Synthesis, Crystal Structures, and Properties of M(NCS)2-3-aminomethylpyridine Coordination Compounds (M = Cd, Zn)

Article abstract of DOI:10.1002/zaac.201700250

Reaction of Cd(NCS)₂ or Zn(NCS)₂ with 3-aminomethylpyridine (3-AMPy) leads to the formation of five compounds with the compositions [Cd(NCS)₂(3-AMPy)₂·(3-AMPy)]_n (1-Cd), [M(NCS)₂(3-AMPy)₂]_n [M = Cd (2-Cd), Zn (2-Zn)] [Cd(NCS)₂(3-AMPy)]_n (3-Cd), and [Zn(NCS)₂(3-AMPy)]₂ (3-Zn). In 1-Cd the Cd cations are linked by the 3-AMPy ligands into layers that consist of rings, built up of four Cd cations and four 3-AMPy ligands. These layers are stacked to form channels, in which the 3-AMPy solvate molecules are located. In the isotypic compounds 2-Cd and 2-Zn the metal cations are also linked into layers by the 3-AMPy ligands with an identical layer topology as that in 1-Cd, but a completely different conformation of the 3-AMPy ligand. In the most 3-AMPy deficient compound 3-Cd, the Cd cations are linked by μ-1,3-bridging thiocyanate anions and 3-AMPy ligands into chains, that are further connected into layers by additional anionic ligands. In 3-Zn two Zn cations are linked by pairs of 3-AMPy ligands into discrete dimers. Thermoanalysis and X-ray powder diffraction (XRPD) investigations show that upon heating 1-Cd transforms into 2-Cd and 2-Zn into 3-Zn. The compounds 2-Cd, 3-Cd, 2-Zn, and 3-Zn present ligand-based luminescence in the blue-green spectral range with maxima between 21276 and 21795 cm^–1.

Full text of DOI:10.1002/zaac.201700250

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201700250
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Synthesis, Crystal Structures, and Properties of M(NCS) -3-
2
aminomethylpyridine Coordination Compounds (M = Cd, Zn)
Tristan Neumann,[a] Luzia S. Germann, Igor Moudrakovski, Robert E. Dinnebier,
[b]
[b]
[b]
Cesar dos Santos Cunha,[a] Huayna Terraschke, and Christian Näther*
[a]
[a]
Dedicated to Professor Thomas Schleid on the Occasion of his 60th Birthday
Abstract. Reaction of Cd(NCS)
idine (3-AMPy) leads to the formation of five compounds with the com-
positions [Cd(NCS) (3-AMPy) ·(3-AMPy)] (1-Cd), [M(NCS) (3-
AMPy) [M = Cd (2-Cd), Zn (2-Zn)] [Cd(NCS) (3-AMPy)] (3-Cd),
and [Zn(NCS) (3-AMPy)] (3-Zn). In 1-Cd the Cd cations are linked by
the 3-AMPy ligands into layers that consist of rings, built up of four Cd
cations and four 3-AMPy ligands. These layers are stacked to form chan-
nels, in which the 3-AMPy solvate molecules are located. In the isotypic
compounds 2-Cd and 2-Zn the metal cations are also linked into layers
by the 3-AMPy ligands with an identical layer topology as that in 1-Cd,
2
or Zn(NCS)
2
with 3-aminomethylpyr-
but a completely different conformation of the 3-AMPy ligand. In the
most 3-AMPy deficient compound 3-Cd, the Cd cations are linked by μ-
1,3-bridging thiocyanate anions and 3-AMPy ligands into chains, that
2
2
n
2
are further connected into layers by additional anionic ligands. In 3-Zn
two Zn cations are linked by pairs of 3-AMPy ligands into discrete di-
mers. Thermoanalysis and X-ray powder diffraction (XRPD) investi-
gations show that upon heating 1-Cd transforms into 2-Cd and 2-Zn into
2
]
n
2
n
2
2
3-Zn. The compounds 2-Cd, 3-Cd, 2-Zn, and 3-Zn present ligand-based
luminescence in the blue-green spectral range with maxima between
–
1
21276 and 21795 cm .
Introduction
Investigations on the synthesis, structures, and properties of
new coordination compounds and polymers are still an impor-
tant topic in coordination chemistry.
cyanate and selenocyanate compounds are also of interest, be-
cause of their variable coordination modes, including the ter-
minal and the bridging coordination.[
cial importance if paramagnetic metal cations are used, be-
is of special interest because of its large magnetic anisotropy
leading to interesting magnetic phenomena like, e.g. a slow
relaxation of the magnetization, which is indicative for single
chain magnet behavior.[
44–49]
Several of such compounds were
[
1–11]
In this context thio-
prepared by thermal decomposition of precursors with a ter-
minal N-coordination of the anionic ligands, which enforces
the formation of the desired coordination polymers with a
12–17]
The latter is of spe-
bridging coordination.[
14]
In this case only microcrystalline
powders are obtained that cannot be characterized by single-
crystal X-ray diffraction. In these cases their structures can
either be solved ab initio from X-ray powder diffraction
cause magnetic exchange can be mediated by the anionic li-
gands leading to different magnetic phenomena.[
18–30]
Unfortu-
nately, most 3d cations are not very chalcophilic and therefore,
such compounds with a μ-1,3-bridging coordination are some-
times difficult to prepare. This is completely different for, e.g.
