The First Thiostannate Compound with Copper(II) Synthesized Under Ambient Conditions: Crystal Structure, Electronic and Thermal Properties

Article abstract of DOI:10.1002/ejic.201900924

The new compound {[Cu(cyclam)]₂[Sn₂S₆]}_n·2nH₂O containing Cu(II) was synthesized at room temperature reacting aqueous solutions of Na₄SnS₄·14H₂O and of [Cu(cyclam)](ClO₄)₂. A crystalline precipitate consisting of small crystallites was formed after a very short reaction time of 2 h. Structure analysis reveals that [Sn₂S₆]^4– anions are joined by the [Cu(cyclam)]²⁺ cations via Cu–S bonds generating layers which are stacked along the crystallographic a-axis. The Cu(II) centers are in a distorted octahedral environment of four N and two S atoms. The distortion is reflected in the EPR spectrum that displays the A_∥ lines characteristic for Cu²⁺ (I = 3/2) and due to g_∥ > g_⊥ > 2.0023, the unpaired electron is located in the d_x²_–y² orbital. The crystal water molecules can be removed at elevated temperatures, while crystallinity of the sample is mainly retained. Storage of the dehydrated sample on air leads to water uptake and recovery of the pristine compound.

Full text of DOI:10.1002/ejic.201900924

DOI: 10.1002/ejic.201900924
Full Paper
Layered Compounds | Very Important Paper |
The First Thiostannate Compound with Copper(II) Synthesized
Under Ambient Conditions: Crystal Structure, Electronic and
Thermal Properties
[a]
[a]
[a]
Assma Benkada, Helge Reinsch, and Wolfgang Bensch*
Abstract: The new compound {[Cu(cyclam)] [Sn S ]} ·2nH O torted octahedral environment of four N and two S atoms. The
2
2
6
n
2
containing Cu(II) was synthesized at room temperature reacting distortion is reflected in the EPR spectrum that displays the A
s
2
+
aqueous solutions of Na SnS ·14H O and of [Cu(cyclam)](ClO ) . lines characteristic for Cu (I = 3/2) and due to gs > g >
4
4
2
4 2
⊥
A crystalline precipitate consisting of small crystallites was 2.0023, the unpaired electron is located in the d 2
2
orbital.
x –y
formed after a very short reaction time of 2 h. Structure analysis The crystal water molecules can be removed at elevated tem-
4
–
2+
reveals that [Sn S ] anions are joined by the [Cu(cyclam)]
peratures, while crystallinity of the sample is mainly retained.
2
6
cations via Cu–S bonds generating layers which are stacked Storage of the dehydrated sample on air leads to water uptake
along the crystallographic a-axis. The Cu(II) centers are in a dis- and recovery of the pristine compound.
