Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane Tetrachloro Manganate with Perovskite Type Structure

Article abstract of DOI:10.1007/s10562-017-2112-7

Abstract: Layered 2D organic–inorganic hybrid perovskite (OIHS) of the diammonium series, 1,5 di-aminepentane tetrachloro mangenate ([NH₃–(CH₂)₅–NH₃] MnCl₄) was prepared by slow evaporation and reducing temperature method and characterized by single crystal X-ray diffraction analysis. Its structure consists of organic cation, [NH₃(CH₂)₅NH₃]⁺² extended in a zigzag fashion and inorganic anion, [MnCl₆]^?2 where Mn²⁺ is coordinated by six Cl^? ion in octahedral fashion. The organic and inorganic segments are alternately stacked along c-axis where inorganic layer is extended through corner-shared octahedra sandwiched by the di-aminopentane molecules. The layers (organic and inorganic) were connected to each other through N–HCl hydrogen bonds and van-der Waals interaction to build cation–anion–cation cohesion. The hybrid crystal had orthorhombic non-centrosymetric system having I2₁2₁2₁ space group with unit cell parameters a = 7.1742(3) ?, b = 7.3817(3) ?, c = 23.9650(10) ?, V = 1269.13 ?³ and Z = 4. The hybrid exhibited excellent catalytic activity towards sulphide and alkene oxidation using aqueous H₂O₂ as an oxidant. Graphical Abstract: OIHS of the diammonium series [NH₃–(CH₂)₅–NH₃] MnCl₄; 1,5 di-aminepentane tetrachloro mangenate were prepared by slow evaporation and temperature decrease method, characterized by single crystal X-ray diffraction. This complex exhibits excellent catalytic activity towards sulphide oxidation and alkene oxidation using aqueous H₂O₂ as an oxidant. [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-017-2112-7

Catal Lett
DOI 10.1007/s10562-017-2112-7
Catalytic Activity of Crystallographically Characterized
Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane
Tetrachloro Manganate with Perovskite Type Structure
Paramita Mondal1,4 · Seham Kamal Abdel-Aal2,3 · Debasis Das4 · Sk Manirul Islam1
Received: 27 March 2017 / Accepted: 9 June 2017
© Springer Science+Business Media, LLC 2017
Abstract Layered 2D organic–inorganic hybrid perovs-
kite (OIHS) of the diammonium series, 1,5 di-aminepen-
tane tetrachloro mangenate ([NH3–(CH2)5–NH3] MnCl4)
was prepared by slow evaporation and reducing tempera-
ture method and characterized by single crystal X-ray dif-
fraction analysis. Its structure consists of organic cation,
[NH3(CH2)5NH3]+2 extended in a zigzag fashion and inor-
ganic anion, [MnCl6]−2 where Mn2+ is coordinated by six
Cl− ion in octahedral fashion. The organic and inorganic
segments are alternately stacked along c-axis where inor-
ganic layer is extended through corner-shared octahedra
sandwiched by the di-aminopentane molecules. The lay-
ers (organic and inorganic) were connected to each other
through N–H···Cl hydrogen bonds and van-der Waals
interaction to build cation–anion–cation cohesion. The
hybrid crystal had orthorhombic non-centrosymetric sys-
tem having I212121 space group with unit cell param-
eters a=7.1742(3) Å, b=7.3817(3) Å, c=23.9650(10) Å,
V=1269.13 Å3 and Z=4. The hybrid exhibited excellent
catalytic activity towards sulphide and alkene oxidation
using aqueous H2O2 as an oxidant.
Graphical Abstract OIHS of the diammonium series
[NH3–(CH2)5–NH3] MnCl4; 1,5 di-aminepentane tetra-
chloro mangenate were prepared by slow evaporation and
temperature decrease method, characterized by single crys-
tal X-ray diffraction. This complex exhibits excellent cata-
lytic activity towards sulphide oxidation and alkene oxida-
tion using aqueous H2O2 as an oxidant.
S
R
R
R1
H2O2/
H2O2/
CH3CN
CH3CN
O
O
S
O
S
R
+
RCHO
R1
R
R1
R
* Seham Kamal Abdel-Aal
O
seham@sci.cu.edu.eg
* Debasis Das
ddas100in@yahoo.com
* Sk Manirul Islam
Keywords Layered 2D organic–inorganic hybrid ·
Perovskite type Mn complex · Alkene oxidation · Sulfide
oxidation · Hydrogen peroxide
manir65@rediffmail.com
1
Department of Chemistry, University of Kalyani, Nadia,
Kalyani 741235, India
2
Department of Physics, University of Cairo, Giza 12613,
Egypt
1 Introduction
3
Egypt Nanotechnology center EGNC, Sheik Zayied city,
Egypt
Nowadays significant attention has been devoted to the
preparation and characterization of organic–inorganic
4
Department of Chemistry, The University of Burdwan,
Burdwan, West Bengal 713104, India
Vol.:(0123456789)
1 3

