Copper polytellurite-chlorides with A2?+ cations ([Formula presented], Pb) obtained by CVT reactions

Article abstract of DOI:10.1016/j.inoche.2016.07.007

Two novel polytellurite-chlorides Pb₅Cu₂(Te₄O₁₁)Cl₈ (1) and CdCu₂(Te₃O₈)Cl₂ (2) were obtained by a chemical vapor transport (CVT-reactions) reactions. The structure of 1 is based on [Pb₅Cu₂(Te₄O₁₁)]^8?+ one-dimensional blocks with full and partially occupied Cl sites around. The structure of 2 can be described as being formed by two types of one-dimensional units formed by Cd,Cu-centered polyhedra and TeO₃, TeO₄ pyramids sharing via common O atoms into electroneutral [CdCu₂(Te₃O₈)Cl₂]⁰ sheets. Obtaining of novel polytellurite-chlorides demonstrates effectiveness of CVT techniques for preparation of different tellurite-based complex layered materials.

Full text of DOI:10.1016/j.inoche.2016.07.007

Copper polytellurite-chlorides with A2 + cations (A = Cd, Pb) obtained by
CVT reactions
Diana O. Zinyakhina, Oleg I. Siidra, Dmitri O. Charkin, Evgeniy V.
Nazarchuk, Rimma S. Bubnova
PII:
DOI:
Reference:
S1387-7003(16)30231-3
doi: 10.1016/j.inoche.2016.07.007
INOCHE 6383
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
8 June 2016
3 July 2016
9 July 2016
Please cite this article as: Diana O. Zinyakhina, Oleg I. Siidra, Dmitri O. Charkin,
Evgeniy V. Nazarchuk, Rimma S. Bubnova, Copper polytellurite-chlorides with A2 +
cations (A = Cd, Pb) obtained by CVT reactions, Inorganic Chemistry Communications
(2016), doi: 10.1016/j.inoche.2016.07.007
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Copper polytellurite-chlorides with A2+ cations (A=Cd, Pb) obtained by CVT reactions
Diana O. Zinyakhinaa, Oleg I. Siidraa,*,
Dmitri O. Charkinb, Evgeniy V. Nazarchuka, Rimma S. Bubnovaa
aDepartment of Crystallography, St. Petersburg State University, Universitetskaya Nab. 7/9, 199034
St.Petersburg, Russia
bDepartment of Chemistry, Moscow State University, GSP-1, Moscow, 119991 Russia
* Corresponding author. Tel. +7 812 3506688. E-mail address: o.siidra@spbu.ru
ABSTRACT. Two novel polytellurite-chlorides Pb5Cu2(Te4O11)Cl8 (1) and CdCu2(Te3O8)Cl2 (2)
were obtained by a chemical vapour transport (CVT-reactions) reactions. The structure of 1 is based
on [Pb5Cu2(Te4O11)]8+ one-dimensional blocks with full and partially occupied Cl sites around. The
structure of 2 can be described as being formed by two types of one-dimensional units formed by
Cd,Cu-centered polyhedra and TeO3, TeO4 pyramids sharing via common O atoms into
electroneutral [CdCu2(Te3O8)Cl2]0 sheets. Obtaining of novel polytellurite-chlorides demonstrates
effectiveness of CVT techniques for preparation of different tellurite-based complex layered
materials.
KEYWORDS: copper, tellurium, polytellurites, CVT-reactions, single crystal x-ray
diffraction, lone-pair
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Crystalline materials with Te(IV) and divalent metal cations have received attention for their
fascinating structural chemistry and physical properties [1-5]. One-sided TeO3, TeO4 or TeO5
coordination environments are very typical for Te4+ cations due to the presence of 5s2 lone electron
pair. Te4+On polyhedra reveal tendency to form various Te4+ Om polyanions in contrast to Se4+- and
n
I5+-centered polyhedra. The degree of Te4+ Om polymerization is affected by the type and number of
n
the other cations within the structure. Tellurite compounds with Cu2+ represent particular interest in
the sense of copper asymmetric coordination environments attributable to Jahn–Teller distortions.