Introduction
(2-aminoethyl)amine), trien (trien
cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) or tepa
tepa = tetraethylenepentamine) form unsaturated metal com-
= triethylenetetramine),
The integration of transition metals into thiostannate frame-
works significantly alters the crystal structures and properties
of the inorganic framework. Pure inorganic bulk thiostannates,
respectively tin sulfides containing transition metals are pre-
pared using the high temperature route, by reaction of ele-
ments in an inert flux, in reactive fluxes or by mechanical
alloying combined with spark plasma sintering. In the past, it
was demonstrated that the solvothermal method is most prom-
ising for the generation of thiostannates containing transition
metal complexes. Considering only compounds that contain the
(
2–
plexes allowing the coordination of S of the inorganic frame-
work to metal cation. Examples include [M(tren)] Sn S (M =
2
2 6
[6,10]
[7]
Mn, Co and Ni),
{[Mn(trien)] [SnS ]} ,
{[M(cyclam)]2-
and {[M(tepa)] [Sn S ]}
M = Co, Fe and Ni). All these compounds contain the anionic
Sn S ] unit, which occurs as an isolated anion like in
2
4 n
[
1]
[11,12]
[
(
[
[
Sn S ]} ·2nH O (M = Co and Ni)
2 6 n 2
2
2 6
[
2]
[3]
[13]
[
4]
4–
2
6
[14]
Ni(tren) ] [Sn S ]·8H O and [Ni(tren)(2amp)] [Sn S ],
or is
2
2
2
6
2
2
2 6
linked to the transition metal complexes by covalent M–S
bonds. The linkage is realized by three different modes: A) two
4
–
2+
[
Sn S ] anion, saturated complexes with the cations Mn ,
2–
2
6
trans terminal S anions form a bond such in {[Fe(1,2-dach) ]-
2
2
+
2+
2+
Co , Ni and Zn are observed with bi- and tridentate amine
molecules like en (en = ethylenediamine), dap (dap = 1,2-di-
aminopropane), 1,2-dach (1,2-dach = 1,2-diaminocyclohexane),
[12]
2–
[
Sn S ]} ·2n1,2-dach;
bonds and two S anions bind to two transition metal com-
B) all four terminal S are involved in
2
6 n
2–
plexes like in {[M(phen) ] [Sn S ]}·phen·H O (M = Co, Fe and
2
2
2
6
2
[16]
2amp (2amp = 2-(aminomethyl)pyridine), dien (dien = diethyl-
[15]
2–
Mn) or in {[Ni(phen) ] [Sn S ]}·2,2′-pipy; C) each S anion
2
2
2 6
enetriamine) and aepa (aepa = N-2-aminoethyl-1,3-propandi-
amine), as exemplified by the compounds [M(en) ] [Sn S ]
binds to one complex, so that four complexes are bound to one
3
[6]
2
2 6
4–
[
(
Sn S ]
unit as observed in {[M(cyclam)] [Sn S ]} ·2nH O
2
6
2 2 6 n 2
[
5,6]
(
M = Mn, Co, Ni and Zn),
[Ni(dap) ] [Sn S ]·2H O, [Ni(1,2-
[12]
3
2
2
6
2
M = Co and Ni).
[
7]
[7,8]
dach) ] [Sn S ]·4H O, [M(dien) ] [Sn S ] (M = Co and Ni),
3
2
2
6
2
2 2
2 6
Only a few thiostannate and tin sulfide compounds contain-
ing Cu or Ag are known so far, whereby both metals exhibit the
oxidation state +I. In addition, Cu(I) and Ag(I) cations have
[
9]
[7]
[
Ni(2amp) ] [Sn S ]·9.5H O and [Ni(aepa) ] [Sn S ]. In con-
3 2 2 6 2 2 2 2 6
trast, tetra- and pentadentate amines like tren (tren = tris-
2
–
bondstotheS anionsofthethiostannateionslikein[1,4-dabH ]-
2
[18]
[
a] Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel,
Max-Eyth-Str. 2, 24118 Kiel, Germany
[17]
[
[
[
Ag SnS ] (1,4-dab = 1,4-diaminobutane), [H en][Ag SnS ],
2
4
2
[20]
2
4
[19]
enH][Cu AgSnS ],
[dienH ][Cu Sn S ],
[enH]6+n-
2
4
2
2
[21]
2 6
E-mail: wbensch@ac.uni-kiel.de
http://www.ac.uni-kiel.de/de/bensch
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201900924.
[
21]
[21]
Cu Sn S ],
[enH] [Cu Sn S ],
[trenH ][Cu Sn S ],
4
0
15 60
3
7
4
12
3 7 4 12
[
22]
[DBUH][CuSnS
] (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene),
3
[
23]
[22]
[H en] [Cu Sn S ],
[1,4-dabH ][Cu SnS ],
where proto-
2
2
8
3
12
2
2
4
©
2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. ·
nated amine molecules provide charge balance and act as
structure directing agents. All these compounds were synthe-
sized under solvothermal conditions using the elements Sn, S,
Cu or Cu S in amine solvents. The compounds Cu Sn1-xSixS3
This is an open access article under the terms of the Creative Commons
Attribution-NonCommercial License, which permits use, distribution and re-
production in any medium, provided the original work is properly cited and
is not used for commercial purposes.
2
2
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[
24]
(
0.4 ≤ x ≤ 0.6) with band gaps of 1.25, 1.35 and 1.45 eV
as Comparison of the complex stability constants of the Co(II),
[
20]
well as (dienH )Cu Sn S , reveal potential as absorber materi- Zn(II), Ni(II) and Cu(II) complexes (Table 1) demonstrates that
2
2
2 6
als for photovoltaic devices.
the Cu(II) centered complex is most stable in this series of com-
The existence of Cu(II) in thiostannates and tin sulfides has pounds. The high stability makes formation of Cu(II) aqua
2
–
not been observed until now. The reason is that Cu(II) is re- complexes unlikely which are prone to react with S anions in
2
–
duced by S anions to Cu(I). Our challenge was to find an solution thus leading to precipitation of CuS or Cu
S.
2
amine ligand that forms stable complexes with Cu(II) leaving
Table 1. Complex stability constants (log K) of Co(II), Zn(II), Ni(II) and Cu(II)
complexes.
2–
sites at the Cu(II) center free for bond formation to S . Indeed,
after a research in the Cambridge Structural Database (CSD) we
found that cyclam generates stable complexes with transition
Ligand Co2+ (log K)[25] Zn2+ (log K)[25] Ni2+ (log K)[25] Cu2+ (log K)[25]
[
25]
Cyclam 12.7
15.0
22.2
27.2
metal cations and especially with Cu(II) (log K = 27.2,
see
Synthetic aspects). Encouraged by this observation we per-
formed syntheses with the [Cu(cyclam)](ClO ) complex under
4
2
hydrothermal conditions as well as at room temperature.
Herein, we present the first copper(II) containing tin-sulfide
Crystal Structures
compound {[Cu(cyclam)] [Sn S ]} ·2nH O, which exhibits a 2D
2
2
6
n
2
Compound I, {[Cu(cyclam)] [Sn S ]} ·2nH O, crystallizes in the
2 2 6 n 2
structure. This compound was prepared by using Na SnS ·
4
4
triclinic space group P 1¯ with one formula unit per unit cell. The
4–
1
4H O as precursor and the stable complex [Cu(cyclam)](ClO )
2
4
2
unique Sn and S atoms of the [Sn S ] anion are located on
2 6
in water at room temperature. In addition, electronic and ther-
mal properties of the title compound were investigated and the
results are presented herein.
general and the Cu atoms of the complexes on special posi-
4
–
tions. The [Sn S ] anion is formed by two edge-sharing
2
6
4
–
[
SnS4] tetrahedra (Figure 1).
Results and Discussions
Synthetic Aspects
The overwhelming number of thiostannates were synthesized
[
26]
using elemental Sn and S in aqueous amine solutions.
The
basic conditions are necessary to generate polysulfide anions,
which react with Sn to form thiostannate ions.[
27]
Applying
Na SnS ·14H O as precursor the addition of amine is not neces-
4
4
2
4–
sary, and recently we have shown that [SnS ] condenses very
fast to form [Sn S ] units under release of H S.
4
4
–
[9,28]
Reacting
2
6
2
[
Ni(cyclen)](ClO ) (cyclen = 1,4,7,10-tetrazacyclododecane) and
4
2
Na SnS ·14H O under hydrothermal conditions we successfully
4
4
2
[
29]
prepared {[Ni(cyclen)] [Sn S O (OH) ]}·2(ClO )·19H O.
clen is a tetraaza macrocyclic ligand that forms TM centred
complexes with two free coordination sites and if TM prefers
Cy-
6
6
12
2
6
4
2
n+
n+
Figure 1. View of the constituent in the structure of compound I. Only se-
lected atoms are labelled and H atoms are omitted for clarity.
an octahedral coordination, bond formation to thiostannate an-
ions is possible, which is observed in the structure where
2
+
2–
[
Ni(cyclen)] cations are bound to the central core unit via S
–
[29]
and OH anions.
Encouraged by this observation we used
The Sn–Sterm bond lengths vary between 2.3877 and
in the present work the [Cu(cyclam)]2 complex with a planar 2.3935 Å, while the Sn–Sbrid bonds scatter between 2.4262 and
environment around Cu(II) and the two apical positions are free 2.4946 Å (Table S1). These values are in the typical range of
for bond formation. The compounds {[Ni(cyclam)] [Sn S ]} · literature data. The S–Sn–S angles are in the range of 93.04–
+
2
2 6 n
2
nH O and {[Co(cyclam)] [Sn S ]} ·2nH O were prepared under 117.25° (Sterm–Sn–Sterm: 111.30°, Sbrid–Sn–Sbrid: 93.04°, Sbrid–Sn–
2 2 2 6 n 2
solvothermal conditions by reacting [Ni(cyclam)](ClO4)2 with Sterm: 108.95–117.25°) indicating a pronounced distortion of the
[
5,11,30]
Na SnS ·14H O or by reacting [Co(cyclam)Cl ]Cl with elemental tetrahedra.
Both Cu(II) cations are in an octahedral envi-
4
4
2
2
Sn and S. For comparison, we heated an aqueous solution of ronment of four N and two S atoms occupying the apical posi-
Na SnS ·14H O with [Cu(cyclam)](ClO ) at T = 120 °C for 1 d tions (Figure 1). The Cu–N/S bonds are Cu–N = 1.992(2)–2.085(1)
4
4
2
4 2
but no thiostannates could be obtained. In the X-ray powder Å and Cu–S = 2.764(9)–2.782(9) Å, with corresponding angles
pattern reflections of Cu S could be identified indicating that around Cu(II) cations (Table S1) indicative for a significant dis-
8
5
[
Cu(cyclam)](ClO ) is not stable under hydrothermal conditions. tortion of the ideal octahedral geometry. However, all Cu–N and
4 2
[
31]
Because the [Cu(cyclam)](ClO ) complex exhibits a good solu- N–Cu–N values are in the range of literature data.
bility in water (solubility = 14.4 g/L, Figure S1), syntheses at bonds are longer than the sum of ionic radii [Cu (CN = 6) =
room temperature were carried out by adding an aqueous solu- 0.73 Å; S : 1.84 Å; sum: 2.57 Å], but shorter than the sum of
tion of Na SnS ·14H O to aqueous solution of the complex. the van der Waals radii (3.4 Å).
The Cu–S
4
2
2
+
2
–
[32]
[
33]
A search in the Cambridge
4
4
2
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Structural Database for the complexes with CuN S cores ried out for any polyhedron. In addition, the MBE must be the
4
2
–
(
mainly thiolates and complexes with SCN ), in which S is in ellipsoid of smallest volume that includes all atoms. Normally,
the apical position, yields Cu–S separations between 2.560 and the vertices of high symmetry polyhedra are positioned on the
.258 Å. These values indicate that Cu–S bonds in the CuN4S2 surface of a sphere. Variation of the symmetry of polyhedra
3
moieties are between the sum of ionic radii and the sum of the causes a transformation of the sphere into an ellipsoid. The
van der Waals radii. For analyzing the distortions of polyhedra, principal ellipsoid radii are R1 ≥ R2 ≥ R3, their average <R> and
[
34]
2
2
a new method was reported by Cumby et al.,
in which the their variance σ (R) or standard deviation σ(R) = √σ (R) present
shape of a polyhedron is approximated by an ellipsoid (mini- the size and the distortion of the polyhedra, respectively. An
mum bounding ellipsoid, MBE). Regardless of coordination important parameter to describe the distortion of the polyhe-
number and geometry, the calculation of the MBE can be car- dra is the shape of the ellipsoid S which is represented by
S = R3/R2 – R2/R1. S is in the range of –1 to 1. A sphere has
S = 0, for an axially compressed ellipsoid S < 0 and for an axially
stretched ellipsoid S > 0. Table 2 shows the volumes and the
shape parameters S of the two Cu centered polyhedra. As can
be seen from the data the polyhedra are axially elongated and
the Cu1 centered polyhedron shows the largest stretching.
Table 2. Volumes and shape parameters of the Cu2+ centered octahedra.
Atom
V [Å3]
S
Cu1 (I)
Cu2 (I)
49.8
45.2
0.227
0.155
4
–
All Sterm atoms of the [Sn S ] moiety are bonded to the
2
6
Cu2+ cations in two different directions forming layers within
the ac plane. The layers are stacked along [100] and in a···AAA···
sequence with the shortest interlayer separation of ≈ 4.4 Å
(measured from coordinate to coordinate).
The water molecules are located between the layers (Fig-
ure 2). Compound I is isostructural to the compounds
[
11,12]
{
[M(cyclam)] [Sn S ]} ·2nH O (M = Co and Ni),
and all three
2
2
6
n
2
compounds belong to the relatively rare two-dimensional thio-
2
+
stannate compounds containing TM cations, like observed in
[
19]
[20]
[35]
[
[
enH][Cu AgSnS ],
[dienH ][Cu Sn S ],
K Ag Sn S
or
2
4
[
2
2
2
6
2
6
3 10
18]
enH ][Ag SnS ].
2
2
4
Spectroscopic Properties
The characteristic bands of the macrocyclic amine molecule can
be identified in the IR spectrum (Figure S2; Table S2). The broad
band at approximately 3441 cm– is attributable to the OH
1
stretching vibration of H O. The N-H stretching vibrations of
2
cyclam are located around 3202–3101 cm– and the Cu–N
stretching mode is observed at about 424 cm . The typical
Sn–S modes occur in the Raman spectrum in the region of
00 to 100 cm . The Sn–S
84 cm . The Sn–S–Sn and Sn S ring vibrations are observed
1
–
1
–1
4
3
stretching mode is located at
term
–
1
2
2
–1
at 341 and 277 cm . The deformation and lattice vibrations of
the [Sn S ] unit occur between 200 and 100 cm , however a
4
–
–1
2
6
reasonable assignment is not possible (Figure S3).
The UV/Vis spectrum of I displays the expected d-d transition
2
+
(
1
Figure 3). For [Cu(H O) ] the transition is located at about
2
6
2
2
[36]
.55 eV (800 nm, E → T ).
The title compound shows a
g
2g
signal at 2.27 eV (546 nm) which is shifted to higher energy
compared to the hexa-aqua complex caused by the differing
bonding properties. Compounds with CuN S cores, in which
4
2
S is in apical position exhibit a single broad band between 1.87
[
37,38]
and 2.26 eV,
which is the envelope of the three possible
2
2
2
2
2
2
[39]
transitions: B → A , B → B and B → E .
The color
1
g
1g
1g
2g
1g
g
of the crystals of the title compound is caused by the transition
at 2.27 eV (546 nm) which corresponds to violet color. The
strong absorption at 2.87 eV (432 nm) is attributed to charge
Figure 2. View of the crystal structure of compound I along [001] (top) and
along [100] (bottom). The H atoms of the complexes are omitted for clarity.
[
37]
transfer transition.
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neously differential thermoanalysis and thermogravimetry
(DTA-TG) were performed. Upon heating two mass steps are
observed in the TG curve (Figure S4). The first step is accompa-
nied by an endothermic signal in the DTA curve at peak temper-
ature of ≈ 140 °C. The mass loss of 4.0 % is in good agreement
with that calculated for the removal of two H O molecules (calc.
2
3.6 %). In the second step the intermediately formed anhydrate
decomposes between 200 and 400 °C in two endothermic reac-
tions (T = 228 and 252 °C). The mass loss of 43.7 % probably
p
matches with the emission of two cyclam molecules and one
H2S molecule (calc. 43.7 %). The X-ray powder pattern of the
black residue obtained after heating the sample to 500 °C con-
tains SnS, Cu S and Cu S (Figure S5). In a further experiment,
2
8 5
heating was stopped after the first step at 165 °C and the light
purple powder was investigated by X-ray powder diffraction.
The powder pattern is very similar to that of the pristine com-
pound, with some reflections being shifted and broadened.
Storing this sample on air at room temperature the title com-
pound is retained, but the crystallinity is slightly reduced as can
be seen comparing the pattern of the pristine material with
that of the rehydrated one (Figure S6). The anhydrate was also
dispersed in methanol to investigate whether a polar solvent
can be incorporated. Nevertheless, the X-ray powder pattern
indicates that the uptake of methanol was unsuccessful (Figure
S7).
Figure 3. Kubelka–Munk-Factor F2 as function of energy calculated from
UV/Vis spectroscopic data.
Electronic Properties
The electron paramagnetic resonance (EPR) spectroscopy is an
interesting method to study the coordination geometry and the
electronic structure. Based on the two important parameters gs
and g the ground state can be determined. For an elongated
⊥
octahedron, a square pyramid or square planar environment of
Cu(II) the ground state is d 2
2
and g > g >2.0023. When the
x –y
s
⊥
dz
2
orbital is the ground state, then g > g = 2.0023 and the
⊥
s
coordination sphere is compressed octahedral or trigonal
[
40]
bipyramidal.
The EPR spectrum of I (Figure 4) reveals only
Conclusion
2+
[41]
three of the four A lines characteristic for Cu (I = 3/2). This
s
is due to the overlap of the signals assigned to g with those
s
The first Cu(II) thiostannate was prepared at room temperature
in good yield applying a simple aqueous synthesis method us-
ing Na SnS ·14H O and [Cu(cyclam)](ClO ) . The crystallites of
assigned to g . Since g (2.26) > g (2.02) > 2.0023, the unpaired
⊥
s
⊥
2
2
[40]
electron is located in the d
orbital.
The metal hyperfine
x –y
4
4
2
4 2
coupling A in this region is ≈ 205 G. These results demonstrate
s
the title compound were formed after 2 h reaction time, which
is much faster than for classical solvothermal syntheses. In the
that the CuN S octahedron is elongated, which is in line with
4
2
relatively long Cu–S bonds (see above) and are in good agree-
4–
structure of I the [Sn S ] anions are covalently bound to the
[
2
6
ment with those of Cu(II) complexes with distorted octahe-
2+
Cu(cyclam)] cations by Cu–S bonds in trans position. In this
dra.[41,42]
way, layers are generated which are stacked along [1–10]. The
Cu(II) cations are in a distorted octahedral environment which is
reflected by the EPR data. According to these data, the unpaired
2
2
electron is located in the d
orbital, which is typical for a
x –y
distortion of the octahedron along the z axis. A further confir-
mation was provided from UV/Vis spectrum, in which only one
broad band is observed which is the envelope of the three
possible electronic transitions. The crystal water molecules can
be thermally removed without collapse of the structure. Further
experiments are under way with other Cu(II) centered com-
plexes to check whether the new synthetic approach can be
used for generation of further new compounds.
Experimental Section
Na SnS ·14H O and [Cu(cyclam)](ClO ) were prepared according to
4
4
2
4 2
[
43]
Figure 4. EPR spectrum for compound I in water/glycerin mixture at 77 K.
literature methods. Generally, the reaction products were filtered,
washed with water and dried at ambient conditions. Caution: Per-
chlorate anions are potentially explosive if heated and must be han-
dled with care.
Thermogravimetric Analysis
To investigate the stability of compound I and if the water mol- Synthesis of {[Cu(cyclam)] [Sn S ]} ·2nH O (I): Na SnS ·14H O
2
2
6
n
2
4
4
2
ecules can be reversibly removed, measurements using simulta- (59.1 mg, 0.1 mmol) was dissolved in 0.5 mL of H O and [Cu-
2
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(
cyclam)](ClO4)2 (46.3 mg, 0.1 mmol) in 0.5 mL of H O. The
with liquid nitrogen (T = 77 K) and equipped with a PremiumX
2
Na SnS ·14H O solution was added to the [Cu(cyclam)](ClO ) solu-
microwave bridge and a Bruker dual mode X-band cavity. The sam-
4
4
2
4 2
tion, stirred for 20 min. and was kept at room temperature. A violet
crystalline precipitate was formed after 2 h (≈ 29 % yield based on
Sn). Elemental analysis: found C: 23.90 %, H: 5.23 %, N: 11.11 %,
calculated: C: 24.18 %, H: 5.28 %, N: 11.28 %.
ples were dissolved in a mixture of H O/Glycerine (4:6) transferred
into a 1 mm quartz tube and measured at 77 K.
2
Thermogravimetric Analysis: Thermogravimetric investigations
were carried out using a Linseis STA PT1600 instrument, in which
the sample was heated in a nitrogen atmosphere with a heating
Structure Determination: The X-ray powder pattern (PXRD) of
compound I could be successfully indexed in a triclinic unit cell with
a Goodness of Fit of 50.6 using TOPAS Academics.[44] The position
of most atoms except for some carbon atoms of the cyclam ligand
–
1
rate of 4 K ∙min .
Acknowledgments
Financial support by the State of Schleswig-Holstein is grate-
fully acknowledged. We thank Inke Jess for the TG measure-
ments. We also thank Dr. Jan Krahmer for the EPR measurement.
could be determined using direct methods as implemented in Expo
45]
2
009.[ The missing carbon atoms of the ligand were subsequently
inserted using the molecular modelling software Materials Stu-
dio.[ The thus obtained model was further optimized by force-
field calculations using the universal force-field[ as implemented
in the forcite routine in Materials Studio. This structurally optimized
46]
47]
Keywords: Copper(II) thiostannate · Room temperature
starting model was afterwards converted into the conventional
crystallographic setting using Platon[ and the structure could be synthesis · Rietveld refinement · Electronic properties ·
successfully refined with the Rietveld method. The positions of all Thermal properties
atoms were freely refined using only bond restrains. The residual
48]
electron density in the Fourier map was attributed to crystal water
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–
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–
1
ation and the resolution are 1064 nm and 3 cm , respectively.
2
UV/Visible Spectroscopy: UV/Vis measurement was done at room
[
temperature with an UV/Vis/NIR two channel spectrometer Cary 5
9
–
1
(
Varian Techtron Pty., Darmstadt, 200–3000 cm ) using BaSO as
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Received: August 27, 2019
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Full Paper
Layered Compounds
A. Benkada, H. Reinsch,
W. Bensch* ........................................... 1–7
The First Thiostannate Compound
with Copper(II) Synthesized Under
Ambient Conditions: Crystal Struc-
ture, Electronic and Thermal Proper-
ties
Mixing aqueous solutions of Na SnS · stannate compound with composition
4
4
1
4H O and of [Cu(cyclam)](ClO ) at {[Cu(cyclam)] [Sn S ]} ·2nH O
con-
2
4 2
2
2 6
n
2
room temperature leads to a fast crys- taining Cu(II).
tallization of the first layered thio-
DOI: 10.1002/ejic.201900924
Eur. J. Inorg. Chem. 2019, 1–7
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© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim