Interpenetrated and Catenated Zinc Thiosulfates Frameworks with dia and qtz Nets: Synthesis, Structure, and Properties

Article abstract of DOI:10.1021/acs.cgd.6b00051

Reactions between Zn(NO₃)₂·6H₂O, Na₂S₂O₃, 4,4′-bipyridine (bpy), 1,2-bis(4-pyridyl)ethene (bpe), 1,2-bis(4-pyridyl)ethane (bpa), and 1,3-bis(4-pyridyl)propane (bpp) under solvothermal conditions resulted in four new zinc thiosulfate hybrid compounds. Compound I has four-membered zinc thiosulfate rings connected by the ligand, 1,3-bis(4-pyridyl)propane (bpp) forming a two-dimensional structure. Compounds II-IV have one-dimensional zinc thiosulfate chains connected by the ligands, bpy (II), bpe (III), and bpa (IV) giving rise to three-dimensional structures. All the four-structures exhibit 3-fold interpenetration. Proton conductivity studies indicate reasonable proton mobility at 34 °C and at 98% relative humidity. The compounds also exhibit Lewis acid character and good photocatalytic activity for the decomposition of cationic dyes.

Full text of DOI:10.1021/acs.cgd.6b00051

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Article
Interpenetrated and Catenated Zinc thiosulfates frameworks
with dia and qtz nets: Synthesis, Structure, and Properties
Srinivasan Natarajan, and Rajendran Karthik
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00051 • Publication Date (Web): 10 Mar 2016
Downloaded from http://pubs.acs.org on March 12, 2016
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Interpenetrated and Catenated Zinc thiosulfates frameworks
with dia and qtz nets: Synthesis, Structure, and Properties
*
Rajendran Karthik and Srinivasan Natarajan
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Framework solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of Science,
Bangaloreꢀ560012, India.
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Corresponding Author, Eꢀmail: snatarajan@sscu.iisc.ernet.in
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Abstract
Reactions between Zn(NO
3 2 2 2 2 3
) .6H O, Na S O , 4,4′ꢀbipyridine (bpy), 1,2ꢀbis(4ꢀpyridyl)ethene (bpe),
1,2ꢀbis(4ꢀpyridyl)ethane (bpa)and 1,3ꢀbis(4ꢀpyridyl)propane (bpp) under solvothermal conditions resulted in
four new zinc thiosulfate hybrid compounds. Compound I has 4ꢀmembered zinc thiosulfate rings connected by
the ligand, 1,3ꢀbis(4ꢀpyridyl)propane (bpp) forming twoꢀdimensional structure. Compound II – IV have oneꢀ
dimensional zinc thiosulfate chains connected by the ligands, bpy, (II) bpe,(III) and bpa (IV) giving rise to
threeꢀdimensional structures. All the fourꢀstructures exhibit threeꢀfold interꢀpenetration. Proton conductivity
studies indicate reasonable proton mobility at 34 °C and at 98% relative humidity. The compounds also exhibit
Lewis acid character and good photocatalytic activity for the decomposition of cationic dyes.
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Introduction
Phosphate and silicate based framework compounds, with interconnected channels and cavities have
been investigated extensively for their many applications in the area of catalysis, luminescence, sorption and
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separation processes. The new family of framework compounds based on carboxylates, known as metalꢀ
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organic frameworks (MOF) or inorganic coordination polymers (CP), are being studied vigorously during the
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past two decades for their many potential applications in sorption and catalysis.
The studies on MOFs and
related compounds have brought out the usefulness of nitrogen containing aromatics as ligands and structure
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builders.
The usefulness of 4,4′ꢀbipyridine in extending the dimensionality of the structure was established
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during the preparation of phosphates and related structures.
This strategy was also adapted for the
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preparation of many other compounds.
We have been interested in the study of phosphates, phosphites, arsenates and other related compounds
over the years to understand the possible pathways of formation of such structures and also for their interesting
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physical properties such as magnetism.
One of the ways to rationalize the formation of compounds with
open structures could be to think in terms of the subtle balance between the acids and bases that are involved in
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the preparation of such compounds. The hardꢀsoft acids and bases (HSAB) theory of Pearson appears to hold
some promise towards the understanding of the formation of the framework structures of phosphates, sulfates,
carbonates etc.
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Of the many anions, the borates were explored recently as a framework builder.
We have also
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investigated the usefulness of thiosulfates in the formation of hybrid structures.
Though modest success has
been achieved in the stabilization of thiosulfate as part of the framework, the issue with regard to the synthesis
of thiosulfate frameworks are many. Thiosulfate, similar to sulfate, is a tetrahedral ion with identical charge (ꢀ
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2). Sulfates were shown to form interesting framework structures during the last decade.
Thiosulfates on the
other hand, appear different and the following points may be relevant: (i) thiosulfate is a heteroꢀanion with three
oxygen and one sulfur atoms; (ii) the two distinct sulfur species have different oxidation states (+6 and ꢀ2,
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ꢀ
2 3
respectively); (iii) the bond strengths of the SꢀO and SꢀS bonds within the (S O ) anion would be different as
indicated by the bond distances (SꢀO ~ 1.45 Å and SꢀS ~ 2 Å). These factors would make the thiosulfates
sensitive under the harsh hydrothermal reactions, normally employed for the synthesis of openꢀframework
phosphates and silicates. The thiosulfate tends to breaks down under high acidic as well as basic pH and also at
higher temperatures forming elemental sulfur. The elemental sulfur would be reactive and form metal sulfides
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readily. From the HSAB theory, thiosulfate anions are soft bases and it is preferable to react with soft acids or
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intermediate acid cations. Our earlier studies on the use of soft acid cations such as Cd was successful in the
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formation of new thiosulfate frameworks.
As a continuation of this theme of research, we have now
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investigated the reactivity of intermediate acid cations such as Zn by employing a panoply of strategies. Our
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efforts have been successful and we have now isolated four new Zinc thiosulfate phases: [Zn(S
2 3
O )(bpp)] I,
[
Zn (S (bpy) ] II, [Zn(S )(bpe)].H O III and [Zn (S (bpa) ].3H O IV. In this paper, we describe the
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synthesis, structure and properties of the zinc thiosulfate compounds.
Experimental Section
Synthesis and initial characterization
3 2 2 2 2 3
The reagents Zn(NO ) .6H O [CDH India, 98%], Na S O ,[Fluka, 99%], 4,4′ꢀbipyridine (bpy)
[Aldrich, 98%], 1,2ꢀbis(4ꢀpyridyl)ethene (bpe) [Aldrich, 98%], 1,2ꢀbis(4ꢀpyridyl)ethane (bpa) [Aldrich, 98%]
and 1,3ꢀbis(4ꢀpyridyl)propane (bpp) [Aldrich, 98%] were used as purchased without any further purification.
3 2 2 2 2 3
In a typical synthesis for I, Zn(NO ) .6H O (0.297 g, 1mM), Na S O (0.158 g, 1mM), bpp ( 0.198 g, 1
mM) were taken in a mixture of 4ml of distilled water and 6ml of methanol. The mixture was stirred at room
temperature for 30 minutes. The homogenized mixture was transferred and sealed into a 23 mL PTFE lined
stainless steel autoclave and heated at 80°C for 72h. On cooling, yellow colored block crystals were filtered
under vacuum, washed with deionized water and dried at ambient conditions. Compound II, III and IV were
prepared employing similar synthetic procedure (Table 1). Elemental Analysis of the products in each case was
carried out using Thermo Finnigan FLASH EA 1112CHN analyzer (Table 1).
The prepared compounds were characterized by powder Xꢀray diffraction (PXRD), IR, UVꢀvisible and
Photoꢀluminescence (PL) spectroscopic studies. The PXRD patterns were recorded in the 2θ range 5ꢀ50°
employing Cu Kα radiation (λ=1.5418Å, Philips X′pert). The observed PXRD patterns were found to be
consistent with the simulated PXRD patterns generated from the single crystal Xꢀray structure (ESI, Figure S1ꢀ
S4). The Infrared (IR) spectroscopic studies were carried out using PerkinꢀElmer, SPECTRUM 1000.
The IR spectra for all the compounds exhibited characteristic bands (ESI, Figure S5).The IR spectra of
ꢀ
1
compounds I – IV were interpreted in five distinct regions. 1) A broad band centered around 3412, 3495 cm
ꢀ
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and 3479, 3570 cm , respectively for III and IV could be due to the symmetric and antiꢀsymmetric stretching
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ꢀ
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of the lattice water molecule; 2) A band at ~ 3072cm indicates aromatic υ(CH) modes of pyridine skeleton; 3)
ꢀ
1
a band in the range of 1660ꢀ1200 cm indicates CꢀH bending vibrations due to symmetric and asymmetric
ꢀ
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stretching modes of the pyridine ring; 4) a sharp band at 1129cm could be due to SꢀO; 5) bands in the range of
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00 – 800 cm could be due to the bending modes of SꢀO and SꢀS of the thiosulfate unit. The observed IR
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bands were similar to those reported in earlier thiosulfate framework compounds
.
Thermogravimetric analysis (TGA) was carried out in flowing oxygen atomosphere (flow rate = 20ml
ꢀ
1
ꢀ1
min ) in the temperature range 30 – 850 ºC (heating rate = 5 ºC min ) (ESI, Figure S6) The TGA studies
indicate that compound I exhibits weight loss in two steps. The first weight loss of 52.6% observed in the
temperature range of 285 – 310 °C corresponds to the loss of 1,3ꢀbis(4ꢀpyridyl)propane and the second more
broader loss of 21.2% observed in the temperature range 490 ꢀ 720 °C corresponds to the loss of one thiosulfate
unit. The total weight loss of 73.8% corresponds with the loss of the 1,3ꢀbis(4ꢀpyridyl)propane and one
thiosulfate unit (calc. 73.9%). Compound II also exhibits one main weight loss followed by a tail. The weight
loss in the narrow range of 400 – 410 °C of ~ 62.3% corresponds to the loss of the 4,4′ꢀbipyridine. The tail end
temperature range of 575 ꢀ 625 °C exhibits a weight loss of 11.4%, which corresponds to the loss of two
thiosulfate moieties. The total weight loss of 73.7% corresponds to the loss of two 4,4′ꢀbipyridine molecules
and two thiosulfate units (calc. 71.8%). Compound III exhibits an initial weight loss of 4.2% in the temperature
range of 30 ꢀ 110 °C, which may be due to the loss of the adsorbed and lattice water molecule. The weight loss
of 54.3 % in the range 140 ꢀ 220 °C, corresponds to the loss of 1,2ꢀbis(4ꢀpyridyl)ethene . A broad weight loss of
14.4% between 220 ꢀ 600 °C, may be due to the loss of one thiosulfate unit. The total weight loss of 72.9%
corresponds with the loss of 1,2ꢀbis(4ꢀpyridyl)ethene and one thiosulfate units and the lattice water molecule
(
calc. 75.6%). Compound IV also exhibits similar weight loss of 4.5% in the temperature range of 170 ꢀ 220 °C,
which would correspond to the loss of three lattice water molecule. The weight loss of 51.1% in the temperature
range of 230 – 480 °C which corresponds to the loss of three 1,2ꢀbis(4ꢀpyridyl)ethane. The weight loss of 19.6
%
observed in the temperature range of 530 ꢀ 770 °C, corresponds to the loss of three thiosulfate unit. The total
weight loss of 74.2% corresponds with the loss of three 1,2ꢀbis(4ꢀpyridyl)ethane and three thiosulfate units and
three lattice water molecule (calc. 75.6%). In all the cases, the PXRD of the calcined products suggested that
the majority of the observed lines correspond to a mixture of ZnSO
phases.
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(ICSD: 150578) and ZnO (ICSD: 182358)
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The solid state diffuse reflectance UVꢀvisible spectroscopic studies were carried at room temperature
PerkinꢀElmer model Lambda 35 UV) (ESI, Fig.S7). The reflectance spectra was then converted into a
(
absoption like spectra employing the KubelkaꢀMunk function. The observed absorbance peaks for the free
ligands bpa, bpy, bpe, bpp and Na are ~307nm (4.03 eV), 305 nm (4.06 eV), 324 nm (3.82 eV), 302 nm
4.10 eV) and 290 nm (4.27 eV) respectively. The absorbance peaks for compounds were observed to be
2 2 3
S O
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centered around ~ 264 and 397 nm (I), ~ 252 and 316 nm (II), ~ 337 and 486 nm (III) and ~ 260 and 312 nm
(IV). The peaks around ~260nm (4.76 eV) could be due to the thiosulfate ion and the peaks around ~310 – 340
nm (4 – 3.64 eV) may be due to the intraligand electron transfer and the peaks around ~486 nm (2.55 eV) may
be due to the charge transfer from the ligand to the metal. The observed values are similar to those observed for
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the cadmium thiosulfate phases.
We have also carried out photoluminescence studies for the compounds I - IV along with free bpy,
bpe, bpa and bpp ligands in the solid state at room temperature (ESI, Figure S8ꢀ11). The main emission peak
for free bpy, bpa was centered around ~ 368 nm, for bpp ~ 385nm (λex=310nm) and for bpe ~ 397nm, when
excited using 310 nm wavelength. These emissions can be attributed to π* → π or π* → n transitions. The
thiosulfate compounds exhibit a redꢀshift of ~60nm compared to the ligands with the emission peaks centered
around 437nm (I and II), 424nm (III) and 440nm (IV) when excited using a wavelength of λex=316nm. This
band could be the charge transfer band from the ligand to the metal center (LMCT).
Single crystal structure determination
A single crystal of each compound was carefully selected under a polarizing optical microscope and
glued to a thin glass fiber. The single crystal data was collected at room temperature 293(2)K on a Oxford
Xcalibur (Mova) diffractometer equipped with an EOS CCD detector. The Xꢀray generator was operated at 50
kV and 0.8 mA using Mo Kα (λ ꢀ= 0.71073 Å) radiation. The cell refinement and data reduction were carried
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out using CrysAlis RED. The structure was solved by direct methods and refined using SHELX97 present in
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the WinGX suit of programs (version 1.63.04a). The hydrogen positions for the ligands were initially located
from the difference Fourier map, and for the final refinement, they were placed in geometrically ideal positions
and refined in the riding mode. The hydrogen positions for the water molecules in III, IV however, could not
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be located from the difference fourier maps. The full matrix leastꢀsquares refinement against |F | was carried out
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using the WinGx suite of programs. The final refinements included atomic positions for all the atoms,
anisotropic thermal parameters for all the nonꢀhydrogen atoms, and isotropic thermal parameters for all the
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hydrogen atoms. The details of the structure solution and final refinement parameters are given in Table 2. The
crystallographic data for the compounds I - IV were deposited with the Cambridge Crystallographic Data
Center (CCDC). The CCDC numbers for the compounds are: I – 940249, II – 940248, III – 940250, IV ꢀ
940251.
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Results and Discussion
2 3 14 2
Structure of [Zn(S O )(C13H N )], I
The asymmetric unit of I contains 21 nonꢀhydrogen atoms, comprising of one crystallographically
independent Zn(II) ion, one thiosulfate and one 1,3ꢀbis(4ꢀpyridyl)propane (bpp). The Zn(II) ions are
tetrahedrally coordinated with one oxygen and a sulfur atom from the thiosulfate unit and two nitrogen atoms
from the 1,3ꢀbis(4ꢀpyridyl)propane unit. The average ZnꢀS, ZnꢀO and ZnꢀN bond distances are 2.296, 1.981 and
2.043 Å, respectively. The SꢀZnꢀO and NꢀZnꢀN bond angles are 105.4(9)° and 104.0(1)° suggesting tetrahedral
coordination. The thiosulfate unit has an average bond angle of 109.4°. The various bond lengths and angles
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observed in I are comparable to those observed for the cadmium thiosulfate compounds.
Selected bond
distances are listed in Table 3.
2 2 3
The ZnN OS and S O tetrahedral units are connected through their vertices forming a simple fourꢀ
membered ring. The fourꢀmembered ring units are connected by bpp units forming a twoꢀdimensional layer
structure (Figure 1a). Two such layers are arranged in a way that they are in a direction perpendicular to each
other as shown in Figure 1b. The arrangements of the layers are such that they are catenated to each other
(Figure 1b). To the best of our knowledge, this is the first observation of catenated layered structure involving
thiosulfate hybrids. In addition, it may be noted that the structure of I has the basic building unit, the 4ꢀ
membered ring, formulated to be the fundamental building unit in the tetrahedral structures of aluminosilicate
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and aluminophosphates.
The observation of the simple 4ꢀmembered ring structure in the present compounds
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suggests that it may be possible to prepare compounds that are similar to the phosphates and silicates.
From a topological view, if we considered the 4ꢀmembered ring as a node, then it would result in a
simple 4ꢀconnected net (Figure 1c). The 4ꢀconnected nets here are catenated by two perpendicular rhombus
grids as shown in Figure 1c.
