Synthesis, crystal structure and characterization a new ionic complex MoO2Cl3(MeOH)·H3tptz·Cl2 (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) as epoxidation catalyst

Article abstract of DOI:10.1016/j.ica.2016.02.015

[MoO₂Cl₃(MeOH)]·H₃tptz·Cl₂ (1) (where tptz is 2,4,6-tris(2-pyridyl)-1,3,5-triazine) was prepared via reaction of MoO₃ with tptz in a stoichiometric ratio of 1:1 in concentrated HCl at room temperature. It was characterized, by means of elemental analysis, FTIR, UV–Vis, ¹H NMR and single-crystal X-ray diffraction. The asymmetric unit of the molybdenum(VI) salt 1 contains a 2,2′,2″-(1,3,5-triazine-2,4,6-triyl)tripyridinium cation, a cis-dioxotrichloridomethanolmolybdenum(VI) monoanion and two chloride anions to achieve electrical neutrality. The oppositely charged components in the structure of 1 are bound together by an intricate system of weak N(O)–H?Cl hydrogen bonds. The interactions between hydrogen bond donor and acceptor giving rise to three dimensional networks. It was also found that compound 1 successfully catalyzes the epoxidation of various alkenes such as cycoloctene, cyclohexene, norbornene, styrene, α-methyl styrene and trans-stilbene with 30–100% conversion and 80–100% selectivity using tert-butyl hydroperoxide (TBHP) as oxidant. The catalyst can be easily recovered from the reaction mixture and reused at least for three times without significant loss of activity. The superior antibacterial activity of 1 against Bacillus subtilis is also described in this presentation.

Full text of DOI:10.1016/j.ica.2016.02.015

Accepted Manuscript
Synthesis, Crystal Structure and Characterization a New Ionic Complex
MoO Cl (MeOH)·H tptz·Cl (tptz=2,4,6- tris(2- pyridyl)-1,3,5-triazine) as Ep-
2
3
3
2
oxidation Catalyst
Mahboobeh Maghami, Faezeh Farzaneh, Jim Simpson, Mohammad Azarkish
PII:
S0020-1693(16)30031-7
http://dx.doi.org/10.1016/j.ica.2016.02.015
ICA 16885
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
18 November 2015
19 January 2016
2 February 2016
Please cite this article as: M. Maghami, F. Farzaneh, J. Simpson, M. Azarkish, Synthesis, Crystal Structure and
Characterization a New Ionic Complex MoO Cl (MeOH)·H tptz·Cl (tptz=2,4,6- tris(2- pyridyl)-1,3,5-triazine) as
2
3
3
2
Epoxidation Catalyst, Inorganica Chimica Acta (2016), doi: http://dx.doi.org/10.1016/j.ica.2016.02.015
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Synthesis, Crystal Structure and Characterization a New Ionic
Complex MoO Cl (MeOH)·H tptz·Cl (tptz=2,4,6- tris(2- pyridyl)-1,3,5-
2
3
3
2
triazine) as Epoxidation Catalyst
a
*a
b
c
Mahboobeh Maghami , Faezeh Farzaneh , Jim Simpson , Mohammad Azarkish
a
Department of Chemistry, Faculty of Physics and Chemistry, Alzahra University,
Tehran 1993891176, Iran
b
Department of Chemistry, University of Otago, PO Box 56, Dunedin 9054, New
Zealand
c
Department of Chemistry, Payame Noor University (PNU), 19395-4697 Tehran, Iran
ABSTRACT
[
MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
(1) (where tptz is 2,4,6-tris(2-pyridyl)-1,3,5-triazine) was
with tptz in a stoichiometric ratio of 1:1 in concentrated
prepared via reaction of MoO
3
HCl at room temperature. It was characterized, by means of elemental analysis, FTIR,
1
UV–Vis, HNMR and single-crystal X-ray diffraction. The asymmetric unit of the
molybdenum(VI) salt 1 contains a 2,2',2''-(1,3,5-triazine-2,4,6-triyl)tripyridinium cation,
a cis-dioxotrichloridomethanolmolybdenum(VI) monoanion and two chloride anions to
achieve electrical neutrality. The oppositely charged components in the structure of 1 are
bound together by an intricate system of weak N(O)-H···Cl hydrogen bonds. The
interactions between hydrogen bond donor and acceptor giving rise to three dimensional
networks. It was also found that compound 1 successfully catalyzes the epoxidation of
various alkenes such as cycoloctene, cyclohexene, norbornene, styrene, α-methyl styrene
and trans-stilbene with 30-100% conversion and 80-100% selectivity using tert-butyl
hydroperoxide (TBHP) as oxidant. The catalyst can be easily recovered from the reaction
mixture and reused at least for three times without significant loss of activity. The
superior antibacterial activity of 1 against Bacillus subtilis is also described in this
presentation.
Keywords:
Dioxo-molybdenum(VI)complex; X-ray structure; Supramolecular; Epoxidation catalyst;
Antibacterial activity
*
Corresponding author, Tel +9821 88258977; fax: +9821 664955291
Email address: faezeh_farzaneh@yahoo.com: farzaneh@alzahra.ac.ir
1

1
. Introduction
Molybdenum is an essential metal that is capable of forming complexes with many
compounds of biological importance. The coordination chemistry of molybdenum has
become a fascinating area of research in recent years because of the presence of
molybdenum in metalloenzymes [1-6]. High-valent molybdenum complexes which bear
cis–MoO units have attracted considerable interest due to their applications in catalytic
2
oxo transfer reactions [7-17]. The ability of molybdenum to form stable complexes with
Schiff base ligands are efficient catalysts both in homogeneous and heterogeneous
reactions [18-22].
The epoxidation of olefins catalyzed by molecular transition metal compounds
continues to be a topic of considerable academic and industrial interest [23-26]. Epoxides
are very important and versatile intermediates for manufacturing a range of important
commercial products such as pharmaceuticals and polymers [27]. Molybdenum-based
catalysts have been widely used in epoxidation reactions [28]. It is well known that
complexes of the type [MoO
ligand) are versatile catalyst precursors for the epoxidation of olefins with TBHP [7, 11,
9]. Treatment of [MoO ] species (X = halide, OR, OSiR ) with Lewis bases (L or L )
2
X
2
(L)
n
] (X= Cl, Br, CH ; L = mono- or bidentate neutral N-
3
2
2
X
2
3
1
2
such as pyridine, 2,2-bipyridine, 1,10-phenanthroline, 4,4-tert-butyl-2,2-bipyridine and
with donor solvents such as acetonitrile and THF leads to adducts of composition
[
MoO
2
X
2
2
L ] [30-35].
Derivatives of 1,3,5-triazine have been received much attention as they have promising
potential as antitumor and antibacterial agents [36]. 2,4,5-Tris(2-pyridyl)triazine (tptz, is
a bulky aromatic compound which has three 2-pyridyl rings bonded to the central 1,3,5-
2

triazine platform. The planar structure of tptz along with large π system also makes it a
suitable candidates for further chemical modifications in pharmacologically active
coordination compounds and also acts as a useful ligands in coordination chemistry [37-
3
8].
In this report, the dioxidomolybdenum(VI) compound [MoO
1) has been synthesised and fully characterized by spectroscopic techniques and single-
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
(
crystal X-ray diffraction. The catalytic activity of compound 1 for the epoxidation of
some olefins as well as its antibacterial efficiency has been investigated against four
different bacteria strains Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus
aureus and Escherichia coli.
2
. Experimental
2
.1. Materials and Physical Techniques
All materials were of commercial reagent grade and used without further purification.
Elemental analyses were performed on a Heraeus CHN-O-Rapid elemental analyzer.
Infrared spectroscopy in the solid state (KBr pellet) was performed on a FT-IR JASCO
-1
4
60 spectrophotometer in the 4000– 400 cm region. UV/Vis spectra were obtained with
1
a Shimadzu UV-260 spectrophotometer. H NMR spectra were recorded on a Bruker
DRX-300 MHz, Avance spectrometer at ambient temperature in DMSO-d . Oxidation
6
products were analyzed by GC and GC–MS using an Agilent 6890 Series with FID
detector, HP-5, 5% phenylmethyl siloxane capillary and an Agilent 5973 Network, mass
selective detector, HP-5 MS 6989 Network GC system.
3

2
2 3 3 2
.2. Synthesis of [MoO Cl (MeOH)]·H tptz·Cl (1)
MoO (0.143g, 1 mmol) dissolved in 5 mL of concentrated HCl was stirred at 70 °C
3
until a pale yellow solution was obtained. A solution of tptz (0.312 g, 1 mmol) in 5 mL of
methanol was then added and the resulting yellow solution left to allow the slow
evaporation of the solvent. After nine days, light-yellow single crystals, suitable for X-
ray diffraction analysis were obtained (yield, 85%). Anal. Calcd. for C19
H
18 Cl
5
MoN
6
3
O :
–
1
C, 34.99; H, 2.30; N, 12.89. Found: C, 34.75; H, 2.62; N, 12.94%. IR (cm ): 488, 658,
6
3
2
96 and 789 (Mo–O), 904 and 939 (Mo=O), 1392 (C=C), 1537, 1542 and 1609 (C=N),
-1
-1
406 (O-H). UV–Vis (MeOH, λmax/nm (ε/M cm )): 588 (42), 534 (33), 282 (38151),
42 (25441), 202 (44307).
2
.3. Catalytic procedure
Catalytic experiments were carried out in a 50 mL glass reaction flask fitted with a
water condenser. In a typical procedure, compound 1 (0.05 g) was dissolved in 5 mL of
acetonitrile. Then, alkene (20 mmol) and TBHP (24 mmol) were added and the mixture
heated at reflux for 3 h. The reaction was monitored at periodic time intervals using gas
chromatography. The oxidation products were identified by comparison of their retention
times with those of authentic samples. At the end of the reaction, the catalyst was
collected by suction filtration on a fine frit, washed with acetonitrile, diethyl ether and
then air dried. The catalyst was reused at least three times without a significant decrease
in catalytic activity or selectivity.
4

2
.4. X-ray Crystallography
X-ray structure determinations
Crystallographic data for compound 1 is shown in Table 1. Diffraction data were
collected on a Bruker APEXII CCD diffractometer using graphite-monochromated Mo-
Kα radiation (λ = 0.71073 Å). Data collections were controlled by APEX2 [39] software
with cell refinement and data reduction performed using SAINT[42]. Multi-scan
absorption corrections were applied using SADABS [39]. The structures were all solved
2
with SHELX [40] and refined by full-matrix least-squares on F using SHELXL-
2
014[40=43] and TITAN200 [41]. All non-hydrogen atoms were assigned anisotropic
displacement parameters. All H-atoms were positioned geometrically and refined using a
riding model with d(C-H) = 0.95 Å for the aromatic and 0.98 Å for the methyl hydrogen
atoms d(N—H) = 0.88 for the N—H hydrogens. The O-H hydrogen atom of the methanol
ligand was not observed in difference Fourier maps and is not reported. Crystals were
very thin and weakly diffracting and significant data could not be obtained beyond 2θ =
1
9°. Despite this the structure solved and refined successfully. Because of the weak data,
the data: parameter ratio is much lower than the ideal value but this is reflected in the
standard uncertainties recorded for all of the reported metrical data. All molecular plots
and packing diagrams were drawn using Mercury [42]. Other calculations were
performed using PLATON [43] and tabular material was produced using WINGX [44].
5

2
.4. Antibacterial activity
The in vitro antibacterial activity was investigated against two Gram-positive (Bacillus
subtilis ATCC 6633 and Staphylococcus aureus ATCC 6538) and two Gram-negative
Escherichia coli ATCC 35218 and Pseudomonas aeruginosa ATCC 27853) bacteria. In
(
order to compare the results, nalidixic acid (30 mg/disc) and vancomycin (30 mg/disc)
were used as standard antibacterial drugs. Determination was carried out by paper-disc
diffusion method [45]. The compound 1 and tptz ligand were dissolved in DMSO at 25
mg/ml concentration. Muller Hinton broth was used for preparing basal media for the
bioassay of the organisms. A lawn culture from 0.5 MacFarland suspension of each strain
was prepared on Muller Hinton agar. Blank paper discs (6.4 mm diameter) were saturated
with a solution of test compounds and placed on the surface of the agar plates. On one
paper disc only DMSO was poured as a control. The plates were incubated at 37 °C for
2
3
3
4 h. The inhibition zone diameters around each disc were measured in mm.
. Results and discussion
.1. Characterization of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
The ionic complex [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
(1) was prepared in high yield
with high purity by combining MoO
3
in concentrated HCl with tptz in a stoichiometric
ratio of 1:1 at room temperature. The tripodal ligand tptz may adopt a number of
structural roles in an oxide material. These include structural incorporation as a terminal
6

monodentate ligand, as a bridging bidentate or tridentate ligand, or as a protonated,
charge-compensating cation [46].
The asymmetric unit of the molybdenum(VI) salt 1 contains a 2,2',2''-(1,3,5-triazine-
2
,4,6-triyl)tripyridinium
cation,
a
cis-dioxotrichloridomethanolmolybdenum(VI)
monoanion and two chloride anions to achieve electrical neutrality (Fig. 1). Selected
bond distances and angles are given in Table 1.
The (triazinetriyl)tripyridinium cation is almost planar with an rms deviation of 0.0672
Å from the best fit plane through all 24 non-hydrogen atoms. This planarity is further
exemplified by the fact that the central triazine ring subtends dihedral angles of 5.3(4),
2
.0(4) and 6.1(4)° with the N4, N5 and N6 pyridinium rings respectively. The Cl4- and
Cl5- anions lie close to the plane of the cation displaced by 0.46(1) and 0.31(1) Å
respectively in the same direction. Each acts as a bifurcated acceptor [47], tethered to the
cation by C—H…Cl hydrogen bonds (Table 2). The Cambridge Crystallographic
Database [48], CCD, (Version 5.35 November 2013 with 3 updates) reveals structures of
seven previously reported salts of the (triazinetriyl)tripyridinium cation, generally with
polyhalide [49] or simple main group [50] and transition metal [50,51] halide
counteranions. In the molybdenum(VI) cation, the molybdenum atom is six coordinated
by two oxide ligands O1 and O2, the O3 oxygen atom of the neutral methanol ligand and
three chlorido anions Cl1—Cl3 giving the overall Mo(VI) complex a single negative
charge. The coordination geometry of the complex is slightly distorted octahedral with
the two oxide ligands and the Cl1, Cl2 and Cl1, Cl3 anions mutually cis. The methanol
ligand is trans to O1. The three oxygen atoms and Cl1 constitute a basal plane with Cl2
and Cl3 in axial positions. The Mo1 atom is displaced by 0.041(7) Å from this plane in
7

the direction of Cl3. The greatest distortion is evident in the considerable deviation of the
O2—Mo1—Cl1 (158.5(5)°) and Cl2—Mo1—Cl3 (165.52(19)°) angles from the
idealized 180° Table 1. The widening of the O1—Mo1—O2 (103.5(7)°), undoubtedly as
a result of steric repulsion, is also significant but greater distortions, up to 114°, have
been observed previously [52]. A search of the CSD revealed only four structures with an
Mo(O
2
)Cl partial coordination sphere. Two of these involved cis-tetrachloro-dioxo-
3
molybdenum(VI) chloride dianions [53,54] while the others more closely resembled the
structure reported here with cis-aqua-trichloro-dioxo-molybdenum(VI) [55] and cis-
trichloro-dioxo-(tetrahydrofuran)-molybdenum monoanions [56]. Bond distances and
angles in these anions were reasonably similar to those reported here for the Mo(VI)
cation.
Packing in the crystal is determined by an eclectic mix of N—H…Cl, C—H…Cl and
C---H…O hydrogen bonds. The cationic (triazinetriyl)tripyridinum moiety is involved in
-
-
four trifurcated N—H…Cl and C—H…Cl contacts to the Cl4 and Cl5 counterions.
These interactions generate planar sheets of cations approximately parallel to the ab plane,
(
Fig. 2). An unusual additional feature of the packing is the presence of Mo1—
Cl1…Cg1 halogen bonds. These were identified in PLATON [44] and, in concert with
C—H…Cl and C—H…O contacts, sandwich alternate molybdenum complexes between
(
triazinetriyl)tripyridinium cations. The primary contact to one face of the sandwich is
the Mo1—Cl1…π interaction while the remaining “triazine slice” is positioned through
contacts in an adjacent row of sandwiches. The adjacent rows run in an obverse fashion
stacking the cations and anions along the c axis direction (Fig. 3). This multitude of
8

intermolecular contacts combines to stack the cations and anions along the c axis
direction (Fig. 4).
The FT-IR spectra of free tptz and compound 1 are shown in Fig. 5 (a, b), respectively.
Predominant vibrational modes for 1 are associated with ν (N–H), ν (C=C), ν (C=N), and
–
1
ring stretching. The medium absorption band at 3406 cm is assigned to ν (O–H) and
demonstrates the existence of a coordinated MeOH molecule. The reported separation
–
1
between ν (C=C) and ν (C=N) is close to 20 cm for polypyridyl compounds [57,58] and
–
1
thus the observed vibrational absorption bands for 1 at 1,609, 1,542, and 1,537 cm may
be due to either different ν (C=N) vibrations on the triazine and pyridyl rings or ν (C=C)
and ν (C=N) with coincidental equivalence of the different aromatic rings. An intense
–
1
band appeared at 1392 cm is assigned to ring stretching of both triazine and pyridyl
rings. The IR spectrum of 1 in KBr matrix confirms the presence of the Mo-O vibration
–
1
–1
band at 939 cm . The broad, strong feature displayed at 904 cm for ν (Mo=O) could
be assigned to the symmetric or asymmetric stretching vibrations [59-61].
The electronic spectrum of 1 was measured in CH OH solution (Fig. 6). The intense
3
–
1
–1
–1
–1
absorption bands at 202 nm (ε = 44307 M cm ), 282 nm (ε = 44,035 M cm ) and
–
1
–1
2
42 nm (ε = 25441 M cm ) are assigned to π→π* and n→π* transitions, respectively.
Unlike the colorless solution of the neutral tptz in acetonitrile, the methanol solution of 1
is yellow, leading to two visible transitions at 534 and 588 nm, as can be seen in Fig. 6.
These absorption bands are most likely arising from the outer-sphere charge-transfer
-
3+
(
OSCT), Cl → [H tptz] . It is well known that some species such as N-methylpyridinium
3
salts undergo an OSCT transition in solution [61-63]. The observation of OSCT band is a
function of the solvating ability of the solvent.
9

1
The H NMR spectrum of compound 1 is shown in Fig.S1. The obtained results support
the crystal structure analysis and suggest that the structure of the
[
MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
is retained in DMSO-d
6
solution. The ideal symmetry of
1
the tptz molecule in solution is D
3
h and this molecule shows four well-resolved H NMR
signals at 7.55, 8.80, 8.90, and 8.98 ppm at room temperature [64]. In comparison, a
3+
small downfield shift for all pyridyl protons of the [H tptz] cation is observed. Different
3
1
to the solid state structure and the H NMR spectrum of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl
2
+
in DMSO-d
ppm.
6
shows that the three protons of the N –H bonds appear at 8.35, 9.2 and 9.5
3
.2. Catalytic studies
Cyclooctene served for exploration of epoxidation reaction. Whereas reaction did not
proceed in the absence of catalyst even under reflux condition, 37 to 98% of cyclooctene
was converted to the corresponding epoxide by using 0.01 to 0.07 g of
[
MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl (1) as catalyst, respectively (Fig. 7). Since the selectivity
2
was observed to decrease beyond using 0.05 g of 1, all other epoxidation reactions were
carried out using the optimum amount of catalyst.
In the next step, the effect of time and solvent on the cyclooctene epoxidation were
investigated (Fig. 8 and 9). As observed in Fig. 8, increasing the reaction time from 1 to
3
9
h using 0.05 g of catalyst was found to increase the reaction conversion from 57 to
5%, beyond which decrease in selectivity occurred concomitantly with increasing in
alkene conversion. On the other hand, changing the solvent was successful since variation
1
0

from dichloromethane to acetonitrile not only increased the cyclooctene conversion from
6 to 95%, but also increase in selectivity toward epoxidation was observed accordingly
Fig. 9). In contrast to dichloromethane and chloroform which partially dissolve aqueous
4
(
TBHP, solvents such as methanol, ethanol and acetonitrile with higher dielectric
constants were expected to be more efficient.
Based on the obtained results, the best reaction conditions were concluded to be
utilization of 0.05 g catalyst in acetonitrile within 3 h.
This method was then applied to epoxidation of cyclohexene, norbornene, trans-
stilbene, styrene and α-methyl styrene. As indicated in Table 4, cyclic alkenes afforded
the corresponding epoxides in more than 90%. Whereas the epoxidation of cyclooctene
and α-methyl styrene led to the corresponding epoxides as the sole product (entries 2 and
4
, Table 4), styrene afforded epoxide in 95% as well as benzaldehyde in 5% as by-
product (entry 5, Table 4) [65]. Interestingly, cyclohexene epoxidation afforded the
corresponding epoxide as major product with some cyclohexene-1-ol and cyclohexene-1-
one as by products.
The stability of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl (1) as the catalyst was studied in
2
epoxidation of cyclooctene by recycling the recovered catalyst for three times (Fig. 10). It
was found that whereas the selectivity did not change, but conversion was decreased from
1
00% to 98% and 95%, respectively. Compared to initial catalyst with 2.74%Mo content,
the reused catalyst showed Mo content of 2.71%, which means a 0.03% reduction in Mo.
The filterate solution also revealed no epoxidation activity for the cyclooctene
epoxidation, confirming the heterogeneity character of the catalyst. Particularly
significant is that, when cyclooctene epoxidation was carried out under optimum reaction
1
1

conditions using the MoO
alkene conversion was observed. This result clearly indicates the key role of compound 1
as the effective catalyst for epoxidation reaction. Recall that the MoO acidic solution
3
acidic solution as catalyst without any ligand, only 4% of
3
was prepared similar to that method indicated in section 2-2 (see experimental) except
that no ligand was added.
Based on the obtained results, the first step of the catalytic cycle seems to involve
transferring of a TBHP proton to one terminal oxygen atoms of MoO group and
2
-
concomitant coordination of t-BuOO to the Lewis acidic metal center, leading to the
formation of the peroxo intermediates [14,22]. The Lewis acidity of the Mo center
increases the oxidizing power of the peroxo group and the olefin is subsequently
deoxidized by nucleophilic attack on an electrophilic oxygen atom of the coordinated
tert-butyl peroxide [66].
3
.3. Antibacterial Activities
The in vitro antibacterial activity of tptz and its complex were studied along with two
standard antibacterial drugs, viz, nalidixic acid and vancomycin. The microorganisms
used in this work include Bacillus subtilis and Staphylococcus aureus (as Gram-positive
bacteria) and Escherichia coli and Pseudomonas aeruginosa (as Gram-negative bacteria).
The results are presented in Table 5 and Fig. 11. The results showed that tptz has a
moderately activity against S. aureus, B. subtilis and P. aeruginosa while it has no
activity against E. coli. Comparing the antibacterial activity of the ligand and complex
indicates that compound 1 exhibits more inhibitory effects than the parent ligand. Such
1
2

increased activity of the metal chelates could be explained on the basis of chelation
theory [67].
It is apparent that the studied complex is more toxic towards Gram(+) strains than
Gram(-) strains. The reason is the difference in the structures of the cell walls. The walls
of Gram(-) cells are more complex than those of Gram(+) cells. Lipopolysaccharides
form an outer lipid membrane and contribute to the complex antigenic specificity of
Gram-negative cells [68].
The antimicrobial activity study revealed that the title compound showed good
antibacterial activities against B. subtilis strains than standard drugs. A thorough
investigation regarding the biological effects of the title Mo complex is essential for
medical practice as a metal-based drug.
4
. Conclusion
The ionic complex [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl (1) exhibits a new inorganic–
2
organic supramolecular polymer and its molecular structure has been determined from
single-crystal X-ray diffraction studies. Compound 1 could be considered as an
inorganic–organic hydrogen-bonded network solid built up from the inorganic isolated
3+
[
MoO
2
Cl
3
(MeOH)] moieties associated to organic [H tptz] units via hydrogen bonds. It
3
was used as catalyst for the epoxidation of some olefins with TBPH. Excellent selectivity
was obtained in the case of cyclooctene and styrene. Whereas the catalyst was reused
three times, its high activity and epoxide selectivity remained almost unchanged. Easy
preparation, mild reaction condition, short reaction time, high yields of the products and
1
3

high selectivity make this catalytic system useful for epoxidation of olefins. Additionally,
compound [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl (1) exhibits antibacterial ability against B.
2
subtilis.
Appendix A. Supplementary data
Crystallographic data (excluding structure factors) for the structural analysis of
MoO Cl (MeOH)]·H tptz·Cl (1) has been deposited with the Cambridge
[
2
3
3
2
Crystallographic Data Centre, No. CCDC 938973 for (1). Copies of this information may
be obtained free of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2
1
EZ, UK. Fax: +44(1223)336-033, e-mail:deposit@ccdc.cam.ac.uk, or www:
www.ccdc.cam.ac.uk.
Acknowledgements
The financial support from the University of Alzahra is gratefully acknowledged and
We thank the University of Otago for the purchase of the diffractometers.
References:
[
[
[
[
[
1] E. I. Stiefel, Science 272 (1996)1599-1660.
2] R.H. Holm, Chem. Rev. 87 (1987) 1401-1449.
3] R.H. Holm, Coord. Chem. Rev. 100 (1990) 183-221.
4] H. Arzoumanian , Coord. Chem.Rev. 191 (1998) 178-202.
5] A. Majumdar, S. Sarkar, Coord. Chem.Rev. 255 (2011) 1039-1054.
[
6] R. Hille, Chem. Rev. 96 (1996) 2757-2816.
1
4

[
7] Y.-L. Wong, Y. Yan, E.S.H. Chan, Q. Yang, T.C.W. Mak, D.K.P. Ng, J. Chem. Soc.,
Dalton Trans. (1998) 3057-3064.
[
8] F.E. Kuhn, A.M. Santos, M. Abrantes, Chem. Rev. 106 (2006) 2455-2475.
9] K.B. Sharpless. R.C. Michaelson,J. Am.Chcm.Soc. 95 ( 1973) 6136-6137.
[
[
10] S. Gago, P. Neves, B. Monteiro, M. Pessêgo, A.D. Lopes, A.A. Valente, F.A.
Almeida Paz, M. Pillinger, J. Moreira, C.M. Silva, I.S. Gonçalves, Eur. J. Inorg.
Chem. (2009) 4528-4537.
[
11] P. Neves, S. Gago, C.C.L. Pereira, S. Figueiredo, A. Lemos, A.D. Lopes, I.S.
Gonçalves, M. Pillinger, C.M. Silva, A.A. Valente, Catal. Lett. 132 (2009) 94-103.
[
12] F.-L. Chai, H.-L. Su, X.-Y. Wang, J.-C. Tao, Inorg. Chim. Acta 362 (2009) 3840-
3
844.
[
[
13] M. Bagherzadeh, L. Tahsini, R. Latifi, L. Keith Woo, Inorg. Chim. Acta 362 (2009)
3
698-3702.
14] J.C. Alonso, P. Neves, M.J. Pires da Silva, S. Quintal, P.D. Vaz, C. Silva, A.A.
Valente, P. Ferreira, M.J. Calhorda, V. Félix, M.G.B. Drew, Organometallics 26
(
2007) 5548-5556.
15] M. E. Judmaier, C. Holzer, M. Volpe, N. C. Mo
1(2012) 9956−9966
[
̈s ch-Zanetti, Inorg. Chem.
5
[
16] S.-B. Ding, Synthesis and Reactivity in Inorg Metal –Organic and Nano –Metal
Chemistry (2013) 43, 877-881
[
17] M. R. Maurya, L. Rana, F.Avecilla, Inorg. Chim. Acta10.1016/j.ica.2015.01.040
[
18] G. Lyashenko, G. Saischek, M.E. Judmaier, M. Volpe, J. Baumgartner, F. Belaj,
V.Jancik, R. Herbst-Irmer, N.C. Mösch-Zanetti, J. Chem. Soc., Dalton Trans.(2009)
5
655-5665.
[
[
[
19] M. Bagherzadeh, R. Latifi, L. Tahsini, V. Amani, A. Ellern, L. KeitWoo,
Polyhedron 28 (2009) 2517-2521.
20] S.M. Bruno, S.S. Balula, A.A. Valente, F.A. Almeida Paz, M. Pillinger, C. Sousa, J.
Klinowski, C. Freire, J. Mol. Catal. A: Chem. 270 (2007) 185-194.
21] M. Bagherzadeh . M. M. Haghdoost a, A. Ghanbarpour a, M. Amini b,H. R.Khavasi
E. Payab a, A. Ellern d, L. Keith WoodInorganica Chimica Acta 411 (2014) 61–66
1
5

[
[
22] M. Masteri-Farahani, F. Farzaneh, M. Ghandi, Catal. Commun. 8 (2007) 6-10.
23] Q.-H. Xia, H.-Q. Ge, C.-P. Ye, Z.-M. Liu, K.-X. Su, Chem. Rev. 105 (2005) 1603-
1
662.
[
[
[
24] S.A. Hauser, M. Cokoja, F.E. Kühn, Catal. Sci. Technol. 3 (2013) 552-561.
25] S. Huber, M. Cokoja, F.E. Kühn, J. Organomet. Chem. 751(2014) 25-32.
26] H. Srour, P.L. Maux, S. Chevance, G. Simonneaux, Coord. Chem. Rev. 257 (2013)
3
030-3050.
[
[
27] K. Ankar Jφrgensen, Chem. Rev. 89 (1989) 431-458.
28] M. Bagherzadeh, M.Amini, A. Ellern, L.K.Woo, Inorg. Chem. Commun. 15 (2012)
5
2–55.
[
[
[
29] F.E. Kuhn, A.D. Lopes, A.M. Santos, E. Herdtweck, J.J. Haider, C.C. Romão, A.G.
Santos, J. Mol. Catal. A: Chem. 151 (2000) 147-160.
30] L.F. Veiros, A. Prazeres, P.J. Costa, C.C. Romão, F.E. Kuhn, M.J. Calhorda, Dalton
Trans. (2006) 1383-1389.
31] S. Bellemin-Laponnaz, K.S. Coleman, P. Dierkes, J.-P. Masson, J.A. Osborn, Eur. J.
Inorg. Chem. (2000) 1645-1649.
[
[
32] G.-S. Kim, D. Huffman, C.W. DeKock, Inorg. Chem. 28 (1989) 1279-1283.
33] M.H. Chisholm, K. Folting, J.C. Huffman, C.C. Kirkpatrick, Inorg. Chem. 23
(
1984)1021-1037.
[
[
34] Z. Petrovski, M. Pillinger, A.A. Valente, I.S. Gonc¸ alves, A. Hazell, C.C. Romao, J.
Mol. Catal. A: Chem. 227 (2005) 67-73.
35] S.Gago, J.E. Rodriguez-Borges, C. Teixeira, A.M. Santos, J. Zhao, M. Pillinger, C.D.
Nunes, ˇZ. Petrovski, T.M. Santos, F.E. Kuhn, C.C. Romao, I.S. Gonc¸ alves, J.
Mol. Catal. A: Chem. 236 (2005) 1-6.
[
[
36] M.N. Patel, P.A. Dosi, B.S. Bhatt, Spectrochim. Acta A86 (2012) 508-514.
37] L. Zhang, X.-Q. Lu, Q. Zhang, C.-L. Chen, B.-S. Kang, Transition Met. Chem. 30
(
2005) 76-81.
[
[
38]S. Rubino, P. Portanova, A. Albanese, G. Calvaruso, S. Orecchio, G. Fontana, G.C.
Stocco, J. Inorg. Biochem. 101 (2007) 1473-1482.
39] Bruker APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA,
2
011.
1
6

[
[
[
40] G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122.
41] K.A. Hunter, J. Simpson, TITAN2000. University of Otago, New Zealand, 1999.
42] C.F. Macrae, I.J. Bruno, J.A. Chisholm, P.R. Edgington, P. McCabe, E. Pidcock, L.
Rodriguez-Monge, R. Taylor, J. van de Streek and P.A. Wood, J. Appl. Cryst., 2008,
4
1, 466-470.
[
[
[
43] A.L. Spek, Acta Cryst., 2009, D65, 148-155.
44] L.J. Farrugia. J. Appl. Cryst., 2012, 45, 849-854.
45] Y.-M. Song, J.-P. Xu, L. Ding, Q. Hou, J.W. Liu, Z.L. Zhu, J. Inorg. Biochem. 103
(
2009) 396-400.
[
[
46] R. S. Rarig, J.J. Zubieta, Inorg. Chim. Acta , 312 (2001) 188-196.
47] G.R. Desiraju, T. Steiner, “The Weak Hydrogen Bond”, Oxford University Press,
New York. (1999) 5.
[
[
48] C. R. Groom, F. H. Allen, Angew. Chem. Int. Ed., 53(2014) 662-671.
49] M. Carla Aragoni, M. Arca, F.A. Devillanova, M.B. Hursthouse, S.L. Huth, F. Isaia,
V. Lippolis, A. Mancini, G. Verani , Eur. J. Inorg. Chem. (2008)3921-3928.
50] T.J. Podesta, A.G. Orpen , Cryst.Growth Des., 5(2005) 681-693.
51] G.A. Barclay, R.S. Vagg, E.C. Watton , Acta Cryst., B33 (1977)3777-3781.
[
[
[
52] B.C. Whitmore, R. Eisenberg. Inorg. Chem., 22(1983)1-5.
[
[
53] Y. Luan, G. Wang, R.L. Luck, Y. Wang, H. Xiao, H. Ding, Chem. Lett., 37(2008)
1
144-1145.
54] J.A. Fernandes, A.C. Gomes, S. Figueiredo, S. Gago, P.J.A. Ribeiro-Claro, I.S.
Gonçalves, F.A. Almeida Paz , Acta Cryst. E66 (2010) m862-m863.
[
[
[
55] C.W. Rodrigues, C. Limberg, H. Pritzkow, Eur. J. Inorg. Chem., (2004) 3644-3650.
56] J. Li, G. Wang, Z. Shi, M. Yang, R.L. Luck, Struct. Chem., 20(2009) 869-876.
57] K. Nakamato (1997) Infrared and raman spectra of inorganic and coordination
compounds, part II: application in coordination, organometallic, and bioinorganic
chemistry, 5th edn. Wiley-Interscience, New York.
[
[
58] M. Maghami, F. Farzaneh, J. Simpson, A. Moazeni, Polyhedron 73 (2014) 22-29.
59] S. Rayati, A. Wojtczak, A. Kozakiewicz, Inorg. Chim. Acta 361 (2008) 1530-1533.
[
60] S. Rayati, N. Torabi, A. Ghaemi, S. Mohebbi, A. Wojtczak, A. Kozakiewicz Inorg,
Chim. Acta 361 (2008) 1239-1245.
1
7

[
61] A.B.P. Lever, Inorganic Electronic Spectroscopy, second ed., Elsevier, Amsterdam,
984.
1
[
[
[
62] R.S. Drago, Physical Methods for Chemists, 2nd edn. Saunders, Philadelphia,1992.
63] H. Kunkely, A. Vogler, Inorg Chim Acta. 357(2004) 1292-1294.
64] P. Paul, B. Tyagi, A.K. Bilakhiya, M.M. Bhadbhade, E. Suresh, G. Ramachandraiah,
Inorg. Chem. 37 (1998) 5733-5742.
[
[
65] A. Günyar, F.E. Kuhn, J. Mol. Catal. A: Chem. 319 (2010) 108-113.
66] F.E. Kuhn, M. Groarke, E. Bencze, E. Herdtweck, A. Prazeres, A.M. Santos, M.J.
Calhorda, C.C. Romão, I.S. Gonçalves, A.D. Lopes, M. Pillinger, Chem. Eur. J. 8
(
2002) 2370-2383.
67] A. Chaudhary, N. Bansal, A. Gajraj, R.V. Singh, J. Inorg. Biochem. 96 (2003) 393-
00.
68] M. Azarkish, T. Sedaghat, Chin. Chem. Lett. 23 (2012) 1063-1066.
[
[
4
Figure captions:
Fig. 1. The asymmetric unit of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl designated as 1 showing
2
the atom numbering with ellipsoids drawn at the 50% probability level. In this and
subsequent diagrams hydrogen bonds are shown as dashed lines.
Fig. 2. Planar layers of (triazinetriyl)tripyridinium cations parallel to the ab plane in the
crystal structure of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl .
2
Fig. 3. Complex molecules sandwiched between pairs of (triazinetriyl)tripyridinium
cations viewed along a.
1
8

Fig. 4. The overall packing of [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl , viewed along c with
2
representative Mo—Cl…π contacts shown as dotted lines.and ring centroids
displayed as coloured spheres.
Fig. 5. FT-IR spectra of (a)TPTZ ligand and (b) [MoO
2
Cl
3
(MeOH)]·H
3
tptz·Cl .
2
Fig. 6. Electronic spectra of [MoO
2
Cl
3
(MeOH)]·H tptz·Cl2. in methanol.
3
Fig. 7. Fig. 7 The effect of amount of catalyst MoO
2
Cl
3
(MeOH) ·H
3
tptz·Cl 1 on
2
cyclooctene epoxidation
Fig. 8 The effect of reaction time of MoO
2
Cl
3
(MeOH) ·H
3
tptz·Cl 1 as catalyst on
2
cyclooctene epoxidation.
Fig. 9. The effect of solvent on the epoxidation of cyclooctene by the
MoO Cl (MeOH)]·H tptz·Cl catalytic system.
[
2
3
3
2
Fig. 10. The results obtained in the oxidation of cyclooctene with TBHP by
MoO Cl (MeOH)]·H tptz·Cl with reused catalyst.
[
2
3
3
2
Fig. 11. Difference between the antibacterial activities metal complex
MoO Cl (MeOH)]·H tptz·Cl (1) with tptz ligand (2) in comparison
with standard antibacterial drugs (3,4).
[
2
3
3
2
1
9

Fig. 1
2
0

Fig. 2

Fig. 3
2
2

Fig. 4
2
3

Fig. 5
2
4

Fig. 6
2
5

Fig. 7
2
6

Fig. 8
2
7

Fig. 9
2
8

Fig. 10
2
9