(XRPD) data or by the synthesis of similar compounds that
might be isotypic to the desired coordination polymers. In this
context, the synthesis of thio- or selenocyanate compounds
II
Cd , that prefers coordination to the S or the Se atom and thus,
II
based on Cd can be helpful, because cadmium also prefers
shows a variety of compounds with different topologies of the
an octahedral coordination and very often forms compounds
that are isotypic to the paramagnetic counterparts. Moreover,
[
31–33]
coordination network.
Moreover, compounds based on
II
II
Cd and Zn with additional co-ligands can show lumines-
cence and several of them were recently reported.[6,34–43]
Our interests focus mainly on the magnetic properties of
thio- and selenocyanate coordination polymers based on the 3d
II
thermal decomposition of Co compounds can also lead to un-
desired tetrahedral complexes, which can be identified using
II
II
analogous compounds based on Zn , that in contrast to Cd
prefers tetrahedral coordination arrangements.
II
II
II
II
metal cations Mn , Fe , Ni , and Co . The last mentioned ion
In the course of our systematic work we also investigated
the influence of the co-ligands on the structural properties of
thio- and selenocyanate coordination compounds. In most
cases we used monodentate pyridine derivatives, which can
coordinate only via the pyridine N atom to the central metal
atoms. To increase the dimensionality of the coordination net-
works we also became interested in bridging N-donor ligands.
In this context 3-aminomethylpyridine (3-AMPy) can be use-
ful, because it can coordinate with both, the pyridine and the
amino N atom to the metal atoms. It is noted that no crystal
*
Prof. Dr. C. Näther
E-Mail: cnaether@ac.uni-kiel.de
[
[
a] Institute of Inorganic Chemistry
Christian-Albrechts-University of Kiel
Max-Eyth-Strasse 2
24118 Kiel, Germany
b] Max Planck Institute for Solid State Research
Heisenbergstrasse 1
70569 Stuttgart, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201700250 or from the au-
thor.
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structures with thio- or selenocyanate coordination compounds
with 3-AMPy are reported in the Cambridge Structure Datab-
ase. However, a few metal complexes are known, where in
[50–54]
most cases a bridging coordination is observed.
There is
only one compound based on Pd, in which the 3-methylami-
nopyridine ligand is coordinated only via the pyridine N atom
to the central metal atom.[
55]
Results and Discussion
Synthesis and Crystal Structures
The reaction of Cd(NCS) with 3-AMPy leads to the forma-
2
tion of three crystalline compounds with different composition.
Two compounds with the composition [Cd(NCS) (3-AMPy) ]
2
2 n
(
2-Cd) and [Cd(NCS) (3-AMPy)] (3-Cd) are formed during
2 n
the reaction of Cd(NCS) in water at room temperature. A dif-
2
ferent crystalline phase [Cd(NCS) (3-AMPy) ·3-AMPy] (1-
2
2
n
Cd) was formed if pure 3-AMPy was used as solvent. With
Zn(NCS) and 3-AMPy two crystalline phases were obtained
2
with the compositions of [Zn(NCS) (3-AMPy) ] (2-Zn) and
2
2 n
[
Zn(NCS) (3-AMPy)] (3-Zn). For all these compounds suit-
2 2
able crystals were grown and characterized by single-crystal
X-ray diffraction and for 3-Cd by XRPD in addition (see Ex-
perimental Section).
[
Cd(NCS) (3-AMPy) ·3-AMPy] (1-Cd) crystallizes in the
2 2 n
monoclinic space group P2 with Z = 2 and all atoms in gene-
1
ral positions. In the crystal structure the Cd cations are coordi-
nated by two terminal N-bonding thiocyanate anions and two
symmetry independent 3-AMPy ligands via both the pyridine
nitrogen as well as the amino group (Figure S1, Supporting
Information). Bond lengths and angles are comparable to those Figure 1. Crystal structure of 1-Cd with view along the a-axis (top)
and perpendicular to the layers along the b axis with N–H···N hydrogen
bonding shown as dashed lines (Cd: orange; S: yellow; N: blue; C:
in other compounds with a similar N coordination and the
coordination polyhedron can be described as a slightly dis-
6
dark grey; O: red; H: light grey). An ORTEP plot can be found in
torted octahedron (Table S1, Supporting Information).
Figure S1 (Supporting Information).
In the crystal structure all Cd cations are linked by the 3-
AMPy ligands into layers, which are parallel to the bc plane
Table 1. Hydrogen bonding /Å,° for 1-Cd.
(Figure 1). These layers consist of rings, where each of them
are built up by four Cd cations and four 3-AMPy ligands and D–H···A
d(H···A)
d(D···A)
ϽD–H···A
are stacked perfectly onto each other. By this arrangement
channels are formed along the a axis, where the 3-AMPy solv- N(12)–H(12B)···N(32)
ate molecules are located (Figure 1). Each of the solvate guest N(22)–H(22B)···N(31)
N(12)–H(12A)···S(1)
2.84
2.22
2.19
2.96
2.98
3.00
2.72
3.743(6)
3.107(8)
3.083(8)
3.818(7)
3.746(8)
3.780(9)
3.582(6)
169.7
165.9
167.6
150.5
138.8
136.9
165.8
C(31)–H(31)···S(2)
molecules is connected to the host structure by intermolecular
C(35)–H(35)···S(2)
N–H···N hydrogen bonding between the pyridine N atoms and
C(36)–H(36A)···S(1)
the amino H atoms of the 3-AMPy ligands (Figure 1: top and
Table 1). There are additional short S···H distances indicating
for intermolecular N–H···S and C–H···S interactions (Table 1).