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Structure of [Zn (S O ) (C H N ) ], II
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The asymmetric unit of II contains 36 nonꢀhydrogen atoms comprising of two Zn(II) ions, two
thiosulfate unit and two 4,4′ꢀbipyridine (bpy) ligands. The zinc atoms Zn(1) and Zn(2), are tetrahedrally
coordinated with one oxygen and one sulfur atom from the thiosulfate units and two nitrogen atoms from the
bpy ligand. The average ZnꢀO, ZnꢀS and ZnꢀN distances are 1.989 Å, 2.260 Å and 2.018 Å, respectively. The
thiosulfate units SꢀS and SꢀO have average bond distances of 2.044 and 1.459 Å. The average bond angles
surrounding Zn(1) is 107.4° and for Zn(2) it is 107.9°. The thiosulfate unit has an average angle of 109.7°. The
bond angles suggest that the participating tetrahedral units are slightly distorted.
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The Zn(II) ion is connected with two thiosulfate units via the oxygen and sulfur atoms forming a oneꢀ
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dimensional chain (Figure 2a). The Zinc thiosulfate chain is arranged in a helical fashion around the 2 screw
axis. The 4,4′ꢀbipyridine (bpy) units connect the chains by bonding with alternate Zn(II) ion forming a twoꢀ
dimensional sheet (Figure 2b). The bpy units were twisted around the central CꢀC bond with an average torsion
angle of 26.4°. The 2D sheets are further connected by another bpy units giving rise to a threeꢀdimensional
structure with large channels (18.7 Х 15.8 Å) (atomꢀatom contact distance not including the vander Waals
radii). (Figure 2c) The large voids in this structure are not sustainable and give rise to interpenetration. In II, we
observed a threeꢀfold interpenetration of the 3D structure (Figure 3b).
From a topological perspective, II can be viewed as a diamondoid net as the participating ligands are
tetrahedral in nature. The diamondoid structure is generally observed where the participating nodes are
tetrahedral in nature. The diamondoid structures have been observed commonly in many metalꢀorganic
61ꢀ66
framework hybrid compounds.
Here, the Zn(II) ions acts as the tetrahedral node (coordinated with two bpy
2
ꢀ
and two S
2
O
3
units). The connectivity between Zn, S
2
O
3
and bpy gives rise to an adamentane type unit, which
6
is common for all the diamondoid networks. (Figure 3a) The schlafli symbol is 6 . The present structure appears
to be the first observation of a diamond net in a thiosulfate structure.
2 3 10 2 2
Structure of [Zn(S O )(C12H N )].H O, III
The asymmetric unit of III contains 21 nonꢀhydrogen atoms comprising of one Zn(II) ion, one
thiosulfate unit, one 1,2ꢀbis(4ꢀpyridyl)ethylene ligand (bpe) and one lattice water molecule. Similar to
compound I and II, the Zn(II) ions are tetrahedrally coordinated with one oxygen and one sulfur atom from
thiosulfate units and two nitrogen atoms from the bpe units. The various observed bond distances and angles
between the participating species are in the ranges expected for this type of bonding (Table 3)
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The Zn(II) ions are bound to the thiosulfate units giving rise to oneꢀdimensional chains, similar to that
observed in II (Figure 4a). The bpe ligand connects alternate Zn centers forming a twoꢀdimensional layer
(
Figure 4b). The 2D hybrid layers are further crossꢀlinked by another bpe unit giving rise to a threeꢀdimensional
structure (ESI, Figure S19(d)) The bpe ligand in inorganicꢀorganic hybrid structures has been subject an intense
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study as it provides opportunities to investigate possible photodimerization of the C=C bonds. Our previous
studies on the use of bpe resulted in a family of cadmium thiosulfate compounds that satisfied the Schmidt’s
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criterion, and allowed us to investigate the photodimerization. In the present case, however, the C=C bond
pairs are at a larger distance of ~ 11.4 Å, which precludes the possibility of photoꢀdimerisation studies in the
present compound.
The extraꢀframework water molecules occupy the oneꢀdimensional channels of width16 Х 24 Å;
(atomꢀatom contact distance not including the vander Waals radii). Similar to the structure of II, the large open
1D channels gave rise to threeꢀfold interpenetration in the structure (Figure 4c). The structure of III also has the
6
same diamondoid net (ESI, Figure S20(c)) with a schlafli symbol of 6 (Zn = tetrahedral node).
3 2 3 3 12 2 3 2
Structure of [Zn (S O ) (C12H N ) ].3H O, IV
The asymmetric unit of IV consists of 60 nonꢀhydrogen atoms, of which three Zn, three thiosulfate
unit, three 1,2ꢀbis(4ꢀpyridyl)ethane and three water molecule are unique. Both the Zn(II) ions are tetrahedrally
coordinated with similar connectivity to that observed in I – III the compounds. The selected bond distances
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and angles are comparable to those observed before (Table 3).
2
ꢀ
In IV, the Zn(II) ions and [S
2 3 1
O ] ions are connected to form a helical chain due to the 6 screw axis
(Figure 5a). In the helical chains, two consecutive Zn atoms Zn(1) and Zn(2) are connected by bpa ligand
forming a twoꢀdimensional sheet (Figure 5b). The Zn(3) atom connects the twoꢀdimensional sheets through the
bpa ligand forming a threeꢀdimensional structure (Figure 5c).The extraꢀframework water molecules occupies
the oneꢀdimensional channel. The structure also exhibits threeꢀfold interpenetration (Figure 6a)
From a topological point of view, the present structure appears to be closely related to the structure of
2
+
2ꢀ
2 3
βꢀquartz (qtz). Interestingly both Zn and (S O ) are tetrahedrally coordinated and are arranged in a hexagonal
4
2
fashion similar to that observed in β–quartz (Figure 6b). The schalfli symbol of the structure, 6 , 8 , was also
similar to that observed for qtz net.
