with pores (1  0.65 nm), whereas 2 has open-framework structural architecture with
17 August 2016
two-dimensional system of channels (1.16  0.74 nm). Channels in open-framework of 3 are occupied by
Accepted 19 August 2016
Available online 24 August 2016
Tl þ cations. ‘Host-guest’ structural organization of 1 and 2 with host Cu2 þ -tellurite units of different
dimensionality formed by oxocentered OCu4 tetrahedra and OCu2Te triangles and guest Cu þ -chloride
Keywords: species is the result of formation from gases in CVT reactions. Oxocentered units determine basic
Copper topologies of the structures of 1 and 2 and influence their stability and properties. [Te6 þ Te46 þ O18]6 
Tellurium
polytellurite-tellurate framework in 3 can be represented as consisting of Kagome-like layers.
Porous compounds
& 2016 Elsevier Inc. All rights reserved.
Open-frameworks
Chemical vapor transport reactions
Host-guest structures
Single crystal x-ray diffraction
Kagome layers
Lone-pair

1. Introduction additional metals) mixed-valence (Cu þ /Cu2 þ ) oxoselenite [16]

Porous inorganic oxide based crystalline materials are well
known for a variety of different applications [1]. Mixed-valence
compounds have very broad applications in the fields from biology
to high-temperature superconducting materials [2]. Transition
metal oxyhalide compounds containing lone-pair cations M-L-O-X,
and transition metal oxides with mixed lone-pair cations M-L-L-O
(M ¼transition metal cation, L¼ lone pair cations, X¼ Cl  , Br  )
usually crystallize in low-dimensional structural architectures due
to the ‘chemical scissors’ [3] role of stereochemically active lone
electron pairs. Such compounds are manifested with the abun-
dance of interesting physical properties such as magnetic frus-
tration [4], catalytic properties, superconductivity etc [5]. d10-
d9electronic configurations transformation of Cu þ to Cu2 þ is
usually characterized by the appearance of uncommon magnetic
properties [6]. sp3d2 to sp3d hybridization of Te4 þ to Te6 þ is traced
with coordination polyhedron transformation from see-saw to
regular octahedral coordination, which provokes a strong aug-
mentation of non-linear optical properties [7]. Nine mixed-valence
Cu þ /Cu2 þ oxychlorides [8–14] and one mixed-valence Te4 þ /Te6 þ
copper oxide [15] are known to date. Ba2Cu4(Te4O11)Cl4 [11] and
Cu3Yb3(TeO3)4Cl6 [14] are the only known mixed-valence Cu þ /
Cu2 þ tellurites. Published to date one ‘pure’ (i.e. without
suggests that similar Te/Se analogs may exist. Tellurites in the
Tl  Cu-Te-O system are unknown but three tellurates were re-
ported: Tl4CuTeO6 and Tl6CuTe2O10 [17], NaTl3Cu4(TeO6)2 [18]. All
of them are represented by low-dimensional structural archi-
tectures, which is unusual for structures with octahedrally co-
ordinated Te6 þ . Recently we have successfully employed CVT
(chemical vapor transport) reactions for obtaining of a number of
copper selenite compounds [19]. Thus it was decided to apply si-
milar method of synthesis for tellurite containing systems with
copper.
Herein we report on the studies of the CuCl-CuCl2-TeO2 and
Tl2CO3-CuO-TeO2 systems, where novel mixed-valence Cu þ /Cu2 þ
and Te4 þ /Te6 þ porous tellurite based compounds were obtained
by CVT (1, 2) and hydrothermal methods (3). |Cu þ Cl3|[Cu22 þ (TeO3)]
(1) demonstrates layered topology with pores (1  0.65 nm),
whereas |Сu1.7 þ
Cl3.8|[Cu24 þ O(TeO3)2] (2) has open-framework
structural architecture with two-dimensional system of channels.
Channels in open-framework of Tl2þ [Cu22 þ Te6 þ Te46 þ O18] (3) are
occupied by Tl þ cations.
2. Experimental section
2.1. Syntheses

n
Corresponding author. All the reagents were analytically pure obtained from Sigma-
E-mail address: o.siidra@spbu.ru (O.I. Siidra). Aldrich and used without further purification. The synthesis of 1

http://dx.doi.org/10.1016/j.jssc.2016.08.028
0022-4596/& 2016 Elsevier Inc. All rights reserved.
216 M.R. Markovski et al. / Journal of Solid State Chemistry 243 (2016) 215–220

Fig. 1. General projection of the crystal structure of 1 along the a axis (Cu(3) sites belong to Cu þ cations) (a). Guest Cu2þ Cl6 dimers are located between porous host cationic
[Cu22 þ (TeO3)]2 þ layers. Ball-and-stick (b) and schematical (d) representation showing arrangement of pores in [Cu22 þ (TeO3)] 2 þ layer along the c axis. Detailed structure of
[Cu22 þ (TeO3)] 2 þ layer, where each of O atoms is central in OCu22 þ Te triangles (c). Brown crystals of 1 under optical microscope (e). (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

and 2 were made by CVT reactions in sealed evacuated silica tubes.
TeO2:CuCl:CuCl2 were mixed in a mortar in the molar ratios
3:0.5:0.5, 2:0.5:0.5, 1:0.5:0.5, 1:1:1, 1:1.5:1.5, put into silica tubes
(  13 cm long) and further evacuated to 10–2 mbar, sealed and
placed horizontally into a furnace, heated at 450 °C for 50 h and
slowly cooled to room temperature with a cooling rate of 3 °C/h.
The temperature gradient between the source (hot) and deposi-
tion (cold) zones of the tube in the furnace was 50 °C. Brown
crystals of 1 (Fig. 1e) were observed in cold zone of the tube with
molar ratio TeO2:CuCl:CuCl2 of 1:1.5:1.5. Yellow-brown prismatic
crystals of 2 (Fig. 2f) were grown also in cold zone of the tube with
molar ratio TeO2:CuCl:CuCl2 of 2:0.5:0.5. Both novel phases were
in association with already known Cu3TeO6 and CuTe2O5, except
for the tube with TeO2:CuCl:CuCl2 of 3:0.5:0.5 where light-green
crystals of Cu2Te2O5Cl2 formed in cold zone. The same CVT method
with identical conditions was used to explore the quaternary
system of TlCl:TeO2:CuCl:CuCl2 with molar ratios of 3:1:0.5:0.5,
2:1:0.5:0.5, 1:1:0.5:0.5, 1:1:1:1, 1:1:1.5:1.5 and no novel phases
were obtained. Dark-brown tints of crystals of 1 and 2 suggested
presence of Cu þ in composition. Aquamarine blue single crystals
of 3 (Fig. 3g) were synthesized using hydrothermal technique.
Tl2(CO)3, CuO and TeO2 were mixed in a mortar in a molar ratio
1.5:3:1 respectively, and combined with 8 mL of KOH (1 M). The
solution was placed in a 23 mL Teflon-lined autoclave. The closed
autoclave was heated at 220 °C during 48 h and then cooled to
room temperature with a cooling rate of 7 °C/h. Single crystals of 1
in association with already known Tl2Te2O5 were filtered and
washed with hexane. The electron-microprobe analyses (HITA-
СHI-TM 3000) were performed for 1, 2 and 3. Qualitative electron
microprobe analysis (Hitachi TM-3000) revealed no other ele-
ments, except Cu, Cl and Te with the atomic number greater than
11 (Na) in 1 and 2 and Tl, Cu and Te in 3.
2.2. X-ray crystallography
Single crystals of 1, 2 and 3 were mounted on a thin glass fibers
for the X-ray diffraction analysis using Bruker APEX II DUO X-ray
diffractometer with a micro-focus X-ray tube operated with MoKα
radiation at 50 kV and 40 mA. The data were integrated and cor-
rected for absorption using a multi scan type model using the
Bruker programs APEX and SADABS. More than a hemisphere of
X-ray diffraction data were collected. Crystallographic information
is summarized in Table 1 and selected interatomic distances in
Table 2.
For powder x-ray diffraction of 1, 2 and 3 ten crystals of each
phase were preliminary checked by single-crystal x-ray and later
crushed and glued with epoxy into balls. X-ray powder diffraction
data were collected with a Rigaku R-AXIS Rapid II single-crystal
diffractometer equipped with cylindrical image plate detector
using Debye-Scherrer geometry (with d¼ 127.4 mm). Experi-
mental and calculated X-ray powder diffraction data (CoKα) are in
good agreement and given in Fig. 1S, 2S. 3S.
 M.R. Markovski et al. / Journal of Solid State Chemistry 243 (2016) 215–220 217

Fig. 2. General projection of [Cu24 þ O(TeO3)2]2 þ cationic framework in the crystal structure of 2 along c (a) and a (c) axes. Mutually perpendicular channels occur in two
different orientations along a and c axis thus forming two-dimensional open-framework system (b). However channels along b axis are absent. Layers forming [Cu24 þ O
(TeO3)2]2 þ framework in 2 are projected in d. O(1) atoms are central in O(1)Cu4 oxocentered tetrahedra (green polyhedra), whereas the rest of oxygen atoms are central in
heterometallic OCu2Te oxocentered triangles. Enlarged pore fragment of the structure of 2 along c axis (e). Yellow-brown crystals of 2 under optical microscope (f). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

3. Results
3.1. Cation coordination
There is one symmetrically independent Te4 þ cation in the
structure of 1 (Fig. 1). Coordination of Te(1) is very typical with
formation of TeO3E (E¼ 5s2 lone-electron pair). Taking into account
longer and weaker Te–Cl bonds coordination environment of Te
(1) can be described as TeO3ECl3 (Table 2). There are three Cu–O
and two Cu–Cl bonds in coordination environments of Cu(1) and
Cu(2) atoms thus forming typical for Cu2 þ cations mixed-ligand
CuO3Cl2 polyhedra. The Cu2 þ cations with similar coordinations
have previously been observed in number of Cu oxochloride
compounds [20], with typical trends of Jahn-Teller d9 ions. Cu
(3) atoms belong to Cu þ cations tetrahedrally coordinated by Cl-
ions with formation of Cu þ Cl4. Bond lengths vary within Cu(3)Cl4
tetrahedra in the range of 2.289(1)–2.579(2) Å (Table 2).
Two nonequivalent Te(1) and Te(2) sites are in the structure of
2 (Fig. 2). TeO3E coordination polyhedra of Te4 þ cations are similar
to those in the structure of 1. Cu(1), Cu(2) and Cu(3) sites corre-
spond to Cu2 þ cations. There are three different coordination
polyhedra of Cu2 þ cations in the structure of 2: Cu(1)O3Cl squares,
Cu(2)O4Cl2 octahedra distorted owing to the Jahn-Teller effect, Cu
(3)O3Cl2 distorted tetragonal pyramids. Note, Cl(3) and Cl(4) sites
are slightly underoccupied. There is a number of low-occupied Cu
sites (Cu(4)-Cu(9)) in the structure of 2. Occupancies of Cl(3), Cl
(4) and Cu(4)-Cu(9) were first freely refined and later fixed to keep
formula of 2 electroneutral. Cu(4)-Cu(9) sites are coordinated ex-
clusively by Cl anions and correspond to Cu þ cations. Existence of
fully ordered polymorph of 2 can be expected but we didn't
succeed in obtaining such via variation of cooling rates during CVT
synthesis procedures.
Tl þ ions occupy one symmetrically independent position in the
structure of 3 (Fig. 3). Tl(1) site is coordinated by nine oxygen
atoms. All Tl–O bonds are in the range of 2.811(5)–3.437(5) Å. TlO8
polyhedron is strongly distorted due to the stereochemical activity
of 6s2 lone electron pair. Two TlO8 polyhedra share common edges
thus forming isolated Tl2O14 dimers. Cu(1) site is occupied by Cu2 þ
cations. Coordination of Cu(1) can be described as strongly dis-
torted CuO6 octahedron (Fig. 3d). There are four Te sites in the
structure of 3. Te(1) and Te(3) form TeO4E polyhedra taking into
account only short and the strongest Te–O bonds, whereas Te
(2) forms TeO3E trigonal pyramids. Thus both of these coordina-
tion environments observed for Te(1)-Te(3) atoms are typical for
Te4 þ cations. In contrast coordination of Te(4) atom located on
inversion center is very symmetrical with formation of TeO6 oc-
tahedron characteristic for Te6 þ .
Bond-valence sums calculated [21] for all the sites in the crystal
structures of 1–3 are in full agreement with their expected oxi-
dations states (in valence units): Cu2 þ sites  2.00–2.06, Cu þ sites
 1.03–1.10, Tl þ site  0.88, Te4 þ sites  3.88–4.17, Te6 þ site
 5.95.
3.2. Structure description
Because of the large size and variability of coordination poly-
hedra around Cu2 þ and Te4 þ cations and the high strength of Me–
O bonds in comparison to Me–Cl bonds (Me ¼metal), it is con-
venient to describe the structures of 1 and 2 in terms of oxocen-
tered units [22] and cation-centered polyhedra with Cu þ . O(1), O
218 M.R. Markovski et al. / Journal of Solid State Chemistry 243 (2016) 215–220

Fig. 3. General projection of the crystal structure of 3 along the c axis with channels filled by Tl þ cations (a). [Cu22 þ Te6 þ Te46 þ O18]2- framework is formed by layers depicted in
upper right and interconnected via tellurite-tellurate chains with Te(4) site (green octahedra) occupied by Te6 þ cations. Schematical representation and orientation of
channels along the c axis (b). Strongly distorted CuO6 octahedron (c). Kagome-like arrangement of tellurium atoms in the structure of 3 (d). Fragment of polytellurite-
tellurate framework with Te6 þ -centered octahedron in the center (e). Arrangement of Tl2O14 dimers separated by stereochemically active lone-pairs within the channels (f).
Aquamarine-blue crystals of 3 (g). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

(2) and O(3) atoms in 1 can be considered as central in hetero-
metallic OCu22 þ Te triangles (Fig. 1c). OCu22 þ Te triangles share
common edges and corners thus forming porous layers projected
in Fig. 1b. Pores have a shape of six-membered elongated rings
with dimensions of  1  0.65 nm. Layers are perpendicular to the
c axis and 0.35 nm thick. Two Cu þ Cl4 tetrahedra share common
edges with formation of Cu2þ Cl6 dimers located in the interlayer
under and above the pores (Fig. 1a).
In addition to O atoms bonded to Te4 þ cations in the structure
of 2 there are also additional O(1) atoms not being parts of TeO32 
anions. These oxygen atoms are tetrahedrally coordinated thus
forming OCu24 þ oxocentered tetrahedra (Fig. 2d). OCu22 þ Te trian-
gles identical to those in 1 share common corners with OCu24 þ
producing porous layers depicted in Fig. 2d. Resulted layers are
further stacked one with each other (Fig. 2a) into open-framework
with two-dimensional system of channels (Fig. 2a,b,c). Mutually
 M.R. Markovski et al. / Journal of Solid State Chemistry 243 (2016) 215–220 219

Table 1 cavities causes repulsion of the Tl þ and Te4 þ cations across these
Crystallographic data and refinement parameters for |Cu þ Cl3|[Cu22 þ (TeO3)] (1) , | cavities. Novel [Te6 þ Te46 þ O18]6- polytellurite-tellurate framework
þ
Сu1.7 Cl3.8|[Cu24 þ O(TeO3)2] (2) and Tl2þ [Cu22 þ Te6 þ Te46 þ O18] (3).
(Fig. 3e) can be represented as consisting of Kagome-like layers
1 2 3 (Fig. 3d) perpendicular to c axis.

Crystal size (mm) 0.1  0.1  0.05 0.08  0.06  0.08 0.06  0.08  0.03
Radiation wavelength 0.71073
(Å ) 4. Discussion and conclusion
Space group P-1 Pbam P21/n
a (Å) 6.248(1) 9.2877(7) 7.605(2) We reported on the syntheses and structural architectures of
b (Å) 6.251(1) 21.0328(16) 11.825(3) the first ‘pure’ (i.e. without additional cations) mixed-valence Cu þ /
c (Å) 9.408 (3) 6.4213(5) 9.849(3)
α (°) 80.674 (6) 90 90
Cu2 þ tellurite chlorides and first mixed-valence Te4 þ /Te6 þ thal-
β (°) 75.611(6) 90 90.978(8) lium polytellurite-tellurate. Lone electron pairs on the Te4 þ ca-
γ (°) 80.849(6) 90 90 tions in 1 and 2 are oriented toward chloride guest species thus
V (Å3) 348.48(17) 1254.38(17) 885.6(4) revealing halophilic behavior of 5s2 lone electron pairs. In the
μ (mm–1) 14.251 14.854 31.903
Dcalc (g cm  3) 4.504 4.64564 6.439
structure of 3 6s2 lone pairs on Tl þ and 5s2 lone pairs on Te4 þ can
Reflection collected 3291 3924 8028 be considered as soft ligands that tend to associate together in a
Independent 1982 860 2310 “hard” environment within special cavities or channels nearly
reflections perpendicular to the c axis. Crystal structures of 1, 2 and 3 are
Rint 0.021 0.064 0.040
R1[I 42s(I)] 0.043 0.055 0.031
characterized by high degree of porosity and based on the fol-
Goodness-of-fit 1.040 1.029 0.983 lowing structural units: porous cationic [Cu22 þ (TeO3)]2 þ layers in 1
Largest diff. peak and 2.658,  4.404 2.708,  3.292 1.882,  1.759 (Fig. 1d); cationic [Cu24 þ O(TeO3)2]2 þ open-framework with two-
hole [e Å3] dimensional system of wide channels in 2 (Fig. 2b);
[Cu22 þ Te6 þ Te46 þ O18]2  open-framework with isolated channels in
perpendicular channels (  1.16  0.74 nm) are parallel to a and c 3 (Fig. 3b). Observed phenomenon of formation of pores and
channels in general is consequence of combination of many cir-
axes (Fig. 2e). Low-occupied sites of Cu þ cations coordinated by Cl
cumstances. ‘Host-guest’ structural organization of 1 and 2 with
anions fill the channels.
host Cu2 þ -tellurite units of different dimensionality formed by
Isolated Te(2)O3E and Te(3)O4E polyhedra share common cor-
oxocentered OCu4 tetrahedra and OCu2Te triangles and guest Cu þ -
ners with CuO6 octahedra thus forming layers depicted in Fig. 3a.
chloride species is the result of formation from gases in CVT re-
Unique [23] in topology tellurite-tellurate chains (Fig. 3c) formed
actions. Likely, during these reactions the tellurites and halides
by Te(1)2O6 dimers and Te(4)O6 octahedra interconnect layers into
play the role of transport agent. High volatility of tellurium oxides
3D framework with channels (  0.75  0.43 nm) elongated along [24] is well known within temperature ranges applied. Oxocen-
the c axis (Fig. 3a). Tl þ cations are located within the channels. tered units determine basic topologies of the structures of 1 and 2
Tl2O14 dimers are separated one from each other by the stereo- and influence their stability and properties. Influence of differ-
chemically active 6s2 lone electron pairs serving as ‘chemical ences in Lewis Acid strength of Cu þ and Cu2 þ subordinate by
scissors’ (Fig. 3f). Tl-Tl distance between Tl2O14 dimers is 5.7 Å. Hard-Soft Acid-Base (HSAB) principle should be also taken in ac-
Lone pairs on Tl þ cations together with lone pairs on Te4 þ in turn count. It is notable that tellurium (IV) can adopt various co-
create narrow channels and cavities. Formation of the lone pair ordination behaviors in contrast to selenium (IV) and its

Table 2
Selected interatomic distances (Å) in the crystal |Cu þ Cl3|[Cu22 þ (TeO3)] (1), |Сu1.7
þ
Cl3.7|[Cu24 þ O(TeO3)2] (2) and Tl2þ [Cu22 þ Te6 þ Te46 þ O18] (3).

1 2 3

Te(1)-O(3) 1.880(4) Te(1)-O(3) 1.875(11)2  Tl(1)-O(2) 2.811(5) Te(3)-O(5) 1.859(4)

Te(1)-O(2) 1.884(4) Te(1)-O(4) 1.896(14) Tl(1)-O(5) 2.844(4) Te(3)-O(9) 1.883(5)
Te(1)-O(1) 1.893(3) Te(1)-Cl(1) 3.117(5) Tl(1)-O(4) 2.921(5) Te(3)-O(6) 2.133(4)
Te(1)-Cl(1) 3.152(4) Tl(1)-O(1) 3.025(5) Te(3)-O(4) 2.187(4)
Te(1)-Cl(2) 3.263(4) Te(2)-O(5) 1.901(13) Tl(1)-O(9) 3.097(5) Te(3)-O(2) 2.798(5)
Te(1)-Cl(3) 3.293(4) Te(2)-O(2) 1.934(10) 2  Tl(1)-O(7) 3.105(4) Te(3)-O(8) 2.931(5)
Te(2)-O(4) 2.494(11) 2  Tl(1)-O(7) 3.355(4)
Cu(1)-O(1) 1.931(4) Te(2)-O(5) 2.908(13) Tl(1)-O(8) 3.437(5) Te(4)-O(4) 1.893(5) 2 
Cu(1)-O(2) 1.951(3) Te(2)-Cl(2) 3.478(7) Te(4)-O(2) 1.937(4) 2 
Cu(1)-O(2) 1.983(4) Te(1)-O(4) 1.875(4) Te(4)-O(8) 1.948(4) 2 
Cu(1)-Cl(2) 2.2919(18) Cu(1)-O(1) 1.9047(1) Te(1)-O(3) 1.929(4)
Cu(1)-Cl(1) 2.6911(17) Cu(1)-O(4) 1.9358(1) Te(1)-O(8) 2.100(5) Cu(1)-O(9) 1.942(5)
Cu(1)-O(4) 1.9592(1) Te(1)-O(3) 2.146(4) Cu(1)-O(1) 1.952(4)
Cu(2)-O(1) 1.942(4) Cu(1)-Cl(2) 2.2597(2) Te(1)-O(1) 2.779(6) Cu(1)-O(2) 1.959(4)
Cu(2)-O(3) 1.959(4) Te(1)-O(6) 2.890(7) Cu(1)-O(5) 1.964(4)
Cu(2)-O(3) 1.993(4) Cu(2)-O(1) 1.920(7) Te(1)-O(5) 2.930(5) Cu(1)-O(8) 2.618(5)
Cu(2)-Cl(3) 2.2775(17) Cu(2)-O(3) 1.922(10) Cu(1)-O(6) 2.938(5)
Cu(2)-Cl(1) 2.6758(17) Cu(2)-O(5) 1.997(8) Te(2)-O(2) 1.868(4)
Cu(2)-O(2) 2.007(9) Te(2)-O(1) 1.870(4)
Cu(3)-Cl(2) 2.2886(17) Cu(2)-Cl(1) 2.845(4) Te(2)-O(7) 1.962(5)
Cu(3)-Cl(3) 2.2925(19) Cu(2)-Cl(4) 2.907(7) Te(2)-O(3) 2.521(5)
Cu(3)-Cl(1) 2.311(2) Te(2)-O(9) 2.822(5)
Cu(3)-Cl(2) 2.579(2) Cu(3)-O(1) 1.922(13) Te(2)-O(4) 3.058(5)
Cu(3)-O(2) 1.991(10) 2  Te(2)-O(6) 3.077(5)
Cu(3)-Cl(1) 2.210(6)
Cu(3)-Cl(2) 2.919(7)
220 M.R. Markovski et al. / Journal of Solid State Chemistry 243 (2016) 215–220

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