Many of copper tellurite halides reveal interesting magnetic properties [6-8]. Insertion of large Pb2+
cations or Cd2+ into copper tellurite chlorides may result in formation of unusual structural
topologies and possible interesting properties. To date only one Pb-Cu tellurite chloride was reported
PbCu2(TeO3)2Cl2 [8] and Cd-Cu tellurite chlorides are unknown. Recently we have employed
chemical vapor transport reactions for obtaining of Cu2+ selenite chlorides with various cations
[9,10]. Thus it was decided to apply the latter method of synthesis for tellurite containing systems.
Herein we report on the synthesis and structural studies of Pb5Cu2(Te4O11)Cl8(1) and
CdCu2(Te3O8)Cl2(2) obtained in evacuated quartz ampoules in CuCl2-TeO2-PbO and CuCl2-TeO2-
CdO system, respectively [11-13].
The structure of 1 contains five symmetrically independent Pb2+ cations, two Cu2+, and four
Te4+ sites. The coordination of all Pb sites is asymmetric due to the presence of the stereochemically
active lone-pairs. Shorter and stronger Pb-O bonds are located in one coordination hemisphere and
longer Pb-Cl in another. Te(1) and Te(2) atoms form TeO3 trigonal pyramids with three short
distances ranging from 1.8614(3) to 1.8908(2) Å for Te(1) and from 1.8365(3) Å to 1.8873(2) Å for
Te(2). Te(3) and Te(4) form TeO4 polyhedra. Te(3) have three short Te-O bonds of 1.8940(2)-
1.9231(3) Å and one long Te(3)-O(4) bond of 2.3982(4) Å. Te(4) coordination is similar to Te(3).
Thus Te sites demonstrate typical for Te4+ coordination environments with formation of Te(1)O3,
Te(2)O3 and Te(3)O4, Te(4)O4 pyramids further interconnected via common corners into [Te4O11]6+
tetrameric units (Fig. 2). Similar [Te4O11]6+ isolated units were previously reported in Pr2Te4O11
[16], Er2Te4O11[17], Sr3Te4O11 [18] and Ni15Te12O34Cl10 [19]. The structure of 1 contains also two
symmetrically independent Cu atoms forming CuO4 squares isolated one from each other and further
complemented by Cl atoms to CuO4Cl2 octahedra with the average <Cu-Cl> bond lengths equal to
2.8921(3)-2.962(5) Å. Taking into account only the strongest A-O (A = Pb, Te, Cu) bonds one-
dimensional [Pb5Cu2(Te4O11)]8+ block in the structure of 1 can be obtained via the list of subsequent
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Fig. 1. General projections of the structure of 1 (below) and 2 (above) and their schematic
representations (lone pairs on Pb2+ and Te4+ are symbolized as e). The structure of 1 (a) represents
type of structural architecture with positively charged [Pb5Cu2(Te4O11)]8+ one-dimensional units and
Cl- anions (partially occupied Cl sites are highlighted) associating with stereochemically active lone
electron pairs in between (b). The structure of 2 (c) consists of neutral [CdCu2(Te3O8)Cl2]0 layers (d)
interconnected via weak A-Cl (A = metal) bonds only. Crystals of 1 and 2 were obtained by the
chemical vapour transport reactions in evacuated quartz ampoules. Crystals of 1 were grown in the
deposition part of the tube, whereas crystals of 2 are observed in the source zone.
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Fig. 2. [Pb5Cu2(Te4O11)]8+ block (a) in the structure of 1 can be obtained according to the following
subsequent transformations: (1) [Pb3Cu2O11)] units (b) are formed by CuO4 squares and one-sided
PbO4 and PbO2 polyhedra which are further stacked via common O(3) atoms and related by
inversion center; (2) tellurite tetramers are inserted (c) in between [Pb3Cu2O11)]; (3) additional Pb(3)
and Pb(5) atoms are attached under and above [Pb3Cu2(Te4O11)] units (d) thus forming
Pb5Cu2(Te4O11)]8+ blocks (e).
transformations listed in Fig. 2. There are a number of Cl sites compensating positive charge of
[Pb5Cu2(Te4O11)]8+ one-dimensional blocks in the structure of 1. Lone-electron pairs on Te4+ and
Pb2+ demonstrate typical halophilic behavior and locate jointly in the areas with Cl sites. Cl(1)-Cl(6)
sites are fully occupied, whereas the rest of Cl sites demonstrate partial occupancies. Partially
occupied Cl(7)-Cl(13) sites are segregated into separate regions of the structure of 1 depicted in Fig.
