Hybrid material constructed from Hg(NCS)2and 2,4,6-Tris(2-pyrimidyl)-1,3,5-triazine (TPymT): Coordination of TPymT in a 2,2′-bipyridine-like mode

Article abstract of DOI:10.1002/ejic.201402832

A unique Hg^II coordination polymer has been synthesized through the reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with a stoichiometric mixture of HgCl₂ and NH₄NCS, thus leading to the formation of a 1D polymeric heteroleptic hybrid material[{Hg(NCS)₂}₂TPymT]_n (1). Two coordination pockets of TPymT in 1 are each coordinated to two Hg^II cations in an unprecedented 2,2′-bipyridine-like mode.

Full text of DOI:10.1002/ejic.201402832

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DOI:10.1002/ejic.201402832
Hybrid Material Constructed from Hg(NCS) and 2,4,6-
2
Tris(2-pyrimidyl)-1,3,5-triazine (TPymT): Coordination of
TPymT in a 2,2Ј-Bipyridine-Like Mode
[
a]
[a]
[a]
Damir A. Safin, Rebecca J. Holmberg, Kevin M. N. Burgess,
[
b]
[a]
[a]
Koen Robeyns, David L. Bryce, and Muralee Murugesu*
Keywords: Organic–inorganic hybrid materials / Mercury / N ligands / Coordination modes / Structure elucidation
A unique HgII coordination polymer has been synthesized
through the reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine
2 2 n
heteroleptic hybrid material [{Hg(NCS) } TPymT] (1). Two
coordination pockets of TPymT in 1 are each coordinated to
II
(
TPymT) with
a
stoichiometric mixture of HgCl
2
and
two Hg cations in an unprecedented 2,2Ј-bipyridine-like
NH NCS, thus leading to the formation of a 1D polymeric
4
mode.
Introduction
stacking interactions, etc.), that might be tuned in terms of
molecular selectivity and recognition, the metal part mainly
determines the overall geometry of the structure (e.g., di-
mensionality). Thus, the nature of a selected metal centre is
a powerful tool to design the targeted structure. Accord-
Coordination polymers (CPs) have been known and ex-
tensively employed since the groundwork of their study was
laid by Nobel Prize winner Alfred Werner.[ He was the
first to utilize such important terms as coordination num-
bers and coordination isomerism. Since that time, CPs were
found to be an intriguing class of hybrid materials, compris-
ing inorganic nodes and organic ligands by coordination
1]
II
ingly, using the Hg atom for the formation of hybrid mate-
rials is attractive since it is a much softer metal centre com-
II
II
pared to its analogues (Zn and Cd ) and, thus, promotes
[
8]
the formation of less predictable final structures. Despite
the numerous alluring applications of Hg compounds in
[
2]
interactions. They have exhibited valuable properties and
II
[3]
are currently employed in wide range of fields. In terms
of crystal engineering of CPs; π electron containing ligands
are of ever-growing interest.
Using metal CP approaches for the preparation of or-
ganic–inorganic hybrid materials provides a synthetic inter-
face between the properties of mononuclear complexes and
energy-saving light bulbs, thermometers, batteries, paper,
paint, as well as in medicine, the study and formation of
II
[4,9]
polymers using Hg is comparatively limited.
Moreover, the coordination chemistry of 2,4,6-tris(2-pyr-
imidyl)-1,3,5-triazine (TPymT) has been extremely poorly
explored since it was first obtained about 55 years ago.[
This might be explained by its general unavailability, poor
solubility in common organic solvents, and by hydrolysis of
the triazine fragment of TPymT in the presence of metal
10]
[
4]
bulk materials. Thus, through using this technique, a wide
variety of structures with unique coordination properties
can be synthesized and studied. This ever-growing part of
modern chemistry has shown applicability in prominent
fields such as catalysis, magnetism, nonlinear optics, and
molecular sensing, while still remaining a challenging field
[
11]
cations under mild conditions,
ligand. However, there have been a few reports on the syn-
thus breaking down the
II [12]
II [13]
I [13a]
thesis of TPymT complexes with Ru ,
Pb ,
Among them, only two crystal structures
were described: a 1D polymeric chain [{Pb (TPymT)-
Tl ,
[
4,5]
of study.
These materials are of great interest not only
II [13a]
and UO2
.
[6]
for their practical applications but also as building units
for extended structures.[7] While the organic components of
2
(
H O)(NO ) ·H O} ] comprising dilead heteroleptic build-
2 2 n
3 4
13a]
coordination polymers are responsible for supramolecular
and secondary interactions (e.g., hydrogen bonds, π···π
[
ing blocks,
gregate [Pb (TPymT) (Lig) ](OTf) {Lig = 4,6-bis[4-(prop-
ylthio)-2,2Ј-bipyridin-6-yl]pyrimidine}.
and a discrete hexalead supramolecular ag-
6
2
3
12
[
13a]
[
[
a] Department of Chemistry, University of Ottawa,
1
0 Marie Curie Private, K1N 6N5, Ottawa, ON, Canada
Thus, the coordination chemistry of TPymT remains
challenging. With this in mind, we have recently turned our
attention to the synthesis and study of TPymT-based coor-
dination compounds. Very recently, we published the first
E-mail: m.murugesu@uottawa.ca
http://mysite.science.uottawa.ca/mmuruges/
b] Institute of Condensed Matter and Nanosciences, MOST -
Inorganic Chemistry, Université Catholique de Louvain,
Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402832.
crystal structure of a TPymT complex with a d-metal cat-
II
ion, namely, a dinuclear Cd complex [Cd (TPymT)-
2
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[
14]
(
H O) (SO ) ]·H O (2). Furthermore, we also reported a thiocyanate ions.[16] Unfortunately, bands for the CS vi-
2 6 4 2 2
[15]
pseudo-polymorph [{Pb (TPymT)(NO ) } ] (3) of a pre- brations are obscured by the presence of the bands charac-
2
3 4 n
viously published lead structure.[
13a]
teristic of the TPymT ligand
[14]
and, thus, cannot be iden-
Herein, we report on the crystal structure of a polymeric tified unequivocally. The Raman spectrum of 1 also exhibits
–
1
[17]
heteroleptic hybrid material [{Hg(NCS) } TPymT] (1), a band at 265 cm , corresponding to HgS vibrations.
2
2
n
1
which was also characterized by means of FTIR, Raman,
The H NMR spectrum of 1 in [D ]DMSO contains two
multiplets at 7.78–7.86 and 9.11–9.21 ppm, corresponding
as well as Hg solid-state NMR spectroscopy, TG/DTA, to the p- and m-protons, respectively, of the pyrimidine
and X-ray powder diffraction analyses. Furthermore, to ex- fragments. The 13C NMR spectrum of 1 in the same solvent
tensively probe the unique structural characteristics of this exhibits a double set of signals at about 130.0, 158.5, and
6
1
13
diffuse reflectance, fluorescence, solution-state H and
C
1
99
II
Hg complex, we have drawn particular attention to the 170.0 ppm, corresponding to the pyrimidine functionalities.
NCS counterion, since it might show coordination versatil- There are also two peaks at δ = 177.6 and 178.3 ppm, aris-
–
ity due to a rich variety of coordination modes (see ing from the triazine carbons. Furthermore, two singlets at
Chart S1 in the Supporting Information).[16]
δ = 140.4 and 142.1 ppm are indicative of the NCS anions.
–
13
Thus, the double set of signals in the C NMR spectrum
together with multiplet peaks in the H NMR spectrum of
1
Results and Discussion
1
might testify to the existence of coordinated and non-
]-
HgCl and NH NCS in water yielded blocklike crystals of DMSO. Two signals for the thiocyanate anions might be
Reaction of TPymT with a stoichiometric mixture of coordinated pyrimidine fragments in a solution of [D
6
2
4
the complex in 86.2% yield (Scheme 1). Crystals of 1 are due to two different coordination modes.
poorly soluble in DMF and DMSO. Note, that all experi-
To shed light on the electronic properties of 1, the diffuse
Hg solid-state NMR reflectance spectrum was recorded on a pure sample. The
spectroscopy, were performed on the crystalline sample of spectrum exhibits a broad absorption band with several
1
99
ments listed below, except for the
1.
maxima, accompanied by a shoulder, in the 200–600 nm
The FTIR and Raman spectra of 1 each contain bands range, corresponding to intraligand transitions of
[
14]
for the aromatic C–H and C=N stretches at 3020–3040 and TPymT
1
and ligand-to-metal or metal-to-ligand charge
540–1560 cm , respectively (Figure S1 in the Supporting transfer (Figure S2 in the Supporting Information).
Information). The latter band is overlapped with a band for Solid-state fluorimetric studies of 1 were undertaken to
the aromatic ring chain vibrations, which were also found examine its photophysical properties. It was found that 1
–
1
–
1
as bands at 1430–1440 and 1000 cm . An intense band at shows a very similar emission band to that of the parent
125 cm in the FTIR and Raman spectra of 1 was attrib- ligand TPymT
uted to the CN stretch of the NCS anions. This band is at λexc = 350 nm (Figure S3 in the Supporting Information).
in the region characteristic of the S-bonded and bridging The excitation spectrum of 1, recorded at λem = 480 nm,
–
1
[14]
2
with maxima at around 460 and 495 nm
–
Scheme 1. Preparation of 1.
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reveals a main contribution from the band centred at about several different crystals of 1 were checked by single-crystal
00–425 nm. This band can be assigned to the absorption X-ray diffraction, testifying to their identity.
of the shoulder at about 430 nm by comparison with dif- According to the X-ray data, 1 crystallizes in the mono-
4
fuse-reflectance spectroscopy data (Figure S2 in the Sup- clinic space group C2/c and comprises an infinite polymeric
porting Information). Thus, the observed emission of 1 is molecule (Figure 1). It was found that TPymT in the struc-
II
attributed to π–π* intraligand fluorescence.
ture of 1 is coordinated to two Hg cations and acts as
The thermal properties of 1 in an air atmosphere were a bis(2,2Ј-bipyridine)-type ligand, exhibiting a bridging μ4-
studied by simultaneous TG/DTA analyses to determine its coordination mode. Complex 1 is the first example that di-
stability (Figure S4 in the Supporting Information). The rectly shows a 2,2Ј-bipyridine-like coordination mode for
molecule of 1 is stable up to 250 °C and completely decom- TPymT. To date the crystal structure database contains 31
posed in three clearly defined steps. The mass loss after the hits for the metal-containing complexes of the closest ana-
first decomposition step of 5.49% is in agreement with the logue of TPymT, named 2,4,6-tris(pyridin-2-yl)-1,3,5-tri-
calculated value of 5.48%, corresponding to the elimination azine (TPT), in which the organic ligand exhibits a 2,2Ј-
[
19]
of cyanogen. The observed final residue of 24.57% after the bipyridine-like coordination mode.
Among them, only
second decomposition step is in excellent agreement with six structures contain the TPT ligand in a bridging μ -coor-
4
the value of 24.52% calculated for HgS, which is burned in dination mode, whereby two coordination pockets are each
an air atmosphere with the formation of elementary Hg and bonded in a 2,2Ј-bipyridine-like manner to a metal centre.
4
+
its further complete evaporation. The latter observation is The structural motifs [Hg TPymT] are linked through
2
–
confirmed by a broad exothermic effect, centred at 580 °C, bridging μ -1,3-N,S-coordinated NCS anions with the for-
2
which corresponds to a melting point (with decomposition) mation of dinuclear eight-membered metallocycles (Fig-
[
18]
of HgS. The thermal decomposition of 1 also reveals two ure 1). These cycles are each in a chair conformation,
II
low-temperature exothermic effects centred at 270 and whereby two Hg cations deviate by about 1.42 Å from the
–
4
20 °C, corresponding to the first and second decomposi- least square plane formed by two NCS anions (Figure S5
tion steps, respectively.
in the Supporting Information). As a result, 1D zig-zag-like
Crystals of 1 suitable for a single-crystal X-ray analysis polymeric chains are formed. These 1D chains are further
II
II
were obtained after the synthesis on standing (1 day) with stacked on top of each other (Figure 1). The Hg ···Hg
slow evaporation of the solvent. It should be noted that separation between two metal cations, coordinated to the
Figure 1. Photograph of crystals (top left) and molecular X-ray structure of 1 (top right) with ellipsoids drawn at the 50% probability
level. Crystal packing of 1-D chains of 1 along the a axis (Hydrogen atoms were omitted for clarity) (bottom).
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same TPymT ligand, is about 6.93 Å, while the same dis- 3.[14,15] Closer inspection of the crystal structure of 1 re-
2
+
tance between two metal centres within the [Hg (NCS) ]
vealed no classical hydrogen bonds but further H···X short
2
2
II
II
[21]
fragment is 5.94 Å. The shortest Hg ···Hg separations be- contacts; however, based on established criteria,
these
tween neighbouring 1D chains are about 6.56 and 6.82 Å. weak interactions are not directing the crystal packing or
II
The coordination of each Hg cation is completed by the molecular structures.
–
sulfur atom of the third NCS anion leading to a pentaco-
A bulk sample of crystalline 1 was studied by X-ray pow-
ordinate environment (Figure 1). The latter coordination der diffraction analysis, and the experimental X-ray powder
sphere can be described either as square-pyramidal or trigo- pattern is in excellent agreement with that calculated from
nal-bipyramidal depending on the parameter τ = (β – α)/60, single-crystal X-ray diffraction (Figure S6 in the Supporting
where α and β are the two largest bond angles around the Information).
metal ion. An ideal square-pyramidal arrangement is de-
scribed by the value of τ = 0, while an ideal trigonal-bi- a bulk powder sample of 1 under cross-polarization magic-
199Hg solid-state NMR experiments were performed on
[
20]
pyramidal arrangement has the value of τ = 1.
The angle-spinning conditions (CP/MAS) conditions. It should
largest bond angles in the coordination sphere are 157.52(6) be noted that the bulk powder sample was obtained using
and 146.13(14)°, which give a τ value of 0.19. This value is 10 times more starting material relative to the synthesis of
closer to that of a distorted square pyramid around the the crystalline sample of 1. The spectra recorded at B =
0
metal atom. The mean basal plane is occupied by two sulfur 4.7 T reveal a large amount of chemical shift anisotropy
atoms, corresponding to both bridging and monodentate and two crystallographically non-equivalent Hg species in
–
NCS anions, and two nitrogen atoms from the second the sample with the ratio 1:0.6 having isotropic chemical
–
NCS and triazine fragments. Although both Hg–S dis- shifts (δiso) of –1130(5) and –1305(5) ppm, respectively (Fig-
tances are very similar (ca. 2.41 Å), the Hg–Nbase plane bond ure 2). The minor component corresponds to the presence
[
22]
lengths differ significantly (ca. 2.57 and 2.76 Å) (Table S1 of a Hg(SCN) byproduct (δ = –1300 ppm).
Hence, 1
2
iso
in the Supporting Information). The apical nitrogen atom clearly contains one Hg site, which is in agreement with
arises from the pyrimidine functionality with an Hg–N the single-crystal X-ray structure. The 1 Hg chemical shift
bond length of about 2.51 Å. An intriguing contact can be tensor of 1 is characterized by the following parameters: δiso
drawn between the Hg(1) and N(19) atoms. The non-coor-
99
II
dinated pyrimidine fragment is situated between two Hg
cations bound to the same TPymT ligand and is positioned
on a twofold axis. As such, both N(19) atoms are about
2.86 Å displaced from metal centres. The interaction is out-
of-plane of the pyrimidine ring and such contacts are read-
ily observed in the CSD database.[ It appears that this
pyrimidine fragment could rotate freely to accommodate
19]
II
the Hg cations in the plane of the ring without steric
II
hindrance. The long bond length (top 1% for the Hg –
Naromatic interactions found in the CSD[ ) in combination
with the inclined pyrimidine indicates that the coordination
number remains 5 and that no interaction (at most a very
weak interaction) should be expected between the metal
centre and the N(19) atom. The dihedral angles between
the planes formed by the triazine and both the coordinated
and non-coordinated pyrimidine rings are about 15 and
19]
29°, respectively. The same angles between the coordinated
and non-coordinated pyrimidine planes are 32°. These
angles are significantly larger than those in the structure of
II
[14]
a discrete dinuclear Cd complex 2 and a polymeric 2D
complex 3,
[
15]
and testify to a higher distortion of the
TPymT ligand in the structure of 1. The C–S bond length
is about 0.03 Å longer in favour of the monodentate NCS–
anion, while the C–N bonds are almost the same (ca.
Figure 2. 199Hg solid-state NMR spectra of a bulk sample of 1
acquired at B = 4.7 T with sample spinning rates of 4 (a), 4.5 kHz
.16 Å) regardless of the coordination mode of the NCS–
1
0
ligands (Table S1 in the Supporting Information). This
(
e), and 5 kHz (f) acquired under CP/MAS conditions. The spec-
1
99
might explain the presence of the unique band, correspond- trum in (c) is an analytical simulation of the Hg spectrum of 1
–
ing to the CN stretches of the NCS anions, in the FTIR (see main text) and (d) is a simulation based on the previously
2
reported NMR parameters for the Hg(SCN) impurity (δiso =
spectrum of 1 (see FTIR description above, Figure S1 in the
Supporting Information). The bond lengths and bond
angles within the TPymT ligand in the structure of 1 are
16]
–
1300 ppm).[ The spectrum in (b) is a simulation of both 1 and
2
Hg(SCN) in the ratio of 1:0.6. The dashed lines indicate the posi-
tion of the isotropic chemical shifts for 1 [green, δiso = –1130(5)
almost the same as those found in the structures of 2 and ppm] and Hg(SCN)
2
[blue, δiso = –1305(5) ppm].
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=
–1130(5), Ω = 2880(40) ppm, and κ = 0.75(0.05). The the reactants dissolved. The resulting pale yellow solution was
cooled to yield pale yellow blocklike crystals, yield 0.020 g (86.2%).
substantial span (Ω) and skew (κ) values are consistent with
the distorted square-pyramidal environment around Hg.
The NMR parameters for 1 are nicely corroborated by den-
sity functional theory (DFT) calculations on a molecular
model of 1 (Figure S7 in the Supporting Information) based
on its crystal structure. Under the zeroth-order regular
approximation (ZORA), as implemented in the Amsterdam
Density Functional (ADF) software,[23] a calculated δiso
value of –1070 ppm is obtained when spin-orbit relativistic
effects are included compared with –536 ppm when relativ-
ity is not considered in the calculations.
1
H NMR: δ = 7.78–7.86 (m, 3 H, p-CH, pyrimidine), 9.11–9.21
1
3
(
m, 6 H, m-CH, pyrimidine) ppm. C NMR: δ = 130.1 (s, p-C,
pyrimidine), 140.4, 142.1 (s, NCS), 158.3, 158.9 (s, m-C, pyrimid-
ine), 169.4, 170.1 (s, i-C, pyrimidine), 177.6, 178.3 (s, triazine) ppm.
C H Hg N S (948.79): calcd. C 24.05, H 0.96, N 19.19; found
19 9 2 13 4
C 24.18, H 1.08, N 19.10.
A bulk powder sample of 1, prepared for the 199Hg solid-state
NMR spectroscopy, was synthesized according to the same pro-
cedure, instead using an aqueous (100 mL) solution of a mixture
of HgCl
2 4
(0.75 mmol, 0.205 g) and NH NCS (1.50 mmol, 0.115 g),
and a suspension of TPymT (0.25 mmol, 0.08 g) in the same sol-
A powder sample of 1 was also studied by X-ray powder vent (150 mL).
diffraction analysis, and the experimental X-ray powder
pattern testifies to a presence of both 1 and Hg(SCN) (Fig-
199
Hg Solid-state NMR Spectroscopy: Spectra were acquired at
199
1
2
L
4.7 T [νL( Hg) = 35.8 MHz and ν ( H) = 200.1 MHz] using a
ure S6 in the Supporting Information). Surprisingly, keep- Bruker 7 mm low-frequency double resonance (HX) probe. MAS
ing the same amount of starting compounds but using the NMR spectra were acquired at three different spinning frequencies
TPymT/HgCl /NH NCS ratio of 1:2:4 led to the same mix- under CP conditions with continuous-wave proton decoupling. A
2
4
1
3
μs H π/2 pulse, a 7 ms contact time, and a 3 s recycle delay were
ture of 1 and Hg(SCN) . However, the yield was signifi-
cantly lower. The same observation was also proven by the
2
used for all experiments. A total of 88720, 55176, and 55679 tran-
sients were acquired for the 4 kHz, 4.5 kHz, and 5 kHz spectra
respectively. The Hg chemical shift was referenced to Hg(CH
at 0 ppm using the secondary reference sample NEt Na[Hg(CN)
iso = –434 ppm).[ All spectra were baseline-corrected. It was
possible to measure accurately the isotropic chemical shifts of the
two Hg species present by overlaying the three experimental spectra
[δiso = –1130(5) ppm and –1305(5) ppm for the major and minor
1
99
Hg solid-state NMR experiment.
1
99
3 2
)
4
4
]
24]
(
δ
Conclusions
In summary, a novel 1D polymeric heteroleptic hybrid
material [{Hg(NCS) } TPymT] (1) was synthesized and
characterized by FTIR, Raman, diffuse-reflectance, fluores-
cence, solution-state H and C as well as Hg solid-state
NMR spectroscopy, TG/DTA, and X-ray powder diffrac-
tion analyses. The molecular structure of 1 was elucidated
199
2
2
n
Hg sites respectively]. Analytical simulations were generated in
the WSolids1 program.
1
13
199
Amsterdam Density Functional (ADF) Calculations: DFT calcula-
tions were performed under the zeroth-order regular approxi-
mation (ZORA) as implemented in the ADF software package
[23]
by single-crystal X-ray diffraction analysis, which revealed, available through the High Performance Computing Virtual Labo-
to the best of our knowledge, the first structurally charac- ratory (HPCVL). The molecular model for 1 used in the calcula-
terized example of a metal complex of TPymT exhibiting a tions is depicted in Figure S6. The exchange correlation functional
BP86 was used under the generalized gradient approximation
2,2Ј-bipyridine-like coordination mode.
(
GGA). The QZ4P basis set was used on all atoms. Calculations
were performed with and without spin-orbit relativistic effects.
These calculations yield the isotropic magnetic shielding constant
Experimental Section
(
σ
iso). Isotropic chemical shift values were obtained by comparing
to calculations performed on a shift reference (i.e., δiso = σiso,ref
iso)/(1 – σiso,ref). For HgMe , σiso,ref = 8279 and 6224 ppm when
spin-orbit relativistic effects are and are not included in the calcula-
–
Physical Measurements: Infrared spectra were recorded with a Var-
σ
2
ian 640 FTIR spectrometer equipped with an ATR in the 500–
000 cm–1 range. Raman spectra in the solid state were obtained
4
tions, respectively. The bond lengths for HgMe
2
are known based
with a FTIR Nicolet Magna 860 with Raman unit and Nd:YVO
4
on previous electron diffraction studies.[
25]
1
13
(
λ = 1064 nm) laser. H and C NMR spectra in [D
6
]DMSO were
obtained on a Bruker Avance 300 MHz spectrometer at 25 °C. Dif-
fuse-reflectance spectra were obtained with a Varian Cary 100 spec-
trometer using polytetrafluoroethylene (PTFE) as a reference. So-
lid-state emission and excitation spectra were obtained with a Per-
kin–Elmer LS 50 luminescence spectrometer. Kubelka–Munk,
emission, and excitation spectra were normalized to allow mean-
ingful comparisons. Simultaneous thermogravimetric (TG) and
differential thermal (DTA) analyses were performed by a SDT 2960
Simultaneous DTA-TGA instrument in a dynamic air atmosphere
X-ray Powder Diffraction Analysis: X-ray powder diffraction analy-
sis of the bulk sample of 1 was carried out using a Rigaku Ultima
IV X-ray powder diffractometer. The parallel beam mode was used
to collect the data (λ = 1.541836 Å).
Single-Crystal X-ray Diffraction Analysis: The X-ray diffraction
data for 1 were collected at 150(2) K on a Mar345 image plate
α
detector using Mo-K radiation (Xenocs Fox3D mirror). The data
were integrated with the crysAlisPro software.[ The implemented
26]
empirical absorption correction was applied. The structures were
–1
(
100 mLmin ) from laboratory temperature to 900 °C with a 10 °C
[
27]
solved by direct methods using the SHELXS-97 program
and
–
1
min heating rate. Elemental analyses were performed on a Per-
kin–Elmer 2400 CHN analyzer.
2
[27]
refined by full-matrix least-squares on |F | using SHELXL-97.
Non-hydrogen atoms were refined anisotropically and the hydrogen
atoms were placed on calculated positions in riding mode with tem-
Synthesis of 1: A hot aqueous (12 mL) solution of a mixture of
2 4
HgCl (0.075 mmol, 0.021 g) and NH NCS (0.15 mmol, 0.012 g) perature factors fixed at 1.2 times Ueq of the parent atoms. Figures
[
28]
was added to a suspension of TPymT (0.025 mmol, 0.008 g) in the
same solvent (20 mL). The mixture was heated at reflux until all of
were generated using the program Mercury.
19 9 2 13 4 r
C H Hg N S , M
–
1
= 948.81 gmol , monoclinic, space group C2/c, a = 6.8236(2), b =
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3
1
6.9056(5), c = 22.4059(5) Å, β = 95.903(2)°, V = 2570.97(12) Å ,
[8] C. Hu, I. Kalf, U. Englert, CrystEngComm 2007, 9, 603.
–3
–1
[9] a) W. Levason, C. A. McAuli, The Chemistry of Mercury,
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Acknowledgments
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Published Online: ᭿
Eur. J. Inorg. Chem. 0000, 0–0
6
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Job/Unit: I42832
/KAP1
Date: 18-12-14 13:04:59
Pages: 7
www.eurjic.org
FULL PAPER
Hybrid Material
D. A. Safin, R. J. Holmberg,
K. M. N. Burgess, K. Robeyns,
D. L. Bryce, M. Murugesu* .............. 1–7
Hybrid Material Constructed from
Hg(NCS)
2
and 2,4,6-Tris(2-pyrimidyl)-
1,3,5-triazine (TPymT): Coordination of
TPymT in a 2,2Ј-Bipyridine-Like Mode
Keywords: Organic–inorganic hybrid ma-
terials / Mercury / N ligands / Coordination
modes / Structure elucidation
Reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-
[{[Hg(NCS)
2
]
2
TPymT}
n
], in which two co-
triazine (TPymT) with a mixture of HgCl
and NH NCS leads to the formation of a
polymeric heteroleptic hybrid material
2
ordination pockets of TPymT are each co-
ordinated to two Hg cations in an unpre-
cedented 2,2Ј-bipyridine-like mode.
II
4
Eur. J. Inorg. Chem. 0000, 0–0
7
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim