Cadmium copper selenite chloride, CdCu2(SeO3)2Cl2, an insulating spin gap system

Article abstract of DOI:10.1016/j.jssc.2021.122518

Novel copper cadmium selenite chloride has been synthesized via vapor transport reaction as well as by solid state process. CdCu₂(SeO₃)₂Cl₂ crystallizes in a monoclinic space group I2/a with cell constants a ?= ?7.8057(3) ?, b ?= ?9.6036(4) ?, c ?= ?10.7817(5) ? and β ?= ?102.362(4)°, Z ?= ?4. Its crystal structure can be described as an open channel three-dimensional framework, formed by [CdO₂Cl₄] and [CuO₄Cl₂] polyhedra interconnected by pyramidal SeO₃ groups. The copper polyhedra form magnetically isolated dimers with a spin gap Δ ?= ?38.7 ?± ?0.8 ?meV, as defined from magnetic susceptibility measurements. The electron band gap estimated by diffuse reflectance method E_g ?= ?2.82 ?± ?0.02 ?eV is in agreement with the yellow-green color of the substance. Density functional theory provides the values of electron (2.4 ?eV) and spin (36.6 ?meV) gaps consistent with experimental observations.

Full text of DOI:10.1016/j.jssc.2021.122518

Journal of Solid State Chemistry 303 (2021) 122518
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Cadmium copper selenite chloride, CdCu2(SeO3)2Cl2, an insulating spin
gap system
,
Alisher F. Murtazoev a, Peter S. Berdonosov a *, Victor A. Tafeenko a, Valery A. Dolgikh a,
,
,d,**
Igor L. Danilovich a, Zlata V. Pchelkina b c, Alexander N. Vasiliev a
a Lomonosov Moscow State University, Moscow, 119991, Russia
b Institute of Metal Physics, RAS, Ekaterinburg, 620041, Russia
c Ural Federal University, Ekaterinburg, 620002, Russia
d National University of Science and Technology “MISiS”, Moscow, 119049, Russia
A R T I C L E I N F O
A B S T R A C T
Keywords:
Synthesis
Selenite
Crystal structure
Lone electron pair
Magnetic dimers
Copper
Novel copper cadmium selenite chloride has been synthesized via vapor transport reaction as well as by solid state
process. CdCu2(SeO3)2Cl2 crystallizes in a monoclinic space group I2/a with cell constants a ¼ 7.8057(3) Å,
b ¼ 9.6036(4) Å, c ¼ 10.7817(5) Å and β ¼ 102.362(4)ꢀ, Z ¼ 4. Its crystal structure can be described as an open
channel three-dimensional framework, formed by [CdO2Cl4] and [CuO4Cl2] polyhedra interconnected by pyra-
midal SeO3 groups. The copper polyhedra form magnetically isolated dimers with a spin gap Δ ¼ 38.7 ꢁ 0.8 meV,
as defined from magnetic susceptibility measurements. The electron band gap estimated by diffuse reflectance
method Eg ¼ 2.82 ꢁ 0.02 eV is in agreement with the yellow-green color of the substance. Density functional
theory provides the values of electron (2.4 eV) and spin (36.6 meV) gaps consistent with experimental
observations.
1. Introduction
Pb3(SeO3)X2 (X ¼ Cl, Br and I) [14–16]. In case of the same composition
lead tellurite only chloride and bromide forms have been described [17,
The search for new compounds with an open framework structure is
an important trend in the materials science due to their valuable func-
tional properties, the optical [1–4] and magnetic [5–9] ones, in partic-
ular. To create an open framework system, the so-called
“structure-directing” agents are used, e.g., Se4þ or Te4þ ions [10]. These
ions possess a lone electron pairs, which, being stereochemically active,
push apart the ions around them and promote the formation of voids. In
turn, the tendency of lone pairs to agglomerate is a decisive factor in the
process of the framework formation. The incorporation of transition
metal ions into the framework structures may result in rather peculiar
magnetic properties due to the formation of weakly coupled groups of
ions such as dimers, trimers, chains with different geometry etc.
Among the variety of chalcogenite halides, there is a vast family of
general composition M3(ZO3)2X2 where M is either one or two different
divalent ions, Z ¼ Se or Te and X ¼ Cl, Br or I. Some compounds contain
only s metal ions, namely Sr3(SeO3)2Cl2 [11], Sr3Te2O6X2 (X ¼ Cl, Br)
[12] and Ba3(TeO3)2Cl2 [13]. The compounds based on the p element are
18]. The copper form the compound Cu3(SeO3)2Cl2 crystallizing in two
different crystal modifications [19,20] and Cu3(TeO3)2Br2 [21,22]
(Table S1). The most interesting for search for exotic magnetic systems
are mixed cationic compounds mentioned family with the composition,
e.g., MM’2(ZO3)2Cl2, (M ¼ alkali earth metal or Pb, M’ ¼ d-metal) [6,
24–28] or M2M’(ZO3)2Cl2 [1,11,24,27–29].
A lot of copper-based compounds has been obtained and studied,
most of them evidencing the low dimensional magnetic response [6,22,
23,25,26]. For example, CaCu2(SeO3)2Cl2 [23] is a spin 1/2 Heisenberg
chain compound with complex frustrated interchain coupling, whereas
PbCu2(ZO3)2Cl2 Z ¼ Se and Te exhibit different spin-chain magnetic
behavior [6]. A common structural feature of these compounds is the
tendency to organize the three-dimensional network of different MOyXn
and M’Oy'Xn' polyhedra. These polyhedra are interconnected by trigonal
pyramids of [ZO3E], where E – is stereoactive pair of electrons. Magnetic
properties of these compounds depend not only on the linkage of
Cu-based polyhedra but also on selenite or tellurite groups, which
* Corresponding author. Department of Chemistry, Inorganic Chemistry Division, Moscow State University, Leninskie Gory 1 build. 3, GSP-1, Moscow, 119991,
Russia.
** Corresponding author. Lomonosov Moscow State University, Moscow, 119991, Russia.
E-mail addresses: berdonosov@inorg.chem.msu.ru (P.S. Berdonosov), anvas2000@yahoo.com (A.N. Vasiliev).
https://doi.org/10.1016/j.jssc.2021.122518
Received 23 June 2021; Received in revised form 12 August 2021; Accepted 13 August 2021
Available online 14 August 2021
0022-4596/© 2021 Published by Elsevier Inc.

A.F. Murtazoev et al.
Journal of Solid State Chemistry 303 (2021) 122518
provide the superexchange pathways as has been shown for CaCu2(-
SeO3)2Cl2 [23] and PbCu2(ZO3)2Cl2, (Z ¼ Se or Te), [6].
2.4. Single crystal X-ray diffraction
The combination of magnetic and nonmagnetic ions in the crystal
structure of chalcogenite halides with composition MM’2(ZO3)2X2 is a
good instrument for the property adjustment. From one side, it should be
mentioned that there is no metal ions combination where two d-metal
ions coexist within MM’2(ZO3)2X2 composition. From other side, there is
no combination of metal ions of 12th group elements with magnetic ions.
Zinc and cadmium may form tetrahedral or octahedral environment and
often constitute the dimers, chains or columns [1,30,31]. The prepara-
tion of these compositions was attempted for Sr2þ ions exploring the
system Zn–Sr–SeO3–Cl, however without success [32]. Recently,
quasi-one-dimensional and quasi-two-dimensional compounds were
found in Zn–Ba–SeO3–Cl system [18]. Finally, the second-harmonic
generation active compounds were found within Pb–Cd–SeO3-X
(X ¼ Cl, Br) family [1]. Some data about MM’2(ZO3)2X2 compounds are
summarized in Table S1 in the supporting information file.
The data of CdCu2(SeO3)2Cl2 crystal were collected using STOE
diffractometer Pilatus 100K detector, plane graphite monochromator and
collimation of Mo Kα (0.71073 Å) radiation by 0.5 diameter of the
monocapillary in a rotation method mode. STOE X-AREA software was
used for cells refinement and data reduction. Data collection and image
processing was performed with X-Area 1.67 (STOE & Cie GmbH,
Darmstadt, Germany, 2013). Intensity data were scaled with LANA (part
of X-Area) in order to minimize differences of intensities of symmetry-
equivalent reflections (multi-scan method). Structure was solved and
refined with SHELXT program [33]. Crystal data and structure refine-
ment values for CdCu2(SeO3)2Cl2 one given in Table 1. Interatomic dis-
tances for CdCu2(SeO3)2Cl2 are listed in Table 2. Further details of the
crystal structure investigation may be obtained from the Cambridge
Crystallographic Data Centre (CCDC). These data can be obtained at
www.ccdc.cam.ac.uk/data_request/cif using the deposition number
CCDC-2061542.
Here, we report the synthesis of the new compound combining the
12th group element cadmium and copper, CdCu2(SeO3)2Cl2, using the
approach of combining within one structure the lone electron pair sele-
nite groups with two different d-metal polyhedrons and its character-
ization through measurements of optical and magnetic properties and
first principles calculations. Such synthesis concept led to dimer system
formation.
2.5. Thermal analysis
Thermal analysis of the samples was carried out using a Pyris Dia-
mond TG/DTA thermal analyzer (PerkinElmer) in an atmosphere of
argon in the temperature range of 40–800 ꢀC. Corundum crucible was
used for sample holding. The weighted portions of powder samples were
2. Experimental section
10–15 mg with a continuous weighing accuracy of 0.2
μg, and the
heating rate was 10ꢀ/min. According to the thermal analysis (Electronic
Supporting Information Fig. S2), the substance under investigation is
stable up to 250 ꢀC. At this temperature, the first small weight loss occurs.
The decomposition starts at about 450 ꢀC at which temperature the big
weight loss is observed.
2.1. Synthesis
Commercially available reactants CdO, CuO, CuCl2, CuCl2⋅2H2O and
selenous acid with purity non less than 98% were used for samples
preparation. Anhydrous SeO2 was prepared by dehydration of H2SeO3
under the 1–5 Torr vacuum at 80–95 ꢀC in a glass tube. A tube was heated
by water bath up to the boiling point. The product was finally sublimated
in the flow of dry air and NO2 mixture. All operations with moisture
sensitive substances were performed in an argon filled glow box.
The single-phase polycrystalline compound CdCu2(SeO3)2Cl2 was
obtained from the mixture of CdO (1 mmol), SeO2 (2 mmol), CuCl2
(1 mmol) and CuO (1 mmol) in a sealed under vacuum 30–40 mTorr
quartz tube. Annealing proceeded according to the foꢂll1owing protocol.
The first step is heating to 300 ꢀC at a rate of 25ꢀСꢀh. and holding at
this temperaꢂtu1re for 24 h. Second step is heating to 480–500 ꢀC at a rate
of 83.3ꢀСꢀh. and holding at this temperature for 6 days. As the result
the yellow green powder sample was obtained.
2.6. Optical properties
The infrared (IR) spectrum was recorded on a PerkinElmer Spectrum
One Fourier spectrometer in a transmission mode in the range of
4000–400 cmꢂ1 with a resolution of 1 cmꢂ1. The powder sample was
Table 1
Crystal data and structure refinement for CdCu2(SeO3)2Cl2.
Empirical formula
Cd Cu2 Se2 O6 Cl2
Formula weight
Temperature
564.30
295(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Unit cell dimensions
Monoclinic
I2/a
2.2. Powder XRD
a ¼ 7.8057(3) Å
b ¼ 9.6036(4) Å
c ¼ 10.7817(5) Å
β ¼ 102.362(4)ꢀ.
789.49(6) Å3
4
Powder XRD was performed on STOE STADI P diffractometer (Cu Kα
1
radiation) using STOE WinXPOW software with ICDD PDF2 database as
reference. Powder pattern was indexed in monoclinic system, I2/a (#15)
space group with cell constants a ¼ 7.829(2)Å, b ¼ 9.633(3) Å,
c ¼ 10.833(3) Å, β ¼ 102.355(17)ꢀ, Z ¼ 4, cell volume ¼ 798.1(6) Å3,
Figure of Merit F(30) ¼ 30.7. The powder pattern is shown on Fig. 1S in
the supporting information.
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
4.748 Mg/m3
17.891 mmꢂ1
1024
0.23 ꢃ 0.17 ꢃ 0.12 mm3
2.870–29.099ꢀ.
ꢂ10 ꢄ h ꢄ 10,
ꢂ13 ꢄ k ꢄ 13,
ꢂ14 ꢄ l ꢄ 14
10777
2.3. Single crystal growth
Crystals of target compound were obtained by chemical vapor
transport reaction from the mixture of CdO (1 mmol), SeO2 (2 mmol),
CuCl2 (0.9 mmol) and CuO (1 mmol) and CuCl2⋅2H2O (0.1 mmol). The
mixture was loaded into 17 cm length and 15 mm diameter quartz tube
which was sealed under vacuum 30–40 mTorr. The transport reaction
took place in a two-zone electronically controlled furnace in temperature
gradient cold zone 400 ꢀC and hot zone 450 ꢀC for 14 days. After the
cooling to the room temperature transparent yellow green crystals were
found in the cold end of the tube.
Reflections collected
Independent reflections
Completeness to theta ¼ 25.242ꢀ
Refinement method
1055 [R(int) ¼ 0.0424]
100.0%
Full-matrix least-squares on F2
1055/0/61
Data/restraints/parameters
Goodness-of-fit on F2
1.064
Final R indices [I > 2sigma(I)]
R indices (all data)
Extinction coefficient
R1 ¼ 0.0257, wR2 ¼ 0.0577
R1 ¼ 0.0295, wR2 ¼ 0.0586
0.0043(3)
1.136 and ꢂ0.704 e. Å
ꢂ3
Largest diff. peak and hole
2

A.F. Murtazoev et al.
Journal of Solid State Chemistry 303 (2021) 122518
the legs of ladder are 5.391 Å. The Cu–Cu distance between two ladders is
4.797(2) Å.
Table 2
Some interatomic distances (Å) for CdCu2(SeO3)2Cl2.
The Cd polyhedrons chains and Cu polyhedrons dimer chains run in
perpendicular directions building up the 3D framework with hollow
channels perpendicular to bc plane of the crystal structure. Selenium
atoms are situated in these channels and sew [CdO2Cl4] and [CuO4Cl2]
polyhedra sharing O atoms from different Cu–Cu dimer chains. Thus, the
crystal structure of cadmium copper selenite chloride may be described
as 3D framework with open channels.
Bond
Distance
Cd(1)–O(1)
Cd(1)–Cl(1)
Cd(1)–Cl(1)
Cu(1)–O(1)
Cu(1)–O(3)
Cu(1)–O(2)
Cu(1)–O(2)
Cu(1)–Cl(1)
Cu(1)–Cl(1)
Se(1)–O(3)
Se(1)–O(1)
Se(1)–O(2)
x2
x2
x2
2.336(3)
2.6319(10)
2.6426 (10)
1.939(3)
1.945(3)
1.970(3)
1.994(3)
2.798(1)
2.783(1)
1.666(3)
1.709(3)
1.730(3)
3.2. Optical properties
IR spectrum of CdCu2(SeO3)2Cl2 is shown on Fig. 2a. The bands with
ν
¼ 866, 846 and 770 cmꢂ1 may be attributed to the usual
ν(Se–O) bond
vibrations, while the bands in a range 680–540 cmꢂ1 originate from
pressed into pellet with optically pure KBr. Ultraviolet–visible (UV–vis)
spectrum was recorded on a Lambda-950 (PerkinElmer) spectropho-
tometer in range of 200–800 nm in a diffuse reflectance regime. The light
beam was focused on the sample surface using a lens into a spot about
2 ꢃ 4 mm in size.
ν
(Se–O–M) vibrations [11,32]. UV–vis diffuse reflectance spectroscopy
(DRS) spectrum is shown in Fig. 2b. It is in agreement with the
yellow-green colour of the examined substance. The band gap estimation
from DRS spectrum by Kubelka - Munk function results in electron band
gap value Eg ¼ 2.82 ꢁ 0.02 eV.
3.3. Magnetic properties
2.7. Magnetic properties
The magnetic properties of CdCu2(SeO3)2Cl2 are typical for a dimer
system. In a wide temperature interval, it presents no evidence for a long-
range magnetic order formation. The temperature dependence of the
The magnetization M in the temperature range 2–300 K in a magnetic
field B up to 9 T has been measured using vibrating sample magnetom-
eter (VSM) of “Quantum Design” Physical Properties Measurements
System PPMS-9T on powder sample.
magnetic susceptibility
χ
¼ M/B taken at B ¼ 0.1 T in a field-cooled
regime is shown in Fig. 3. The magnetic susceptibility
χ
passes through
broad maximum at Tmax ~290 K. In accordance with Tmax ~0.64J ratio
[34], this value defines the exchange interaction parameter within a
dimer J ~ 450 ꢁ 10 K (spin gap Δ ¼ 38.7 ꢁ 0.8 meV). At low temper-
atures, the behaviour of magnetization is dictated by the defects/im-
3. Results and discussion
3.1. Crystal structure
purities which follows the Curie law
χ
¼ C/T. Assuming defects with spin
There are three independent positions of Cd, Cu and Se atoms in the
crystal structure of CdCu2(SeO3)2Cl2. Cd atoms are surrounded by 4 Cl
and 2 O which form distorted octahedron with short Cd–O distances
2.336 Å and longer Cd–Cl distances 2.63–2.64 Å (Table 2). Cu atoms
exhibit usual Jahn-Teller distorted 4 þ 2 surrounding [CuO4Cl2]
(Table 2). Cu–O distances are in range 1.939–1.994 Å and there are two
Cl atoms in distances 2.798 and 2.783 Å. Selenium atoms are located at
the top of the trigonal pyramidal SeO23ꢂ groups with Se–O distances
1.666–1.730 Å. [CdO2Cl4] octahedra share their common Cl–Cl edges
and form the chains along [100] direction of the structure (Fig. 1a and
Fig. S3). Distorted copper polyhedra form double chains running along
[001] direction of the crystal structure (Fig. 1b). These chains are orga-
nized by [Cu2O6Cl4] dimers with Cu–Cu distances 3.100(2) By common
Cl apexes these dimers form the two-leg ladders. Cu–Cu distances along
S ¼ 1/2 and g-factor g ¼ 2, their quantity is estimated as 0.8%. The
paramagnetic response of impurities is supported by the field depen-
dence of magnetization M(B) taken at 2 K, as shown in the inset to Fig, 3.
3.4. Density functional calculations
Density-functional band structure calculation for CdCu2(SeO3)2Cl2
was performed within generalized gradient approximation (GGA) using
the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional [35]
as implemented in Vienna ab initio simulation package VASP [36,37].
The energy cutoff for the plane-wave basis was set to 500 eV and energy
convergence criteria was set to 10ꢂ6 eV. For the Brillouin zone integra-
tion a 6 ꢃ 6 ꢃ 6 Monkhorst-Pack mesh was used. Correlation effects were
Fig. 1. Chains of [CdO2Cl4] octahedra and double chains of Cu2O6Cl4 dimers form 3D framework (left panel), the view on ab plane of the CdCu2(SeO3)2Cl2 crystal
structure with Cd atoms omitted (right panel).
3

A.F. Murtazoev et al.
Journal of Solid State Chemistry 303 (2021) 122518
Fig. 2. IR transmission spectra (left panel), Tauc plot for Kubelka - Munk band gap estimation for CdCu2(SeO3)2Cl2. UV–vis DRS spectrum is shown in the inset
(right panel).
Fig. 3. The temperature dependence of magnetic susceptibility
χ ¼ M/B in
CdCu2(SeO3)2Cl2 taken at B ¼ 0.1 T in a field-cooled regime. The inset repre-
sents the field dependence of magnetization M taken at T ¼ 2 K. Violet dash-dot
line represents dimer model approximation, the blue-dash line – Curie-Weiss
dependence and the red line is the sum of these two parts for magnetic sus-
ceptibility χ. (For interpretation of the references to colour in this figure legend,
the reader is referred to the Web version of this article.)
taken into account within the static mean-field DFT þ U approach in
rotationally invariant form introduced by Lichtenstein et al. [38]. We
used the Coulomb repulsion parameter U ¼ 8.5 eV and Hund's exchange
JH ¼ 0.95 eV [39]. These calculations result in the energy gap value of
2.4 eV, as shown in Fig. 4. The partial Cu-d and O-p densities of states are
shown in Fig. 4 (middle and lower panels). One can see that the top of the
valence band is formed by O-p states while the bottom of the conduction
band consists from empty Cu-d states. The exchange interaction param-
eter J within Cu–Cu dimer was extracted from the total energy difference
of four different spin configurations (see Fig. 5) using the mapping
procedure within DFT þ U method [40]. There are eight copper ions in
the unit cell of CdCu2(SeO3)2Cl2. According to this consideration in order
to obtain the exchange interaction between two Cu sites, lets take Cu2
and Cu5 (see Fig. 5) to evaluate exchange interaction within Cu dimer,
one needs to calculate the total energy of four spin configurations: E1, E2,
E3, E4, in which spins on Cu2 and Cu5 sites are ↑↑, ↑↓, ↓↑, ↓↓, while the
spin orientations on other Cu site are the same for all four configurations
(Fig. 5). Then J¼(E1þE4-E2-E3)/4 S2, where S ¼ 1/2 for Cu2þ ion [40].
We obtained J ¼ 425 K which is in good agreement with the value
estimated from the maximum of magnetic susceptibility. Using the same
procedure for the Cu2 and Cu7 ions we calculate the exchange
Fig. 4. The total (upper panel) and partial Cu-d (middle panel) and O-p (lower
panel) density of states in CdCu2(SeO3)2Cl2 calculated within GGA þ U method.
The dotted line marks the position of the Fermi level.
interaction between dimers, which turns up to be only 0.4 K.
4. Conclusions
CdCu2(SeO3)2Cl2 is the first representative of MM’2(ZO3)2Cl2 system
where both metal ions, M and M’, are transition metals. As predicted, its
crystal structure represents an open channel three-dimensional frame-
work. The copper polyhedra form magnetically isolated dimers with a
spin gap 38.7 ꢁ 0.8 meV, while the gap in electronic spectrum is
2.82 ꢁ 0.02 eV. Density functional theory provides the values of electron
(2.4 eV) and spin (36.6 meV) gaps comparable with experimental ob-
servations. These data define CdCu2(SeO3)2Cl2 as
a novel low-
dimensional system characterized by the presence of the spin gap. This
fact has interest both experimentally and theoretically.
During the manuscript evaluation process, the communication about
CdCu2(SeO3)2Cl2 has appeared in the literature [41]. The compound was
obtained by hydrothermal process and shows the same magnetic
4

A.F. Murtazoev et al.
Journal of Solid State Chemistry 303 (2021) 122518
Fig. 5. Four spin configurations used to calculate exchange interaction J between Cu2 and Cu5 sites in CdCu2(SeO3)2Cl2.
Cu3Bi(SeO3)2O2X (X ¼ Cl, Br and I), J. Mater. Chem. 11 (2001) 1152–1157,
https://doi.org/10.1039/B007920K.
behavior. It may be notices that hydrothermally prepared CdCu2(-
SeO3)2Cl2 possess little bit bigger unite cell parameters that obtained by
solid state or vapor transport reactions.
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CRediT authorship contribution statement
Alisher F. Murtazoev: Methodology. Peter S. Berdonosov: Meth-
odology, Conceptualization, Writing
– original draft. Victor A.
Tafeenko: Methodology. Valery A. Dolgikh: Methodology, Conceptu-
alization, Supervision. Igor L. Danilovich: Methodology. Zlata V.
Pchelkina: Methodology, Writing – original draft, Funding acquisition.
Alexander N. Vasiliev: Conceptualization, Writing – review & editing,
Funding acquisition.
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This work has been supported by M.V. Lomonosov Moscow State
University Program of Development and by Megagrant program P220 of
the Government of Russian Federation, project 075-15-2021-604. by
program “Quantum” AAAA-A18-118020190095-4 by Act 211 of the
Government of Russian Federation. The electronic structure calculations
have been supported by RFBR grant 20-32-70019.
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