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Structural comparison:
Four new Zinc thiosulfate phases (I ꢀ IV) have been prepared by varying the length of the nitrogen containing
secondary ligands. While compound I has a catenated twoꢀdimensional arrangement, the compounds II – IV
have oneꢀdimensional Zinc thiosulfate chains crossꢀlinked by the pyridine ligands giving rise to interpenetrated
threeꢀdimensional structures. In I, a simple 4ꢀmembered ring of Zinc thiosulfate connected by the bpp ligand.
As mentioned before, the observation of a 4ꢀmembered ring in I is encouraging and may lead to the formation
of newer thiosulfate structures similar to the sulfate and phosphate structures.
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It has been known that three important structures, viz, the diamond (dia), the SrAl2 (sra) and the
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quartz (qtz) net represent hybrid structures based on tetrahedral node.
Presently, we have isolated the
diamond net (II and III, (ESI, Figure S24(a,b)) and the quartz net (IV). In addition, it can be noted that the
compositions of III and IV are the same, but a closer look at the connectivity within the structure reveal subtle
differences. In III, the bpe ligand connects two zinc thiosulfate one dimensional chains through alternate Zn
centers, whereas in IV, the bpa ligand connects through the Zn(3) center (Figure 5c). The difference in the
connectivity is also reflected in the different net structures observed for the compounds III and IV. It is also
known that the formation of tetrahedral node depends not only on the metal, but also the coordinating ability.
69ꢀ71
Zn centers, normally, have octahedral coordination in many inorganicꢀorganic hybrid structures.
In the
present structure, the zinc species exhibits only tetrahedral coordination, which resulted in the 4ꢀconnected net
structures.
Proton Conductivity:
The presence of lattice water molecules in the structures of III and IV prompted us to investigate the
possible proton migration in these compounds. Proton mobility is one of the important properties that is being
7
2ꢀ79
actively investigated in the area of inorganicꢀorganic hybrid compounds.
Proton conductivity measurements
on III and IV were carried out by employing ACꢀimpedance spectroscopy studies (Alpha, Novocontrol). The
6
samples were scanned in the frequency range of 0.1−10 Hz (signal amplitude: 0.12 V). For the studies, the
samples were pelletised and placed in between the two steel electrodes at 98% relative humidity and at room
ꢀ6
ꢀ5
ꢀ1
ꢀ1
temperature. Proton conductivity values of ~ 6.24 × 10 and 9.38 × 10 Ω cm (34 °C and 98% RH) were
observed for the compounds III and IV, respectively (Figure.7(i)). The proton conductivity values, though not
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very high, are within the ranges exhibited by many hybrid compounds.
The activation energy for the proton
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migration in these compounds were found to be 0.26 eV (III) and 0.49 eV(IV). (Figure. 7(ii)) which suggest a
Grotthus mechanism.
Heterogeneous and photocatalytic studies:
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The inorganicꢀorganic hybrid compounds generally exhibits Lewis acid behavior. During our
investigations of cadmium thiosulfate hybrid compounds, we have established the Lewis acid character by the
4
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cyanosilylation studies. The present compounds were also explored for Lewis acidity by a simple ketal
formation studies. The results of the study are summarized in Table 4.
For the Lewis acid catalytic reaction, 100 mg of the catalyst (compound I - IV) was taken in a 10mL
roundꢀbottom flask along with 5mL of toluene as the solvent. 7mM of ethylene glycol and 7mM of aliphatic
ketone were added to this and the reaction mixture was refluxed at 60°C for 12h. The catalyst was separated
from the reaction mixture by simple filtration, washed with water and dried at amibient conditions. The spent
catalytic compounds were examined using PXRD, which suggested no appreciable changes. The products were
1
analysed using H NMR spectra (ESI, Figure S12ꢀ14). In all the cases, we observed near quantitative
conversion of the ketones to ketals. This study confirms that the zinc thiosulfate hybrid compounds could be
useful as a Lewis catalyst. The catalyst was found to be active with similar conversions for upto 4 cycles.
The band gap values for these compounds were found to be ~ 3.12 eV, 3.92 eV, 3.67 eV and 3.97 eV
for I, II, III and IV, respectively. The observed band gap values correspond to the bipyridine to metal energy
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transfer (LMCT) and slightly higher than the conventional semiꢀconductors such as TiO
2
and ZnO.
Since
TiO and ZnO have been examined as a possible photocatalyst under the UVꢀlight (λmax = 365 nm), we
2
examined the present compounds for the photocatalytic decomposition of organic dyes. To this end, we have
examined two cationic dyes, methylene blue (MB) and methyl violet (MV) as the model pollutants.
In a typical experiment, 100ppm (MB) and 50 ppm (MV) solution of the dyes in water was taken along
4
2
with the catalyst (I - IV) (2g/L). The experiemental conditions were similar to those reported earlier. The
compounds I - IV exhibits photocatalytic activity and we observed ~ 75 % decomposition of the dyes (ESI,
Fig.S15, 16). After photocatalytic studies,the compounds I - IV were examined using PXRD, which indicated
that the compounds have similar PXRD with a slight reduction in the crystallinity. Repeat reactions on the same
used catalysts suggest that the compounds are active with similar results.
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Conclusion
Four new zinc thiosulfate based hybrid compounds have been successfully synthesized and
characterized. All the compounds exhibit 3ꢀfold interpenetration in their structures. The compounds exhibit
reasonable proton mobility at room temperature, photocatalytic activity under UVꢀradiation and Lewis acidic
character. The number of available thiosulfate based hybrid structures is limited and the present solids provide
important members to this class of compounds. The present study indicates that it may be profitable to
investigate other unusual anions such as dichromate, chromate etc. Work towards this theme is currently under
progress.
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Acknowledgement
SN thanks the Department of Science and Technology (DST), and Council of Scientific and Industrial
Research (CSIR) Government of India, for the award of research grants. S.N. also thanks DST for a J. C. Bose
National Fellowship.
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0
6
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Ajmal, A.; Majeed, I.; Malik, R. N.; Idriss, H.; Nadeem, M. A. RSC Adv. 2014, 4, 37003.
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Abingdon, Oxfordshire, England.
84.
Sheldrick, G. M. SHELXLꢀ97 Program for Crystal Structure Solution and Refinement,
University of Göttingen, Göttingen, Germany, 1997.
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Farrugia, J. L. WinGx suite for smallꢀmolecule single crystallography, J. Appl. Crystallogr.,
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999, 32, 837.
Wilson, S. T.; Lok, B. M.; Messina, C. A.; Cannan, T. R.; Flanigen, E. M. J. Am. Chem. Soc.
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Luo, S. ꢀH.; Jiang, Y. ꢀC.; Wang, S. –L.; Kao, H. ꢀM.; Lii, K. –H. Inorg. Chem. 2001, 40,
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88.
Mahata, P.; Prabu, M.; Natarajan, S. Inorg. Chem. 2008, 47, 8451.
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9.
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Mahata, P.; Sundaresan, A.; Natarajan, S. Chem. Commun. 2007, 4471.
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Bailey, A. J.; Lee, C.; Feller, R. K.; Orton, J. B.; Draznieks, C. M.; Slater, B.; Harrison, W. T.
A.; Simoncic, P.; Navrotsky, A.; Grossel, M. C.; Cheetham, A. K. Angew. Chem., Int. Ed.
2008, 47, 8634.
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Ayi, A. A.; Choudhury, A.; Natarajan, S.; Neeraj, S.; Rao, C. N. R. J. Mater. Chem. 2001, 11,
1181.
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Choudhury, A.; Neeraj, S.; Natarajan, S.; Rao, C. N. R. J. Mater. Chem. 2001, 11, 1537.
Rao, V. K.; Chakrabarti, S.; Natarajan, S. Inorg. Chem. 2007, 46, 10781.
Chen, B.; Liang, C.; Yang, J.; Contreras, D. S.; Clancy, Y. L.; Lobkovsky, E. B.; Yaghi, O.
M.; Dai, S. Angew. Chem., Int. Ed. 2006, 45, 1390.
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Huang, S.ꢀH.; Wang, S.ꢀL. Angew. Chem., Int. Ed. 2011, 40, 5319.
Chughtai, A. H.; Ahmad, N.; Younus, H. A.; Laypkovc, A.; Verpoort, F. Chem. Soc. Rev.
2015, 44, 6804.
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Bureekaew, S.; Sato, H.; Matsuda, R.; Kubota, Y.; Hirose, R.; Kim, J.; Kato, K.; Takata, M.;
Kitagawa, S. Angew. Chem., Int. Ed. 2010, 49, 7660.
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Huang, S.ꢀH.; Lin, C.ꢀH.; Wu, W.ꢀC.; Wang, S.ꢀL. Angew. Chem., Int. Ed. 2009, 48, 6124.
Vilar, R. Angew. Chem., Int. Ed. 2003, 42, 1460.
9.
00. Kanoo, P.; Matsuda, R.; Higuchi, M.; Kitagawa, S.; Maji, T. K. Chem. Mater. 2009, 21, 5860.
01. Rao, C. N. R.; Behra, J. N.; Dan, M. Chem. Soc. Rev. 2006, 35, 375.
102. Blatov, V. A. 2006, http://www.topos.ssu.samara.ru.
103. Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl. Crystallogr. 2000, 33, 1193.
104. Ohrstrom, L.; Larsson, K. MoleculeꢀBased MaterialsꢀThe Structural Network Approach,
Elsevier, 2005.
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105. Maspoch, D.; RuizꢀMolina, D.; Vaciana, J. Chem.Soc. Rev. 2007, 36, 770.
1
1
1
1
06. Paul, G.; Choudhury. A.; Rao, C. N. R.; J. Chem. Soc., Dalton Trans. 2002, 3859.
07. Chen, C.ꢀY.; Lii, K.ꢀH.; Jacobson, A. J. J. Solid State Chem. 2003, 172, 252.
08. Ohmori, O.; Fujita, M. Chem. Commun. 2004, 1586.
0
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09. Rogow, D. L.; Fei, H.; Brennan, D. P.; Ikehata, M.; Zavalij, P. Y.; Oliver, A. G.; Oliver, S. R.
J. Inorg. Chem. 2010, 49, 5619.
110.
Gao, W.; Jing, Y.; Yang, J.; Zhou, Z.; Yang, D.; Sun, J.; Lin, J.; Cong, R.; Yang, T. Inorg.
Chem. 2014, 53, 2364.
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Figure Captions
2 3
Fig. 1. (a) Figure shows the twoꢀdimensional layers in [Zn(S O )(bpp)] I
(b) Figure shows the catenation in the structure (sticks represent bpp).
10
11
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(
c) The topological view of the structure of I showing the interpenetration
2 3 2 2 3 2 2
Fig. 2. (a) View of the ꢀZnꢀS O ꢀZnꢀ 1D infinite chains in [Zn (S O ) (bpy) ] II
2 3
(b) Figure shows the connectivity between bpy and ꢀZnꢀS O ꢀZnꢀ chains
(
c) View of the 3D structure of II
Fig.3. (a) The connectivity showing the adamentane unit in II
(b) The threeꢀfold interpenetrated structure of II
2 3 2
Fig. 4. (a) The 1D infinite chains observed in [Zn(S O )(bpe))].H O III
(b) Figure shows the connectivity between bpe and the Zinc thiosulfate 1D chains in III
(c) View of the threeꢀdimensional structure. Note the threeꢀfold interpenetration. The lines are the
guides to the eye
Fig. 5. (a) The Zinc thiosulfate 1D chains in [Zn
arrangement.
3 2 3 3 12 2 3 2
(S O ) (C12H N ) ].3H O IV Note the formation of helical
2 3
(b) Figure shows the connectivity between ꢀZnꢀS O ꢀZnꢀ helical chains and the bpa ligand in IV
(c) The threeꢀdimensional view of the structure of IV
Fig.6
(a) Figure shows the threeꢀfold interpenetration in the structure of IV
(b) The node and net connectivity showing the qtz structure.
Fig. 7.
Nyquist plot for the (a) compound III and (b) compound IV
The Arrhenius plot for the proton conductivity studies of (c) compound III and (d) IV
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Table 1. Synthetic conditions employed for the preparation of the compounds I -IV
a
S.
Composition
Time Temp Product
Yield
(%)
No
(h)
(°C)
1
2
3
.
.
.
1mM Zn(NO
3
)
2
+ 1mM Na
O(4ml)
2
S
2
O
3
+ 1mM bpp + 72
80
[Zn(S O )(C H N )], I
77
2
3
13 14
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
MeOH (6ml) + H
2
1mM Zn(NO
3
)
)
2
2
+ 1mM Na
2
2
S
2
2
O
3
+ 2 mM bpy 72
+ 1mM bpe 72
80
80
80
[Zn(S
O
)(C10
H
10
N
2
)]2, II
75
2
3
+
MeOH (6ml) + H
2
O(4ml)
1mM Zn(NO
+ 1mM Na
O(4ml)
S
O
[Zn(S O )(C H N )].H O, III 76
3
3
2
3
12 10
2
2
+
MeOH (6ml) + H
2
4.
1mM Zn(NO
3
)
2
+ 1mM Na
O(4ml)
2
S
2
O
3
+ 1mM bpa + 72
[Zn
3
(S
2
O
3
)
3
(C12
H
12
N
2
)
3
2
].3H O, 74
MeOH (6ml) + H
2
IV
bpy = 4,4′ꢀbipyridine, bpp = 1,3ꢀbis(4ꢀpyridyl)propane, bpe = 1,2ꢀbis(4ꢀpyridyl)ethene , bpa = 1,2ꢀbis(4ꢀ
pyridyl)ethane
a
CHN analysis for I calc (%) C 41.5%; H 3.7%; N 7.4%; Found(%): C 41.6%; H 3.7%; N 7.5%; For II calc (%)
C 35.9%; H 2.4%; N 8.3%; Found(%): C 35.0%; H 2.6 %; N 8.3%; For III calc (%) C 38.3%; H 2.6%; N 7.4%;
Found(%): C 37.6; H 2.5%; N 7.1%; For IV calc (%) C 38.1%; H 3.2%; N 7.4%; Found(%): C 36.9%; H 3.5%;
b
N 6.9%; yields are calculated based on the respective metals. Compositions are given in millimoles.
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2 3 14 2
Table 2. Crystallographic data and structure refinement of parameters for compound [Zn(S O )(C13H N )] I,
[Zn
2
(S
2
O
3
)
2
(C10
H
10
N
2
)
2
] II, [Zn(S
2
O
3
)(C12
H
10
N
2
)].H
2
O III, [Zn
3
(S
2
O
3
)
3
(C12
H
12
N
2
)
3 2
].3H O IV.
Structural
parameter
I
II
III
IV
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
ZnS O N C H
Zn S O N C H
ZnS O N C H
Zn S O N C H
3 6 12 6 36 36
2
3
2
13 14
2
4
6
4
20 16
2
4
2
12 10
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
374.65
671.43
Orthorhombic
Pbc2 (no. 29)
377.77
1139.43
Orthorhombic
Pcab (no. 61)
12.165(2)
12.189(2)
19.303(3)
90
Monoclinic
P2 /n (no. 14)
Hexagonal
1
1
P6
1
15.7740(3)
13.1191(2)
11.9058(2)
90
9.260(5)
15.959(5)
10.379(5)
90
16.3547(15)
16.3547(15)
29.085(3)
90
b (Å)
c (Å)
α (°)
β (°)
90
90
109.375(5)
90
90
γ (°)
90
90
120
3
V (Å )
2862.2(8)
8
2463.79(7)
4
1446.9(11)
4
6737.4(11)
6
Z
T/K
293
293
293
293
ꢀ
3
ρ (calc/mgm )
1.683
1.976
1.725
1.704
ꢀ1
ꢁ
(mm )
2.015
2.621
2.001
2.495
λ (Mo Kα/Å)
θ range ( °)
Rint
0.71073
1.67 to 28.34
0.0837
0.71073
2.58 to 26.00
0.0576
0.71073
0.71073
1.44 to 27.57
0.0823
2.39 to 27.56
0.0261
R indexes [ I > 2
σ
R
1
= 0.0406
wR = 0.0955
= 0.0758
wR = 0.1080
R
1
= 0.0293
wR = 0.0719
= 0.0348
R
1
=0.0563
wR = 0.1544
=0.00701
wR = 0.1672
R
1
= 0.0571
wR = 0.1388
1
R = 0.0698
(I)]
2
2
2
2
R indexes (all data)
R
1
R
1
R
1
wR = 0.0752
wR = 0.1446
2
2
2
2
2
O
2
2
2
1/2
2
2
2
R
1
=∑ | F
O
| ꢀ | F
C
||/∑ | F
O
|; wR
2
= {∑ [w (F
ꢀ F
C
)]/ ∑ [w (F
O
) ]} . w = 1/[ρ (F
O
) + (aP) + bP]. P = [max
2
2
C
(
F
O
, O) + 2 (F
)/3, where a= 0.0932 and b=0.0000 for I, a= 0.1000 and b= 0.0000 for II, a= 0.1270 and b=
6.9285 for III, where a= 0.0789 b= 28.7117 for IV.
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2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
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4
4
4
4
4
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5
5
5
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Table 3. Selected bond distances in Zinc thiosulfate compounds [Zn(S O )(C H N )] I, [Zn (S O ) (C H N ) ]
2
3
13 14
2
2
2
3 2
10 10 2 2
II, [Zn(S O )(C H N )].H O III, [Zn (S O ) (C H N ) ].3H O IV.
2
3
12 10
2
2
3
2
3 3
12 12 2 3
2
Bond
Distance (Å)
Bond
Distance (Å)
Bond
Distance (Å)
I
Zn(1)ꢀS(1)
Zn(1)ꢀO(1)
Zn(1)ꢀN(1)
2.2956(11)
1.981(3)
2.027(3)
Zn(1)ꢀN(2)
S(1)ꢀS(2)
2.059(3)
2.0378(14)
1.477(3)
S(2)ꢀO(2)
S(2)ꢀO(3)
1.444(3)
1.433(3)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
S(2)ꢀO(1)#1
II
Zn(1)ꢀS(1)
Zn(2)ꢀS(3)
2.2660(17)
2.2548(17)
Zn(1)ꢀN(3)
Zn(2)ꢀN(4)
2.048(4)
2.067(4)
S(2)ꢀO(3)#1
S(4)ꢀO(4)#2
1.476(4)
1.492(4)
Zn(2)ꢀO(4)
Zn(1)ꢀO(3)
Zn(1)ꢀN(1)
Zn(2)ꢀN(2)
1.981(4)
1.997(4)
2.055(4)
2.031(4)
S(1)ꢀS(2)
S(3)ꢀS(4)
S(2)ꢀO(1)
S(2)ꢀO(2)
2.036(2)
2.051(2)
1.447(3)
1.446(4)
S(4)ꢀO(5)
S(4)ꢀO(6)
1.436(3)
1.461(4)
III
IV
Zn(01)ꢀS(1)
2.2936(16)
1.984(4)
2.018(4)
Zn(01)ꢀN(2)
S(1)ꢀS(2)
2.028(4)
2.029(2)
1.371(6)
S(2)ꢀO(2)#1
S(2)ꢀO(3)
1.438(4)
1.497(6)
Zn(01)ꢀO(2)
Zn(01)ꢀN(1)
S(2)ꢀO(1)
Zn(1)ꢀS(3)
Zn(2)ꢀS(2)#3
Zn(3)ꢀS(6)
Zn(1)ꢀO(1)
Zn(2)ꢀO(6)
Zn(3)ꢀO(9)#4
Zn(1)ꢀN(1)
Zn(1)ꢀN(3)
2.274(2)
2.282(2)
2.284(2)
2.006(7)
2.005(7)
2.014(6)
2.034(6)
2.020(6)
Zn(2)ꢀN(2)#1
Zn(2)ꢀN(4)#2
Zn(3)ꢀN(5)
Zn(3)ꢀN(6)
S(1)ꢀS(2)
2.021(5)
2.027(6)
1.998(6)
2.020(5)
2.043(3)
2.029(3)
2.047(3)
1.454(6)
S(1)ꢀO(2)
S(1)ꢀO(3)
S(4)ꢀO(4)
S(4)ꢀO(5)
S(4)ꢀO(6)
S(5)ꢀO(7)
S(5)ꢀO(8)
S(5)ꢀO(9)
1.404(7)
1.465(7)
1.345(7)
1.461(10)
1.411(7)
1.450(6)
1.467(6)
1.463(6)
S(3)ꢀS(4)
S(5)ꢀS(6)
S(1)ꢀO(1)
Symmetry transformations used to generate equivalent atoms: For I: #1 ꢀx,ꢀy+1,ꢀz+1; For II: #1 ꢀx+1,ꢀy+1,zꢀ1/2; #2
x,ꢀy+5/2,z+1/2; For III: #1 xꢀ1/2,ꢀy+3/2,zꢀ1/2; For IV: #1 ꢀx+y,ꢀx,zꢀ1/3; #2 x,y+1,z; #3 ꢀx+y+1,ꢀx+1,zꢀ1/3; #4
y+1,ꢀx+y+1,zꢀ1/6
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Table 4. Cyclic ketal formation reactions employing for the compounds I - IV
Reactant
Product
Yield (%)
Blank
I
II
III
IV
<
5
95
93
94
92
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Acetone
2ꢀbutanone
3ꢀpropanone
<
5
94
93
92
92
91
93
90
91
< 5
23
ACS Paragon Plus Environment

Crystal Growth & Design
Page 24 of 31
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
a)
(b)
(
c)
Karthik and Natarajan Figure 1
24
ACS Paragon Plus Environment

Page 25 of 31
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
(
a)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(
b)
(
c)
Karthik and Natarajan Figure 2
25
ACS Paragon Plus Environment

Crystal Growth & Design
Page 26 of 31
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(a)
(
b)
Karthik and Natarajan Figure 3
26
ACS Paragon Plus Environment

Page 27 of 31
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
(a)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(
b)
(
c)
Karthik and Natarajan Figure 4
27
ACS Paragon Plus Environment

Crystal Growth & Design
Page 28 of 31
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
b)
(
a)
(
c)
Karthik and Natarajan Figure 5
28
ACS Paragon Plus Environment

Page 29 of 31
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(a)
(
b)
2
9
Karthik and Natarajan Figure 6
ACS Paragon Plus Environment