N(32)–H(32A)···S(2)
[
Cd(NCS) (3-AMPy) ] (2-Cd) and [Zn(NCS) (3-AMPy) ]
The metal cations are linked by bridging 3-AMPy ligands
2
2 n
2
2 n
(2-Zn) are isotypic and crystallize in the monoclinic space into layers, that are parallel to the (–1 0 1) plane (Figure 2
group P2 /n with Z = 2. The metal cations are located on cen- bottom). As in 1-Cd, the layers are built up by four metal
1
ters of inversion and are coordinated by two N-terminal trans- cations and four 3-AMPy ligands, but because the conforma-
coordinating thiocyanate anions and four 3-AMPy ligands, of tion of the 3-AMPy ligands is completely different, the shape
which two are trans coordinating with the pyridine N atom, of the layers is different. The layers are further connected by
and two with the amino nitrogen atom (Figure 2 top and Figure weak intermolecular N–H···S interactions into a three-dimen-
S2, Supporting Information). The coordination polyhedron sional network (Figure 2: bottom and Table 2).
around the metal cations can be described as slightly distorted
octahedra. The M–N distances correspond to those in similar (3-Cd) exhibit the same ratio between the metal thiocyanate
compounds (Table S2, Supporting Information). and the co-ligand 3-AMPy but show completely different crys-
[Zn(NCS) (3-AMPy)] (3-Zn) and [Cd(NCS) (3-AMPy)]
2 2 2 n
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tetrahedron (Table S3, Supporting Information). The Zn cat-
ions are linked into centrosymmetric dimers via two bridging
-aminomethylpyridine ligands (Figure 3 top). Within the di-
3
mers both pyridine rings are coplanar but shifted relative to
each other in order that one of the pyridine rings is located
above one C–H hydrogen atom of the second ring. The dis-
tance between the midpoints of both pyridine rings is around
3.821 Å. These dimers are further linked into chains along the
crystallographic a axis via intermolecular N–H···S hydrogen
bonding between one of the two amino H atoms and the thio-
cyanate S atom, which act as the acceptor (Figure 3 bottom
and Table 2). There are additional short contacts between some
of the C–H···H atoms and the thiocyanate S atoms, which are
indicative for a weak C–H···S hydrogen bonding network
(Table 2).
Figure 2. Crystal structure of 2-Zn as a representative with view on
the (–1 0 1) plane (top) and parallel to the layers (bottom) with N–H···S
hydrogen bonding shown as dashed lines (Zn/Cd: brown; S: yellow; N:
blue; C: dark grey; O: red; H: light grey). ORTEP plots can be found
in Figure S2 (Supporting Information).
Table 2. Hydrogen bonding /Å,° for 2-Cd, 2-Zn, and 3-Zn.
D–H···A
-Cd
C(12)–H(12)···S(1)
N(12)–H(12A)···S(1)
N(12)–H(12B)···S(1)
d(H···A)
d(D···A)
ϽD–H···A
Figure 3. Crystal structure of 3-Zn with view of the dimers (top) and
along the crystallographic b axis (bottom) with intermolecular N–H···S
hydrogen bonding shown as dashed lines (Zn: brown; S: yellow; N:
blue; C: dark grey; O: red; H: light grey). An ORTEP plot can be
found in Figure S3 (Supporting Information).
2
3.01
2.76
2.63
3.725(2)
3.658(2)
3.504(2)
133.0
169.6
160.5
2-Zn
C(12)–H(12)···S(1)
N(12)–H(12A)···S(1)
N(12)–H(12B)···S(1)
2.96
2.88
2.66
3.7014(19)
3.7569(17)
3.5184(17)
136.4
163.0
156.7
Diffuse scattering was observed for 3-Cd in form of streaks
between the very broad Bragg reflections in the reconstructed
precession images along the c* axis, indicating severe disorder
within the crystal. Despite the poor crystal quality indexing
suggested a primitive orthorhombic unit cell with a =
3-Zn
N(12)–H(12A)···S(2)
C(14)–H(14)···S(2)
C(15)–H(15)···S(1)
C(16)–H(16B)···S(1)
2.66
2.85
2.92
3.02
3.573(4)
3.785(4)
3.852(4)
3.917(4)
176.8
166.9
166.9
151.3
7.1120(4) Å, b = 16.1654(8) Å, and c = 19.55770 (1) Å.
Analysis of the systematic extinctions suggested space group
Pbca, in which the structure was solved but the refinement
tal structures. 3-Zn crystallizes in the monoclinic space group leads to very poor reliability factors (R Ͻ 20%). Therefore
1
P2 /n with Z = 4 and all atoms lying on general positions. The additional XRPD analysis was performed. Indexing of the
1
Zn cations are tetrahedrally coordinated by two terminal N- measured powder pattern (see Figure S4, Supporting Infor-
bonded thiocyanate anions and two symmetry equivalent 3- mation) lead to a pseudo orthorhombic unit cell with a slightly
aminomethylpyridine ligands. One coordinates via the pyridine distorted beta angle of 90.415(12) and P2 /c as the most appro-
1
N atom, whereas the second coordinates via the amino N atom priate space group. The structural model of the single-crystal
to the central metal atoms (Figure 3 top and Figure S3, Sup- X-ray diffraction analysis was used as a starting point for the
porting Information). Bond lengths and angles are comparable Rietveld analysis after the symmetry was reduced from Pbca
[63]
to literature values and the angles indicate a slightly distorted to P2 /c by ISODISORT.