1 and reveal possible pathways for ionic conduction.
The structure of 2 contains one Cd2+ cation, one Cu2+, and two Te4+ sites (Fig. 3). Cd atoms
are coordinated by four O with the Cd-O bond lengths in the range of 2.313(1) - 2.414(1) Å and two
Cl atoms at distances of 2.540(2) Å thus forming irregular CdO4Cl2 polyhedra. Te atoms form two
types of polyhedra: TeO3 and TeO4. Te(1) atoms form three short Te(1)-O bonds in the range of
1.883(1)-1.911(1) Å, whereas Te(2) form four short Te(2)-O bonds each in the range of 1.868(1)-
2.165(1) Å. The crystal structure of 2 contains one symmetrically independent Cu site coordinated
by four O atoms thus forming CuO4 squares (Fig. 3). CuO4 squares share common edges thus
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forming Cu2O8 dimers (Fig. 3). CdO4Cl2 polyhedra and Cu2O8 dimers via common corners produce
one-dimensional
Fig. 3. Cations coordination environments in the structure of 2 (a, b). Cu2O6 dimers and CdO4Cl2
share via common corners into one-dimensional units (a), whereas TeO4 and TeO3 pyramids form
[Te3O8]4- trimers (b). General projection of [CdCu2(Te3O8)Cl2]0 units along the b axis (c).
Orientation of Cd-Cu oxochloride (d) and [Te3O8]4- units (e) in the structure of 2.
chains in the structure of 2 (Fig. 3a,c). TeO3 and TeO4 pyramids form [Te3O8]4- polyanions. The
structure of 2 can be described as being formed by two intertwisting one dimensional units formed
by Cd,Cu-centered polyhedra and tellurite pyramids thus forming electroneutral [CdCu2(Te3O8)Cl2]0
sheets parallel to the (001) plane (Fig. 2). The interlayer space is occupied by lone-pairs on Te4+
cations. Compounds with electroneutral layers formed by lone-pair and transition elements were
recently described as promising materials in different fields [20-22]. However crystal structure of 2
is the first example of such kind of structural architecture with Cd2+ cations.
In conclusion, our exploration of copper-tellurite systems with Pb2+ and Cd2+ produced two
novel polytellurite-chlorides with complex structural topologies and demonstrates effectiveness of
CVT techniques for preparation of different Te-based complex layered materials. Tellurites and
metal halides play the role of transport agents. This method hasn’t been used before for obtaining of
Cd and Pb containing tellurites. However, difficulties of this method to obtain pure phases should be
taken into account. Formation of Cu2O8 dimers in the structure of 2 could be of interest from the
viewpoint of interesting magnetic properties. We are in the process of exploring new tellurite based
compounds with copper by this method and their properties.
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Acknowledgments
This work was supported by St. Petersburg State University through the internal grant
3.38.238.2015 and RFBR 15-35-20632. Technical support by the X-Ray Diffraction Resource
Centre of Saint-Petersburg State University is gratefully acknowledged.
Appendix A. Supplementary data
CSD entries 431271 and 431270 contain structural data for 1 and 2, respectively. Supplementary
data for this paper can be found online at http://dx.doi.org/XX.XXXX/*.
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Figure 1
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Figure 2
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Figure 3
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Graphical abstract
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Graphical abstract legend
Single crystals of new copper polytellurite chlorides with Cd and Pb were prepared by
chemical vapor transport reactions → Both of compounds demonstrate novel structure types → The
structure of 1 represents type of structural architecture with positively charged [Pb5Cu2(Te4O11)]8+
one-dimensional units and Cl- anions associating with stereochemically active lone electron pairs in
between → The structure of 2 consists of neutral [CdCu2(Te3O8)Cl2]0 layers interconnected via
weak A-Cl (A = metal) bonds only with lone electron pairs on Te4+ in between
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