First organic-inorganic hybrid material based on AgNO3 and 3-pyridine containing 2-thiohydantoin

Full text of DOI:10.1016/j.mencom.2007.03.007

Mendeleev
Communications
Mendeleev Commun., 2007, 17, 77–79
First organic-inorganic hybrid material based on
AgNO and 3-pyridine containing 2-thiohydantoin
3
†
Sergey Z. Vatsadze,* Alexander G. Majouga, Elena K. Beloglazkina,
Andrey V. Mironov and Nikolay V. Zyk
Department of Chemistry, M. V. Lomonosov Moscow State University, 119992 Moscow, Russian Federation.
Fax: +7 495 932 8846; e-mail: szv@org.chem.msu.ru
DOI: 10.1016/j.mencom.2007.03.007
The reaction of 2-(methylthio)-3-phenyl-5-(pyridine-3-ylmethylene)-3,5-dihydro-4H-imidazol-4-one (L) with AgNO in MeCN–
3
CH Cl results in the formation of coordination polymer framework. Single crystal X-ray study of the product reveals the presence
2
2
of non-interpenetrating 2D nets possessing a rare topology.
Coordination polymers, including those in which extended
inorganic metal–ligand networks are linked by exo-polydentate
organic ligands (so-called organic-inorganic hybrid materials),
received considerable attention due to their potential use as
catalytic, luminescent, magnetic and non-linear optic materials.1
Multidimensional networks based on metal centres linked by
CHO
AcOH
PhNCS + H NCH COOH +
2
2
N
Ph
N
Ph
N
O
S
O
S
rigid bridging components such as 4,4'-bipyridine are well
known.2,3 Less attention has been paid to the use of flexible
Me
N
N
MeI
H
KOH
bridging units in the construction of extended networks, but this
approach looks quite attractive because the flexibility and con-
formation freedoms of such ligands might offer the possibility
for the formation of unprecedented frameworks with tailored
properties and functions. Recently, some representative examples
N
N
1
2
Scheme 1
I
of the Ag coordination compounds based on N,S-containing
4
,5
flexible ligands have been reported.
-Thiohydantoins substituted at the C-5 position exhibit a
The reaction of 2 with AgNO in the acetonitrile/dichloro-
methane system leads readily to product 3 (Scheme 2) . A single
3
§
2
wide range of pharmacological activities including antiviral,
antitumor and antimycobacterial ones. They present the important
structural features of several aldose reductase inhibitors.6 Given
this level of biological activity, the synthesis of coordination
compounds, which incorporate the thiohydantoin fragment,
could have significant impact in the field of drug design and
drug delivery. 2-Thiohydantoins are known as ligands capable
crystal X-ray study of 3 reveals that the complex is polymeric,
and complexation occurs via sulfur and pyridine nitrogen.
In crystals of 3, each silver atom has distorted tetrahedral
coordination arrangements being linked to sulfur atom from
one ligand, pyridine nitrogen atom from another ligand and
two oxygens from distinct nitrates. Additional weak interac-
¶
,7
‡
II
III
For 1: to a mixture of phenyl isothiocyanate (1.62 g, 12 mmol),
of coordinating Hg or Tl ions via nitrogen and/or sulfur
glycine (0.75 g, 10 mmol) and pyridine carboxaldehyde (1.07 g, 10 mmol)
8
donor atoms; they can also form supramolecular networks by
15 ml of glacial acetic acid was added. The mixture was heated for 4 h
hydrogen bonds like NH···S and NH···O.9
under reflux. The precipitate formed was filtered off and recrystallised
In this paper, the synthesis of heterotopic multidentate
ligand 2-(methylthio)-3-phenyl-5-[(Z)-pyridin-3-ylmethylene]-
1
2
from acetic acid. Yield, 1.64 g (61%); mp 216 °C. H NMR ([ H ]DMSO)
6
d: 12.45 (br. s, 1H, NH), 8.94 (d, 1H, H -Py, J 18.8 Hz), 8.51 (d, 1H,
α
3
,5-dihydro-4H-imidazol-4-one 2 is described. We also began
H -Py, J 8.3 Hz), 8.25 (d, 1H, H -Py, J 8.3 Hz), 7.42 (m, 6H, H -Py,
α'
γ
β'
–
1
to study the complexation ability of the ligand towards transi-
tion and main group metals. Here, we report the synthesis and
crystal structure of the coordination compound [(AgL) (NO ) ]
H-Ph), 6.71 (s, 1H, =CH). IR (KBr, n/cm ): 3260 (NH), 1730 (C=O).
Found (%): C, 63.93; H, 3.72; N, 14.65. Calc. for C H OSN (%):
1
5
11
3
C, 64.06; H, 3.91; N, 14.95.
2
3 2 n
For 2: 3-phenyl-5-[(Z)-3-pyridinemethylidene]-2-thiohydantoin (10 mmol)
was suspended in ethanol (5 ml) and water (5 ml). To this mixture 0.5 ml
of a 15% aqueous solution of KOH was added, followed by 20 mmol of
MeI. After stirring for 15 min at room temperature, the precipitate was
(
where L = 2).
Compound 1 was prepared by three-component condensation
from phenyl isothiocyanate, glycine and 3-pyridine carbox-
aldehyde (Scheme 1). Ligand 2 was obtained by the alkylation
1
2
filtered off. Yield, 71%; mp 167 °C (EtOH). H NMR ([ H ]DMSO) d:
of 1 with methyl iodide in basic media.‡
6
9
.22 (s, 1H, H -Py), 8.69 (d, 1H, H -Py, J 8.3 Hz), 8.53 (d, 1H, H -Py,
α α' γ
Ligand 2 possesses three potential donating sites, namely,
thioether-type bivalent sulfur atom, imine nitrogen atom from
the pyridine ring and imine nitrogen atom from the thio-
hydantoin ring. Previously, it was shown that, in the case of
the ligand with a 2-pyridine fragment, a chelate complex was
obtained in the reaction with cobalt chloride.
J 4.4 Hz), 7.46 (m, 6H, H -Py, Ph), 6.88 (s, 1H, CH=), 2.70 (s, 3H, Me).
β'
–1
IR (KBr, n/cm ): 1730 (C=O), 1650 (C=N), 1600 (C=C). Found (%):
C, 65.22; H, 4.09; N, 14.25. Calc. for C H OSN (%): C, 65.00;
1
6
13
3
1
0
H, 4.41; N, 14.24.
§
For 3: the solution of 10 mg (0.034 mmol) of 2 in 3 ml of methylene
chloride was slowly diffused over 3 ml of an acetonitrile solution con-
taining 6 mg (0.034 mmol) of AgNO . After two days, yellow crystals
3
†
A lecturer at the Higher Chemical College of the RAS.
suitable for X-ray analysis were obtained.
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Mendeleev Commun., 2007, 17, 77–79
O
N
O
N
O
O
O
O
O
S(1)
C(12)
C(5)
Ag
C(4)
S
N
S
N(2)
Ag(1)
C(1)
C(3)
N(11)
O(2)
O(3)
2
+ AgNO3
N
C(2)
N(10)
C(14)
O(1)
C(7) C(6)
N(1)
Ag
C(15)
C(8)
C(13)
C(18)
C(17)
O
O
O
O(9)
N
N
O
n
C(16)
O
Ph
N
3
Figure 1 ORTEP representations of 3 showing atom numbering scheme
hydrogen atoms are omitted for clarity, the thermal ellipsoids representing
50% probability). Selected bond lengths (Å) and angles (°): Ag(1)–S(1)
2.601(4); Ag(1)–N(2) 2.317(10); Ag(1)–O(2) 2.462(12); Ag(1)–O(3)
(
O
S
Me
S
N
2
.309(12); S(1)–Ag(1)–N(2) 104.3(3); O(2)–Ag(1)–O(3) 108.9(4); N(2)–
=
Ag(1)–O(2) 88.6(4); N(2)–Ag(1)–O(3) 112.9(4); S(1)–Ag(1)–O(2) 117.3(2);
S(1)–Ag(1)–O(3) 121.5(4); Ag(1)–S(1)–C(12) 93.9(4).
N
N
Benzene rings are placed in the channels formed by six silver
atoms from four dimers. The dihedral angles of both skeleton
rings with the benzene ring are equal to 60.8(5)° and 68.9(5)°,
respectively. It should be mentioned that some atoms of this
ring have abnormally high atomic displacement parameters
(ADP), rapidly increasing from C(13) to C(15) and C(16). The
orientation of thermal ellipsoids shows the partial rotation
around the axis through C(13) and perpendicular to the ring
plane and partial incline of C(14)–C(16) aside from H(14). Due
to the positioning of benzene rings in the channel their exact
position in each particular unit cell may vary within a certain
range of angles.
Scheme 2
tion between Ag(1) and O(1) atoms of nitrate groups with an
interatomic distance of 2.76 Å should be regarded as secondary
interaction. Two formula units are linked together by opposite
ends of ligands in a head-to-tail orientation thus forming a
1
8-membered metallamacrocycle (Scheme 2). The picture of
two neighbouring (C H AgN O S) dimers is shown in
1
6
13
4
4
2
Figure 1. The distances between silver atoms within the dimers
are 10.51 Å.
The heteroaromatic cycles of the ligands are almost parallel
to each other with dihedral angles between them not exceeding
Nitrate anions act as µ-bridging bis(monodentate) ligands
in between silver atoms. This linking results in the formation
of infinite zig-zag chains of alternating anions and cations
arranged along the crystallographic axis c [Figure 2(a)]. The
shortest Ag–Ag separation within these chains is 5.71 Å.
Apparently, the bridging nitrates bring together [Ag L ] dimers
1
0°. The distance between N(11) and H(3) (2.47 Å) points to
weak intramolecular hydrogen bonding. Both pyridine and thio-
hydantoin rings are almost in-plane, the dihedral angle between
respective mean planes equals to 8.5°. The shortest carbon–
carbon contact within the dimers is C(3)···C(3) 3.22 Å, which
indicates13 a strong π–π interaction between adjacent ligands.
We believe that this interaction is a result of coordination of
sulfur to silver, which brings the linked molecules to such a
close distance.
2
2
to form double layers, which lie in bc crystallographic plane
(a)
¶
Crystallographic data for 3: crystals C H N O SAg, yellow prisms,
1
6
13
4
4
crystal size, 0.42×0.19×0.15 mm, are monoclinic, space group P2 /c;
1
3
a = 7.3026(13), b = 23.289(3) and c = 10.2812(24) Å; V = 1688.9(6) Å ,
–
3
Z = 4, dcalc = 1.829 g cm . Data were measured on a Syntex P21 dif-
fractometer [293 K, graphite monochromator, l(MoKα) = 0.71073 Å,
w-scan with 0.3° step]. The structure was solved by direct methods, all
non-hydrogen atoms were found in turn by Fourier and difference
Fourier synthesis, then refined by full matrix least squares in isotropic
and anisotropic approximations. The refinement converged with R = 0.074.
Difference Fourier synthesis revealed residual peaks at positions cor-
responding to hydrogen atoms. Coordinates of all possible hydrogen
[
except for C(20)] sites were calculated and refined with distance
restrictions and fixed isotropic displacement parameters, which reduced
R down to 0.069. 8452 reflections, of which 6239 were unique; 2438
of these were included in the refinement; data corrected for Lorentz
(b)
1
1,12
and polarization effects; solution by direct methods
and refinement
1
2
on |F| by full-matrix least-squares procedures; 263 parameters; non-
hydrogen atoms were refined in an anisotropic approximation. H atoms
were included, and refined in an isotropic approximation with a fixed
common atomic displacement parameter; R = 0.069, R = 0.139.
w
Atomic coordinates, bond lengths, bond angles and thermal param-
eters have been deposited at the Cambridge Crystallographic Data Centre
(CCDC). These data can be obtained free of charge via www.ccdc.cam.uk/
conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336 033; or deposit@ccdc.cam.ac.uk).
Any request to the CCDC for data should quote the full literature citation
and CCDC reference number 251159. For details, see ‘Notice to Authors’,
Mendeleev Commun., Issue 1, 2007.
Figure 2 Crystal packing of 3, mutual arrangements of silver coordination
tetrahedra are shown. (a) Front view of the 2D double layers (projection
along the crystallographic axis a, hydrogen atoms are omitted for clarity).
(b) Back view of 2D double layers (projection along the crystallographic
axis c, hydrogen atoms are omitted for clarity).
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Mendeleev Commun., 2007, 17, 77–79
connected to each other by bridging nitrate anions with final
formation of 2D double layers. The topology of the 2D layers is
a rare case of 2D network topologies found in the literature.
This work was supported by the Russian Foundation for
Basic Research (grant no. 06-03-33077).
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2
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Figure 2(a)]. Two adjacent dimers in a layer are not connected
4
5
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2
6
7
2
Figure 3) is similar to that of single 2D net in the crystal
1
4
structure of Zn(bix) (NO ) ·4.5H O [bix = bis(imidazole)xylene].
2
3 2
2
8
9
In contrast to the literature analogue, in crystals of 3 2D nets
do not interpenetrate but rather form distinct facially interacted
stacks. Double layers stack along a* reciprocal axis (parallel to
bc crystallographic plane) [Figure 2(b)]. Interlayer distances are
rather large, the shortest ones are C(17)–O(3) (3.26 Å, benzene
ring–nitrate group) and C(5)–N(11) (3.54 Å, pyridine ring–
thiohydantoin ring). Thus, only weak interlayer bonding may
be suggested. This fact is confirmed by coherent twinning in an
almost 1:1 ratio resulting from opposite layer orientation within
one crystal.
In conclusion, the ability of heterotritopic ligand 2 to form
infinite coordination frameworks with silver nitrate inorganic
counterparts was demonstrated. In the resulting product, a
ligand exploits two of its donating sites, i.e., the thioether sulfur
atom and the imine pyridine nitrogen atom. Two ligands
coordinate two metal centres in a head-to-tail manner so as to
form 18-membered metallamacrocycles. These units are further
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1
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Received: 20th November 2006; Com. 06/2826
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