All atoms are lying on general
1
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positions. The asymmetric unit (ASU) consists of two Cd cat- IR and Raman Spectroscopy
ions, four thiocyanate ions and two 3-AMPy ligands. This is
in excellent agreement with the solid state NMR (ssNMR) re-
sults. Peak splitting was observed in the 113Cd spectrum, an
indication for two symmetry independent Cd sites in the asym-
metric unit (see Figure S5, Supporting Information). Further-
more, all signals originating from the 3-AMPy were found to
be split, again suggesting two symmetry independent sites in
the ASU (Figure S6, Supporting Information).
IR and Raman measurements were performed to investigate
if one can differ between the terminal and the bridging coordi-
nation of the anionic ligands using the value of the CN stretch-
ing vibration. For terminal N-bonded NCS anions the CN
–1
stretch is expected at about 2050 cm , whereas it is shifted to
[
14]
higher values if they act as bridging ligands.
For 2-Cd the
–1
CN stretch is observed at 2067 cm in the IR and at 2067 and
073 cm in the Raman spectra, which is in the range ex-
–1
2
The Cd cations are coordinated by each two S and N bond-
ing thiocyanate anions and two 3-AMPy ligands, of which one
is coordinated by the pyridine N atom, whereas the other is
coordinated by the amino N atom (Figure 4). The two S
bonded anions and the two 3-AMPy N atoms are each cis coor-
dinating, whereas the N bonding anionic ligands are trans co-
pected for terminal bonded anionic ligands (Figure S12, Sup-
porting Information). For 3-Cd two bands are observed in the
–1
Raman spectrum at 2086 and 2106 cm , which cannot be re-
solved in the IR spectrum (Figure S13, Supporting Infor-
mation). This is in agreement with the presence of two dif-
ferent μ-1,3-bridging thiocyanate anions and the fact that the
ordinating. The cadmium cations are linked by each one 3- Cd cations are alternately linked by only one anionic ligand or
AMPy ligand and one μ-1,3-bridging thiocyanate anion into by a single NCS bridge and one 3-AMPy ligand. In 2-Zn
chains along the a axis, that are further connected into layers bands between 2073 and 2078 cm–1 are observed, which
by single bridging anionic ligands (Figure 4).
means a shift towards higher wavenumbers compared to the
isostructural 2-Cd (Figure S14, Supporting Information). Fi-
nally, for 3-Zn, in which only terminal N-bonded anions are
present, the CN stretch is found at 2081 cm in the IR and
at 2095 cm–1 in the Raman spectrum (Figure S15, Supporting
Information). This is at the borderline to that expected for
bridging anionic ligands and shows that only on the basis of
spectroscopic investigations one cannot surely differ between
a terminal and bridging thiocyanate coordination.
–1
Thermoanalytical Investigations
To investigate the thermal properties of all compounds, mea-
surements using simultaneously differential thermoanalysis
and thermogravimetry (DTA-TG) were performed. 1-Cd exhi-
bits two mass losses upon heating in the TG curve, that are
accompanied with three endothermic effects in the DTA curve
(Figure S16, Supporting Information). The experimental mass
loss in the first step is larger than that calculated for the re-
moval of one solvate 3-AMPy ligand (Δmexp = 32%, Δmcalcd.
=
19.6%), which originates from the fact that the synthesis
must be performed in the pure ligand and therefore, all samples
contain additional 3-AMPy. This is in good agreement with
the first endothermic effect at 74 °C that corresponds to the
boiling point of the ligand. XRPD measurements of the residue
of the first TG step correspond to 2-Cd, confirming the trans-
formation of 1-Cd into 2-Cd (Figure 5). On further heating
two endothermic and one exothermic signal are observed,
which are accompanied with an additional mass step. The
XRPD pattern of the residue formed in the second mass step
is completely different from that of all Cd compounds pre-
sented here, indicating the decomposition of 2-Cd (Figure S17,
Supporting Information).
Figure 4. Crystal structure of 3-Cd with view along the crystallo-
graphic b axis (Cd: orange; S: yellow; N: blue; C: dark grey; O: red;
H: light grey).
Based on the structural data, XRPD patterns were calculated
and compared with the experimental patterns, which proves
that 2-Cd, 3-Cd, 2-Zn, and 3-Zn were obtained as pure phases
Similar TG experiments for 2-Cd show one poorly resolved
mass step at about 194 °C, followed by an exothermic event
(Figures S7–S10, Supporting Information). In contrast, 1-Cd
is always contaminated with 2-Cd, even if Cd(NCS) is re- (Figure S18, Supporting Information). As expected, the XRPD
2
acted in pure 3-aminopyridine without additional solvent (Fig- pattern of the intermediate formed in the first TG step is iden-
ure S11, Supporting Information).
tical to that obtained after the second mass loss of 2-Cd. For
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Figure 5. Experimental XRPD pattern (λ = Cu-Kα1) of a mixture of
-Cd and 2-Cd (top) and of the residue obtained after the first mass
loss of this mixture (middle) as well as calculated pattern for 2-Cd
bottom).
1
Figure 6. Samples 2-Cd, 3-Cd, 2-Zn, and 3-Zn under day light (left)
and near UV light (400 nm, right) measured with an optical fiber.
(
Since Cd2+ and Zn2+ do not show radiative electronic transi-
tions, it is expected that the emissive properties of these com-
3
-Cd only one continuous mass loss is observed starting at
[57]
pounds are caused by ligand-based luminescence.
As pre-
about 192 °C, that corresponds to the decomposition of this
compound (Figure S18).
DTA-TG investigations for 2-Zn show three mass losses
upon heating, of which the first one is accompanied with a
very sharp endothermic signal in the DTA curve (Figure S19,
Supporting Information). The experimental mass loss of
viously explained in the literature for other Cd and Zn2+ co-
ordination polymers,[ this luminescence properties are as-
signed to the π*Ǟπ transitions of the aromatic units of the
organic ligand. This fact agrees with the strong overlap of the
emission spectra of compounds 2-Cd, 3-Cd, 2-Zn, and 3-Zn
with the emission spectrum of the 3-AMPy ligand (Figure 7),
applying the excitation energies listed on Table 3. The emis-
2+
57]
1
8.5% in the first two steps is much lower than that expected
for the removal of one 3-AMPy ligand (Δmcalc = 27.1%),
which would be expected if a complete transformation into 3-
Zn would occur (Figure S19). However, the measured XRPD
pattern of the residue matches well with the calculated XRPD
pattern of 3-Zn but there are some additional peaks that can
be assigned to untransformed 2-Zn, which can be traced back
to the fact that the TG curve is not well resolved (Figure S20,
Supporting Information).
2+
–1
sion spectra of all Cd (e.g. ν˜ = 25125 cm for 2-Cd and
ex
2+
2
6316 cm–1 for 3-Cd) and Zn (e.g. ν˜ ex = 27027 cm–1 for 2-
Zn and 25189 cm for 3-Zn) samples (Figure 7 and Figures
S22–S25, Supporting Information) are overlapped and com-
posed by a broad band within the blue-green spectral range,
–1
–1
extended mostly between approximately 14000 cm and
–
1
–1
2
2
6000 cm , with maxima varying between 21276 cm and
1795 cm–1 and full width at half maximum (FWHM) varying
between 4241 cm and 5905 cm . The emission band of the
–1
–1
–1
3-AMPy ligand ( ν˜ ex = 27027 cm ) is located in the same spec-
Luminescence Measurements
Under day light, the 2-Cd, 3-Cd, 2-Zn, and 3-Zn com-
pounds are colorless (Figure 6), in agreement with the respec-
tive reflection spectra shown in Figure S21 (Supporting Infor-
mation). All these samples present reflectance values above
–1
approximately 90% for energies lower than 22000 cm , ab-
sorbing nearly no light in the visible spectral range. In contrast,
the reflectance strongly decreases in the UV spectral range
and reaches its minimum values for energies higher than
–
1
3
5714 cm , coinciding with the absorption maximum re-
corded for the pure 3-AMPy ligand molecule. The reflection
spectra allowed, in addition, the estimation of the bandgap en-
ergy[ of approximately 4.5 eV for 2-Cd and 3-Cd as well as
56]
4
.4 eV for 2-Zn and 3-Zn. Under excitation with monochro-
Figure 7. Emission spectra of 2-Cd (black curve), 3-Cd (red curve),
-Zn (blue curve), 3-Zn (pink curve), and 3-AMPy (green curve), ap-
plying excitation energies are listed in Table 3.
matic light at 400 nm, the samples 2-Cd, 3-Cd, 2-Zn and 3-
Zn present a blue-green luminescence.
2
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–
1
4
tral range with FWHM of 7127 cm and maximum at The resulting white precipitate of BaSO was filtered off and the fil-
–
1
trate was concentrated to complete dryness resulting in white residues
of Cd(NCS) and Zn(NCS) . All crystalline powders were prepared by
stirring of the reactants in solution at room temperature. The residues
were filtered off and washed with water and air-dried.
2
0230 cm (Figure S26, Supporting Information). Hence, the
2
+
2+
2
2
similar optical properties of Cd and Zn coordination poly-
mers are expected due to their similar chained- and layered-
based structural properties. In addition, the slight deviation be-
2
+
2+
tween the spectra measured for the Cd and Zn compounds
Synthesis of 2-Zn: Single crystals suitable for X-ray crystal structure
and the ligand may occur, because 2-Cd, 3-Cd, 2-Zn, and 3- determination were obtained by the reaction of Zn(NCS) (27.2 mg,
2
Zn were measured in the solid state, whereas ligand 3-AMPy 0.15 mmol) with 3-aminomethylpyridine (68.9 μL, 0.6 mmol) in
is liquid at room temperature.
1.5 mL ethanol at room temperature within several days. A crystalline
powder was obtained by the reaction of Zn(NCS) (272.32 mg,
1.5 mmol) in an excess of 3-aminomethylpyridine (611.0 μL,
.0 mmol) in 5 mL ethanol after stirring for 5 d. C14 Zn
397.8332 g·mol ): calcd. C 42.27, H 4.05, N 21.12, S 16.12%; found:
C 42.463, H 4.06, N 21.023, S 15.498%. IR (ATR): ν˜ max = 3279 (m),
242 (m), 3160 (m), 3055 (w), 2978 (w), 2944 (w), 2865 (w), 2074
s), 1593 (m), 1480 (m), 1447 (m), 1427 (m); 1360 (w), 1331 (w),
2
Table 3. Maximum, excitation energy, and FWHM of measured emis-
sion spectra /cm–1 of 2-Cd, 3-Cd, 2-Zn, 3-Zn, and 3-AMPy.
6
(
16 6 2
H N S
–
1
Compound Emission maximum Excitation energy FWHM
2
3
2
3
3
-Cd
-Cd
-Zn
-Zn
21753
21719
21795
21276
20230
25125
26316
27027
25189
27027
5128
4241
5905
5294
7127
3
(
1
9
248 (w), 1228 (w), 1189 (m), 1133 (m), 1052 (m), 990 (s), 964 (m),
33 (m), 895 (w), 850 (w), 806 (m), 780 (m), 713 (s), 645 (m9; 627
-AMPy
–
1
(
(
m), 568 (s) cm . Raman ν˜ max = 3247 (w), 3160 (w), 3063 (w), 2980
–
1
w), 2947 (w), 2078 (s), 1495 (w), 1038 (w) cm .
Synthesis of 3-Zn: Single crystals suitable for X-ray crystal structure
determination were obtained by the reaction of Zn(NCS) (54.4 mg,
.3 mmol) with 3-aminomethylpyridine (17.2 μL, 0.15 mmol) in
.5 mL ethanol at room temperature within several days. A crystalline
(544.64 mg,
.0 mmol) and 3-aminomethylpyridine (152.7 μL, 1.5 mmol) in 5 mL
Conclusions
2
0
1
New coordination compounds based on Cd(NCS)2 and
Zn(NCS) with 3-aminomethylpyridine as ligand are reported.
2
powder was obtained by the reaction of Zn(NCS)
3
2
In contrast to related compounds with a ratio between
Cd(NCS) and the pyridine derivative of 1:2, in 1-Cd and 2-
–1
2
8 8 4 2
ethanol after stirring for 5 d. C H N S Zn (289.6903 g·mol ): calcd.
C 33.17, H 2.78, N 19.34, S 22.14%; found: C 30.719, H 2.507, N
Cd the metal cations are not linked by the anionic ligands into
a 1D or 2D coordination network, as usually observed in this 18.848, S 20.675%. IR (ATR): ν˜ max = 3266 (w), 3213 (w), 3130 (w),
class of compounds. Because the amino N atom is also a very 3066 (w), 2081 (s), 1609 (m), 1584 (m), 1484 (w), 1441 (m), 1393
strong donor, each four coordination sites of the cations are (w), 1345 (w), 1311 (w), 1257 (w), 1199 (w), 1144 (m), 1064 (m),
1
035 (w), 997 (m), 972 (m), 950 (m), 826 (w), 805 (m), 707 (m), 655
blocked by the co-ligand and thus, the thiocyanate anions are
only terminal coordinated. Bridging anionic ligands can only
–
1
(
m), 565 (m) cm . Raman ν˜ max = 3068 (m), 2934 (m), 2878 (w),
–
1
2095 (s), 1495 (m), 1035 (m) cm .
be observed for a ratio between Cd(NCS) and 3-AMPy of
2
1
:1, which is the case in 3-Cd, where the metal cations are
Synthesis of 1-Cd: Single crystals suitable for X-ray crystal structure
determination were obtained by the reaction of Cd(NCS) (22.8 mg,
2+
linked into layers by single thiocyanate anions. Zn is less
2
2
+
chalcophilic than Cd and thus, no bridging anionic ligands 0.1 mmol) with 3-aminomethlypyridine (407.3 μL, 4.0 mmol) in a
are expected. IR and Raman investigations prove that one can- closed test tube at room temperature after several days. However, all
not differ between a terminal and a bridging coordination of batches were always contaminated with crystals of 2-Cd (Figure S11,
Supporting Information).
the anionic ligand, because the values observed for the CN
stretch overlap. Compared to similar compounds with pyridine
Synthesis of 2-Cd: Single crystals suitable for X-ray crystal structure
derivatives as co-ligands, the compounds are thermally more
2
determination were obtained by the reaction of Cd(NCS) (45.7 mg,
stable, which might also be traced back to the relative strong
bonds between the cations and the amino nitrogen atom. Due
0.2 mmol) with 3-aminomethylpyridine (20.37 μL, 0.2 mmol) in 3 mL
of dest. water in a closed test tube at 120 °C for 6 d. A crystalline
2
+
2+
to their similar crystal structure, the Cd and Zn compounds powder was obtained by the reaction of Cd(NCS)2 (114.3 mg,
present similar optical properties with bandgap between 4.4 eV 0.5 mmol) with 3-aminomethylpyridine (407.3 μL, 4.0 mmol) in
–
1
and 4.5 eV. Likewise, the emission spectra strongly overlap in 5.0 mL demineralized water.
C
14
H16CdN
6
S
2
(444.8532 g·mol ):
calcd. C 37.80, H 3.63, N 18.89, S 14.42%; found: C 38.604, H 3.625,
N 18.277, S 13.736%. IR (ATR): ν˜ max = 3271 (m), 3239 (m), 3160
m), 3051 (w), 2969 (w), 2940 (w), 2870 (w), 2840 (w), 2067 (s),
599 (m), 1581 (m), 1479 (m), 1446 (m), 1428 (s), 1361 (w), 1331
the blue-green spectral range, coinciding also with the emis-
sion spectra of the 3-AMPy linker and enabling to assign their
optical properties to ligand-based luminescence.
(
1
(
(
7
w), 1245 (w), 1228 (w), 1188 (m), 1151 (w), 1120 (s), 1049 (m), 1035
w), 985 (s), 960 (m), 931 (m), 894 (w), 844 (m), 802 (s), 774 (m),
10 (s), 645 (s), 621 (m), 552 (s) cm . Raman ν˜ max = 3243 (w), 3163
Experimental Section
–
1
Syntheses: Ba(NCS)
tained from Alfa Aesar and ZnSO
from Merck. All chemicals were used without further purification.
2
·3H
2
O and 3-aminomethylpyridine were ob-
(wb), 3063 (w), 2968 (w), 2940 (w), 2873 (w), 2073 (m), 1602 (w),
1581 (w), 1495 (m), 1228 (w), 1189 (w), 1123 (w), 1050 (w), 1036
(s), 842 (w), 805 (w), 773 (w), 646 (w), 625 (w) cm .
4
·H O, CdSO ·8/3H O were obtained
2
4
2
–
1
Cd(NCS)
amounts of ZnSO
2
and Zn(NCS)
2
were prepared by the reaction of equimolar Synthesis of 3-Cd: Single crystals suitable for X-ray structure deter-
·8/3H O and Ba(NCS) .3H O in water. mination were obtained by the reaction of Cd(NCS) (45.7 mg,
4
·H O, CdSO
2
4
2
2
2
2
Z. Anorg. Allg. Chem. 0000, 0–0
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6
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
0.2 mmol) with 3-aminomethylpyridine (20.37 μL, 0.2 mmol) in 3 mL
ponent for the crystallite size and a Lorentzian component for micro-
of dest. water in a closed test tube at 120 °C for 6 d (obtained from strain broadening were freely refined. Free refinement of atomic coor-
the same batch as 2-Cd). A crystalline powder was obtained by the dinates was hindered by the reduced information content of a XRPD
reaction of Cd(NCS)
pyridine (203.7 mg, 2.00 mmol) in 5.0 mL demineralized water.
C H CdN S (336.7103 g·mol ): calcd. C 28.54, H 2.39, N 16.64, S
8 8 4 2
2
(457.1 mg, 2.0 mmol) with 3-aminomethyl-
pattern and apparent stacking faults. The atoms were within their con-
vergence radius but bond lengths and the coordination arrangement
was chemically not reasonable. Therefore the whole asymmetric unit
–1
1
9.05%; found: C 27.375, H 2.168, N 15.623, S 18.000%. IR (ATR): was described as rigid body using the z-matrix notation with optimized
ν˜ max = 3308 (w), 3252 (w), 3167 (w), 2864 (w), 2087 (s), 1599 (m), bond lengths and angles and its position and orientation were refined
583 (w), 1488 (w), 1456 (w), 1431 (m), 1393 (w), 1348 (w), 1289 without restrains. In the final refinement of the average structure all
w), 1206 (w), 1167 (w), 1100 (m), 1059 (m), 1036 (w), 1014 (m), lattice parameters, zero error, peak profile contributions, an overall
92 (w), 967 (m), 941 (m), 902 (w), 814 (w), 792 (m), 764 (w), 703 thermal displacement parameter and the positions of the two symmetry
1
(
9
–1
(
(
(
m), 646 (m), 611 (m), 506 (m) cm . Raman ν˜ max = 3094 (wb), 2952 independent cadmium ions were refined freely, while all other sites
w), 2860 (w), 2106 (m), 2086 (s), 1495 (w), 1059 (w), 1037 (m), 812 were fixed.
w) cm .
–1
Single-crystal Structure Analyses: Data collections were performed
XRPD and Rietveld Refinement: The measurements were performed with an imaging plate diffraction system (IPDS-2) from STOE & CIE
with a Stoe Transmission Powder Diffraction System (STADI P) with
Cu-Kα1 radiation (λ = 1.5406 Å) equipped with a MYTHEN 1 K detec-
tor from Dectris and a Ge(111) monochromator from STOE & CIE. SHELXL-2014.
α
using Mo-K radiation. Structure solution was performed with
[
64]
2
SHELXT
and structure refinement was performed against F using
[
65]
A numerical absorption correction was applied
Selected crystal data and details of the refinement are listed in Table 4. using programs X-RED and X-SHAPE of the program package X-
[
66]
Area.
All non-hydrogen atoms were refined with anisotropic dis-
Table 4. Selected crystal data and details of the Rietveld refinement
for 3-Cd.
placement parameters. The C–H and N–H hydrogen atoms were posi-
tioned with idealized geometry and were refined isotropic with Uiso(H)
=
–1.2 Ueq(C, N) using a riding model. The absolute structure of 1-Cd
3
-Cd
was determined and is in agreement with the selected setting (Flack-x
parameter: –0.05(2). Finally, it is noted that structure refinement of 3-
Cd in space group P2 /c assuming pseudo-merohedral twinning do not
1
lead to a significant improvement of the reliability factors. Selected
crystal data and details of the structure determination are summarized
in Table 5.
Formula
MW /g·mol–1
Crystal system
Space group
Wavelength /Å
a /Å
16 16 8 4 2
C H N S Cd
673.43
monoclinic
P2 /c
1.5406
19.613(2)
7.1813(6)
1
b /Å
c /Å
α /°
β /°
16.2698(17)
90
90.414(12)
90
2291.5(4)
295
4
1.952
18.384
78.76
6.40
4.72
0.81
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1564365 (1-Cd), CCDC-1564368 (2-Cd), CCDC-
γ /°
V /Å3
T /K
Z
1564867 (3-Cd), CCDC-1564366 (2-Zn), and CCDC-1564367 (3-Zn)
–
3
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
Dcalc /g·cm
–
1
μ /mm
θmax /°
Solid State NMR Spectroscopy: 13C and 113Cd Solid state NMR mea-
surements were performed at 100.63 and 88.73 MHz, respectively,
with a Bruker Avance-III 400 MHz instrument at magnetic field of 9.4
T. A standard Bruker BL4 double resonance 4 mm Magic Angle Spin-
a)
R
R
R
R
wp /%a)
p
/%
exp /% a)
Bragg /%
a)
3.95
2
ning (MAS) probe was used with the samples packed in ZrO ceramic
spinners and spun at 10 kHz ( Cd) or 12 kHz ( C). Cross-polariza-
tion from protons was implemented with a ramped contact pulse on
a) As defined in TOPAS.
113
13
3-Cd was gently ground and filled into a Ø 0.5 mm diameter glass proton channel and accompanied by high power proton decoupling.
capillary (No. 0140, Hilgenberg). The capillary was spun during the The cross-polarization conditions were tuned on signals from solid
1
13
13
experiment (7–79° 2θ over 10 h) for better particle statistics. The Paw-
3 2 2
Cd(NO ) ·x4H O ( Cd), and glycine ( C), which have also served
[58]
[59]
113
13
ley
V5[60].
and Rietveld
refinements were performed using TOPAS
as secondary chemical shift standards ( Cd δiso = –100.0 ppm,
C
[67]
δiso = 176.46 ppm). The experiments were optimized both for cross-
polarization contact time and repetition delay, which were set to 10
Indexing of the XRPD pattern of 3-Cd was performed by an iterative
use of singular value decomposition as implemented in TOPAS V5
113
13
ms ( Cd), 4 ms ( C), and 4s, respectively. A total of 4000 accumula-
tions were collected in each case for a sufficiently good signal-to-noise
ratio.
leading to a monoclinic space group (P2
1
/c) with the lattice parameters
The peak profile was described using the funda-
mental parameter approach as implemented in TOPAS.[62] The back- The assignments in the spectra were made based on CASTEP DFT
[61]
listed in Table 4.
ground was modelled by Chebychev polynomials (12th order).
calculations performed in a Material Studio 2017 by BIOVIA using
the experimental crystal structures.
The symmetry of the crystal structure, obtained from the single-crystal
X-ray diffraction experiment was reduced from Pbca to P2
forming the basis {(0,1,0),(0,0,1),(1,0,0)} using ISODISTORT.
lattice parameters, peak profile, microstructure using a Gaussian com-
1
/c by trans-
Optical Spectroscopy: Luminescence spectra were measured with a
HORIBA Jobin Yvon GmbH (Unterhaching, Germany) spectrometer
(Fluorolog3) at room temperature, equipped with a iHR-320-FA Triple
[
63]
The
Z. Anorg. Allg. Chem. 0000, 0–0
www.zaac.wiley-vch.de
7
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Table 5. Selected crystal data and details of the single crystal structure refinements.
-Cd 2-Cd
1
2-Zn
3-Zn
Formula
MW /g·mol–1
Crystal system
Space group
a /Å
C
20
H
24
N
8
S
2
Cd
C
14
H
16
N
6
S
2
Cd
C
14
H
16
N
6
S
2
Zn
16 16 8 4 2
C H N S Zn
552.99
monoclinic
P2
9.2289(3)
12.3272(4)
10.9800(3)
109.602(2)
1176.76(6)
170
444.85
monoclinic
P2 /n
8.1534(4)
12.4300(5)
8.9795(5)
99.610(4)
897.3(1)
170
397.82
monoclinic
P2 /n
8.2288(4)
11.9503(7)
8.9177(4)
100.648(4)
861.8(1)
200
579.35
monoclinic
P2 /n
1
1
1
1
7.6639(6)
13.0508(9)
11.842(1)
107.372(6)
1130.4(2)
200
b /Å
c /Å
β /° 3
V /Å
T /K
Z
D
μ /mm
λ /Å
2
2
2
4
3
calc /mg·m
1.561
1.130
1.647
1.456
1.533
1.674
1.702
2.512
–
1
θ
max /°
26.994
9571
28.00
7524
27.003
7724
27.005
9828
Refl. collected
Unique reflections
5083
2156
1875
2469
R
int
0.0198
4745
0.0365
1821
0.0417
1557
0.0683
2021
Refl. [F
o o
Ͼ 4σ(F )]
Parameters
283
107
106
136
R
wR
1
[F
2
o
Ͼ 4σ(F
o
)]
0.0330
0.0796
1.079
0.0269
0.0717
1.050
0.0259
0.0632
1.088
0.0541
0.1292
1.121
GOF
Δρmax/min /e·Å–3
0.583/–0.445
0.546/–0.496
0.363/–0.262
1.315/–0.487
Grating spectrograph, R928P Photomultiplier and a 450 W xenon
lamp. The photographs of the samples under near UV light were taken
selecting the 400 nm wavelength of the Xe lamp with aid of the spec-
trometer monochromator. For avoiding the detection of the excitation
light by the camera, a long pass 420 nm filter was placed before the
lenses. Reflection and absorption spectra were recorded at room tem-
perature with a Varian Techtron Pty UV/Vis/NIR two-channel Cary
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Received: July 27, 2017
2650–2663.
Published Online: ᭿
Z. Anorg. Allg. Chem. 0000, 0–0
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9
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
T. Neumann, L. S. Germann, I. Moudrakovski,
R. E. Dinnebier, C. dos Santos Cunha, H. Terraschke,
C. Näther* ....................................................................... 1–10
Synthesis, Crystal Structures, and Properties of M(NCS) -3-
2
aminomethylpyridine Coordination Compounds (M = Cd, Zn)
Z. Anorg. Allg. Chem. 0000, 0–0
www.zaac.wiley-vch.de 10
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim