Synthesis and crystal structure of β-CuSe2O5, a new polymorph of copper diselenite

Article abstract of DOI:10.1016/j.mencom.2017.01.019

In contrast to the layered structure of the previously known polymorph of copper diselenite, the crystal structure of a new polymorph, β-CuSe₂O₅, is based on a 3D framework and has a higher structural complexity than the α-phase.

Full text of DOI:10.1016/j.mencom.2017.01.019

Mendeleev
Communications
Mendeleev Commun., 2017, 27, 61–63
Synthesis and crystal structure of b-CuSe O ,
2
5
a new polymorph of copper diselenite
a,b,c
a
a
Vadim M. Kovrugin,*
Ilya V. Kornyakov, Vladislav V. Gurzhiy,
a
b
b
a
Oleg I. Siidra, Marie Colmont, Olivier Mentré and Sergey V. Krivovichev
a
b
c
Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University,
1
99034 St. Petersburg, Russian Federation. E-mail: kovrugin_vm@hotmail.com
Unité de Catalyse et Chimie du Solide (UCCS), UMR 8181 CNRS, Université Lille 1 Sciences
et Technologies, 59655 Villeneuve d’ASCQ, France
Laboratoire de Réactivité et Chimie des Solides (LRCS), UMR 7314 CNRS, Université de Picardie Jules
Verne, 80039 Amiens Cedex, France
DOI: 10.1016/j.mencom.2017.01.019
2 5
β-CuSe O
In contrast to the layered structure of the previously known
polymorph of copper diselenite, the crystal structure of a
new polymorph, b-CuSe O , is based on a 3D framework
Cu(1)
0
.5 mm
Cu(1)
2
5
and has a higher structural complexity than the a-phase.
Se(2)
Se(1)
Recently, a large number of theoretical and experimental studies
were devoted to industrially important inorganic copper com­
pounds. At the same time, selenium­containing oxo compounds
(
a)
(b)
O(1)
1
0
.5 mm
0.4 mm
α-CuSe
O(4)
are versatile materials in terms of a broad structural diversifica­
O(3)
2
,3
4+
β-CuSe
2
O
5
2
O
5
O(2)
tion. The electronic properties of Se lead to materials with
4,5
O(4)
specific physical properties owing to the presence of lone­pair
electrons along with the Jahn–Teller effect typical of Cu ions
with the d electron configuration.
(c)
Cu(1)
O(5)
2
+
O(5)
Se(2)
Cu(1)
9
1
23.58°
O(1)
O(2)
O(2)
Previously, we studied novel crystalline phases prepared by
chemical vapour transport (CVT) reactions in the Cu–Se oxy­
O(3)
O(4)
Se(1)
O(3)
chloride system, which demonstrated a fascinated variety of
O(1)
structural architectures.6–9 Many of the synthesized copper oxide
phases prepared by this technique contain so­called ‘additional’
oxygen atoms, which are coordinated solely by copper cations.
Figure 1 Optical microscopy images of (a) b­CuSe O and (b) a­CuSe O
5
10
2
5
2
crystals; (c) coordination of Se O and Cu O groups in b­CuSe O . Inter­
2
5
2
10
2
5
In addition to a series of new compounds with complex crystal
structures, our crystallization experiments using CVT reactions
also lead to the formation of two polymorphs of simple selenite
phases. Both of them, i.e., recently reported new modification of
atomic distances are given in angstrom units. Displacement ellipsoids are
drawn at a 50% probability level.
†
A mixture of CuO (2 mmol, Alfa Aesar, 99%), CuCl2 (1.5 mmol,
11
Aldrich, 99%), SeO (1 mmol, Alfa Aesar, 99%), NaCl (1 mmol, Alfa
selenious acid H SeO3 and the new form of CuSe O presented
2
2
2
5
Aesar, 99%), and PbO (0.5 mmol, Aldrich, 99%) was used for the
in this work, are very hygroscopic and metastable at room
temperature and atmospheric pressure.
preparation of single crystals of b­CuSe O . Precursors were predried at
2
5
100°C for 2 h and further rapidly mixed and ground in an agate mortar
The only known polymorph of CuSe O (denoted herein as
2
5
2
in air for 5 min. Then, the mixture was also dried at 100°C for 1 h.
Afterwards, it was loaded into a silica ampoule (~15×0.9 cm), which
1
a­CuSe O ) was first described in 1976, and then re­inves­
2
5
1
3
tigated in 2006. The a­modification is of interest for its
–2
was evacuated for 20 min to a pressure of 10 mbar and then sealed.
specific magnetic behaviour, which was the subject matter of
The ampoule was placed horizontally in a tubular furnace so that the
precursor­filled zone was situated in the central part of the furnace, while
the opposite precursor­free zone was turned out toward the furnace edge.
This edge remained uncapped in the course of the experiment to create
temperature gradient DT ≈ 50°C between the two zones of the ampoule.
The furnace was heated to 550°C for three days. Then, the temperature
was lowered to 400°C during 6 h. Afterwards, the furnace was switched
1
4–16
extensive studies.
Analysis of the new modification of
CuSe O (denoted as b­CuSe O ), as detailed below, reveals its
2
5
2
5
17
close structural relations to CuTe O . The latter also has been
2
5
intensively studied owing to its unusual magnetic and vibrational
1
8–20
properties.
Herein, we report the synthesis and structural characteriza­
off. Block­shaped blue single crystals of b­CuSe O5 were found in a
2
tion of a new modification of copper diselenite, b­CuSe O , and
2
5
small amount in the deposition zone of the ampoule in association with
discuss structural relations between the two polymorphs.
11
transparent needles of recently reported new polymorph of H SeO . The
2
3
Single crystals [Figure 1(a)] of b­CuSe O 1 have been
2
5
resulted crystals of these two phases were metastable and hygroscopic at
room temperature and ambient pressure, and they were gradually dissolved
in the next three days.
†
prepared by CVT reactions at 550°C in a sealed silica ampoule
from a mixture of CuO, CuCl , SeO , NaCl, and PbO taken in a
2
2
©
2017 Mendeleev Communications. Published by ELSEVIER B.V.
–
61 –
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.

Mendeleev Commun., 2017, 27, 61–63
1
3
17
Table 1 Crystallographic data for a­CuSe O , b­CuSe O 1, and CuTe O .
2
5
2
5
2
5
Crystal
M/g mol–1 Space group
a/Å
b/Å
c/Å
b/deg
V/Å3
Z
dcalc/g cm–3 m/mm–1
1
3
a­CuSe O
301.46
301.46
398.75
C2/c
12.3869(19) 4.8699(7)
7.9917(13) 111.953(15) 447.13
4
4
4
4.478
4.545
5.755
21.08
21.39
17.73
2
5
b­CuSe O
P2 /c
6.918(3)
6.871(2)
8.8172(4)
9.322(2)
7.5714(4)
7.602(2)
108.570(2) 440.56(4)
2
5
7
1
1
CuTe O
P2 /c
109.08(1)
460.17(2)
2
5
1
molar ratio of 2:1.5:1:1:0.5. Note that the CVT experiments
performed in a temperature range of 250–550°C (50°C per step)
(a)
with a mixture of CuO and SeO taken in a ratio of 1:2 did not
2
result in the crystallization of 1, but they led to the formation of
13
21
11
a­CuSe O [Figure 1(b)], Cu(HSeO3)2, and b­H SeO . The
2
5
2
3
absence of the b­polymorph in this case can be explained by the
–
absence of Cl ions involved in the CVT reactions. Earlier, it was
2
,6,8
–
demonstrated
that the selenite systems containing Cl anions
exhibit a noticeably greater structural variety than Cl­free systems
and that chlorine acts as both a transport agent and a structure­
forming component in such systems. Note that, despite the
preliminary drying of precursors, final products have been found
to contain hydroselenites, which suggest that absorbed water
together with hydrogen halides can also play an important role
in the system.
b
a
c
(
b)
The structure of 1 was studied using single­crystal X­ray
‡
diffraction analysis. The new phase b­CuSe O is isotypic with
2
5
17
the previously reported CuTe O , which so far was reported to
2
5
exist in one form only. Selected structural data for a­CuSe O ,
2
5
b­CuSe O , and CuTe O are given in Table 1.
2
5
2
5
The crystal structure of 1 contains one crystallographically
independent Cu site, which has a Jahn–Teller­distorted octahedral
coordination with the four short Cu–O bonds (1.948–1.975 Å)
b
that define a CuO square complemented by two longer Cu–O
4
bonds (2.268 and 2.680 Å).
c
In the structure of 1, there are two Se sites in a triangular
pyramidal coordination with Se atoms located at the apices, in
agreement with the stereochemical activity of lone electron pairs.
Two SeO pyramids share a common O(1) atom to form a Se O
3
2
5
Figure 2 Projections of the crystal structure of b­CuSe O . Cu, Se, and O
2 5
atoms are shown by cyan, orange, and red balls, respectively.
diselenite group [Figure 1(c)]. The bridging Se–O(1) distances
br
(
1.823 Å) are essentially longer than the terminal Se–O bonds
t
(
1.675 Å). This type of a dimeric unit is quite common for metal
linked via diselenite groups are oriented along [101], as shown
in Figure 2(a).
selenites, and it was observed, e.g., in the series of compounds
with the general formula MSe O (M = Mn, Co, Cu, Pd, Zn,
2+
17
In the two isotypic phases, b­CuSe O and CuTe O , the
2
5
2
5
2
5
Cd, Pb, Mg, Ca, Sr, and Ba). The structural analysis of phases in
this group revealed the steric flexibility of the diselenite group
main difference between their lattice parameters is in the b
parameter, which differs by Db ≈ 0.5 Å. Structurally this can be
easily explained by the fact that the distance along the b­axis
between the copper dimers parallel to (010) is controlled by the
size of the Se O and Te O groups.
due to the rotation of selenite pyramids around the O bridging
br
corner. It is also noteworthy that, in most cases, the diselenite
group has a twofold symmetry axis with one crystallographically
independent Se site, whereas compound 1 and several phases
2
5
2
5
In contrast to the 3D framework structure of b­CuSe O5
2
2
2
23
24
with large cations, such as BaSe O , SrSe O , CaSe O , and
consisting of copper dimeric units (Figure 2), the crystal structure
2
5
2
5
2
5
2
5
PbSe O , contain two inequivalent Se sites.
of a­CuSe O is based upon the corrugated chains of corner­
2
5
2
5
In the crystal structure of b­CuSe O , two CuO octahedra
sharing octahedra linked by Se O groups to form layers parallel
2
5
6
2 5
share a common O∙∙∙O edge to form a dimeric Cu O unit with
to (100). Owing to such contrasting architectures of the two
2
10
3
the Cu∙∙∙Cu distance of 3.267 Å [Figure 1(c)]. The shortest inter­
dimeric Cu∙∙∙Cu distance is about 5.17 Å. The copper dimers
polymorphs, they differ in their unit­cell volumes (447.13 Å
3
for the a­phase vs. 440.56 Å for the b­phase) and density
4.478 vs. 4.545 g cm , respectively). Therefore, it is of interest
–
3
(
‡
to compare two polymorphs in terms of their structural complexity
expressed by a Shannon information content per atom and per
Intensities of 3386 reflections were measured with a Bruker X8 APEX II
CCD diffractometer [l(MoKa) = 0.71073 Å, a q range of 3.1–31.5°]
and 1459 independent reflections (Rint = 0.030) were used in a further
refinement. The unit­cell parameters are given in Table 1. The structure
of 1 was solved by a direct method and refined by the full­matrix least­
squares technique against F in the anisotropic approximation. The refine­
ment converged to wR = 0.0362 and GOF = 1.061 for all independent
2
6,27
unit cell.
The calculations using the ToposPro28 software indicated that
the b­polymorph (I = 3.00 bits per atom, I = 96.00 bits per
G
G,total
2
cell) is more complex than the a­polymorph (IG = 2.25 bits
per atom, IG,total = 36.00 bits per cell). The higher complexity of
the framework­based b­phase compared to the layered a­phase
agrees quite well with their higher density mentioned above. In
general, we suggest that the b­phase reported here can be a low­
temperature (or high­pressure) polymorph of copper diselenite.
Generally, a high­temperature polymorph is structurally simpler
2
2
reflections [R1 = 0.0167 was calculated against F for 1305 observed
reflections with F2 > 2s(F )]. All calculations were performed using
2
SHELXL­2013 program.32
CSD 431114 contains the supplementary crystallographic data for this
paper. These data can be obtained from FIZ Karlsruhe, 76344 Eggenstein­
Leopoldshafen, Germany, http://www.fiz­karlsruhe.de/.
–
62 –

Mendeleev Commun., 2017, 27, 61–63
9 V. M. Kovrugin, M. Colmont, O. Mentre, O. I. Siidra and S.V. Krivovichev,
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the data on density and unit­cell volumes, strongly suggest that
the a­ and b­modifications of CuSe O are high­ and low­tem­
perature polymorphs, respectively. This conclusion is consistent
with the 2D and 3D characters of their structures, respectively,
which is frequently observed in polymorphic inorganic com­
pounds (that is, the structural dimensionality of a low­tempe­
rature polymorph is higher than that of its high­temperature
1
2
5
1
1
2
664.
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This work was supported by the ANR (grant no. ANR
011­JS­08 00301) within the framework of the Multi­InMaDe
project. The Fonds Europeen de Developpement Regional
FEDER), CNRS, Region Nord Pas­de­Calais, and Ministere
de l’Education Nationale de l’Enseignement Superieur et de la
Recherche are acknowledged for funding the X­ray diffracto­
meters. S.V.K. andV.M.K. acknowledge the support of the Russian
Science Foundation (theoretical studies; grant no. 14­17­00071)
and the Russian Foundation for Basic Research (experimental
studies; grant no. 15­35­20632).
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