P. Mondal et al.
multi-layered perovskites hybrids (OIHs) to tailor their
structural features and tuning their physical as well as
chemical properties. The general formula of diammo-
nium halide perovskite hybrids are A2MX4, where A is
an organic cation, M, a divalent cation while X is a halo-
gen. The perovskite type OIHs of diammonium series hav-
ing formula [NH3–(CH2)n–NH3]MX4 (where n=2, 3, 4…
etc. and M=Mn, Cu, Pb, Fe, Co; X=Cl, Br, I) had exten-
sively been investigated for their interesting physical and
chemical properties, reduced dimension and presence of
numerous structural phase transitions [1–10]. The struc-
tures and properties of OIHs depend on the characteristics
of the organic cation [NH3–(CH2)n–NH3]++ (alkyl chain
a promising approach. However, the development and
implementation of catalytic processes to eliminate the
use of hazardous reactants and reduce waste generation
is an important goal. In this context, use of H2O2 as green
oxidant is an alternative approach.
Herein, we report the synthesis, X-ray single crys-
tal structure, sulphide and alkene oxidation activities
of a new layered 2D OIHs of the diammonium series,
(NH3–(CH2)5–NH3] MnCl4). To the best of our knowl-
edge, alkene and sulphide oxidation using aqueous H2O2
in presence of catalytic amount of Mn-hybrid (C5MnCl)
has been performed for the first time.
length and attached functionalities), the inorganic anion
− −
MX4
(coordination geometry of the cation) and nature
of halide [3–10]. Studies in this area lead to innovation
of advanced materials, solar cells, smart microelectronic,
micro-optical, photonic components and self-assembled
quantum well applications [5, 6, 8]. The simplest 2D lay-
2 Experimental
2.1 Preparation of [NH3–(CH2)5–NH3] MnCl4
ered hybrids consist of MX−2 corner-sharing metal halide
Perovskite hybrid of [NH3–(CH2)5–NH3] MnCl4
was prepared by reacting ethanol solution of both
[NH3–(CH2)5–NH3] Cl2 and MnCl4. 4H2O (1:1 mol ratio)
6
octahedra separated by mono-layers of the organic moiety.
The cavities between the octahedron were occupied by the
terminal NH3 of the organic moieties, [NH3–(CH2)n–NH3]
via formation of N–H···Cl hydrogen bonds with the halide
of the octahedron.
at 70 ͦ C for 1 h followed by gradual cooling to room tem-
perature. Thereby, pink crystals precipitated out. Chemi-
cal analysis and single crystal X-ray diffraction analysis
indicated its chemical formula as [NH3–(CH2)5–NH3]
MnCl4 (henceforth C5MnCl).
Selective oxidation of organic sulfides to sulfoxides is
one of the key reactions in the domain of organo oxidation
chemistry because of the prospective use of sulfoxides as
synthetic intermediates for the creation of many chemically
and biologically active molecules [11, 12]. The prime syn-
thetic path for the preparation of these expensive materi-
als is via oxidation of the corresponding sulfides. Several
reagents used for this key transformation includes stoichio-
metric or catalytic amounts of both organic and inorganic
reagents [13–15]. The exploitation of ‘green oxidants’ such
as molecular oxygen and hydrogen peroxide are attractive,
since they are readily available, inexpensive, and environ-
ment friendly, with a formation of water as sole by-product
[16]. Oxidation of sulfides with H2O2 is slow; hence exten-
sive studies have been performed to develop new catalysts
for this reaction [16–19]. Disadvantages of this sulfoxida-
tion reaction include difficulties to arrest the oxidation at
the sulfoxide stage, and formation of toxic waste. Hence,
there is a need to develop new catalysts to overcome these
drawbacks.
2.2 Characterization
2.2.1 Single Crystal X‑ray Diffraction Analysis
The single crystal X-ray crystallographic data were col-
lected on Enraf–Nonius 590 Kappa CCD single crystal
diffractometer with graphite monochromator using MoKα
(λ= 0.71073 Å). The intensities were collected at room
temperature (298 K) using φ–ω scan mode; the crystal
to detector distance was 40 mm. The cell refinement and
data reduction were carried out using Denzo and Sca-
lepak programs [25] The crystal structure was solved
by the direct method using SIR92 program [26] which
revealed the positions of all non-hydrogen atoms and
refined by the full matrix least square refinement based
on F2 using maXus package [27]. Short average multi-
scanning absorption corrections were applied to all data
using SORTAV program [28]. The temperature factors of
all non-hydrogen atoms were refined anisotropically, then
hydrogen atoms were introduced as a riding model with
C–H = 0.96 Å and refined isotropically. Molecular graph-
ics were prepared using ORTEP and Mercury softwares
[29].
Alkene oxidation is one of the basic reactions in indus-
trial organic synthesis because aldehydes and ketones are
key intermediates for the manufacture of wide variety of
valuable products [20, 21]. Aldehydes and ketones find a
range of applications in the industry of perfumery, phar-
maceutical, dyestuff and agrochemicals [22–24]. So, alk-
ene oxidation under mild conditions is challenging while
transition metal catalyzed the oxidation of the former is
1 3

Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing…
Table 1 Single crystal X-ray diffraction parameters of C5MnCl
3 Results and Discussion
C5MnCl
3.1 Description of the Structure of C5MnCl
Empirical formula
Mr
C5H16N2MnCl4
300.94
The structure of C5MnCl consists of organic dication
[NH3–(CH2)5–NH3]+2 extended in a zigzag structure and
Space group
A
B
C
β
V
Z
Dx
Orthorhombic I212121
7.1742 (3) Å
7.3817 (3) Å
23.9650 (10) Å
90°
2−
inorganic dianion MnCl4 coordinated by six Cl atoms
in octahedral topology, [MnCl6]2−. The organic and inor-
ganic structures were alternatively stacked along c axis,
where inorganic layers were extended corner-shared octa-
hedra sandwiched by the di-aminopentane molecules. The
layers (organic and inorganic) were connected with each
other through N–H···Cl hydrogen bonds and van-Der Waals
interaction as to build cation–anion–cation cohesion. The
hybrid crystallized in orthorhombic space group I212121,
having unit cell parameters: a=7.1742(3) Å, b=7.3817(3)
Å, c=23.9650(10) Å, V=1269.13 Å3 and Z=4. The
structure was solved by using 2760 independent reflec-
tions down to R value of 0.053. While Table 1 shows the
crystallographic parameters of C5MnCl, Fig. 1 presents its
molecular structure. Figure 2 show the unit cell along 010
plane.
1269.13 (9) Å3
4
1.575 Mg m−3
Mo Kα
Radiation type
λ
θmax
μ
T
0.71073 Å
34.97°
1.84 mm−1
298 K
Shape
Color
Cube
Pink
Measured reflection
Independent reflections
7557
2760
Observed reflections
1482
Criterion
Rint
H
K
L
R (all)
R (gt)
wR (ref)
wR (gt)
S (ref)
∆/σmax
∆ρmax
∆ρmin
Reference
I>2.00 sigma(I)
0.055
−10 →11
−11→11
−32 →38
0.122
0.053
0.171
0.134
0.895
3.2 UV–Vis and FTIR Spectra Analysis
It is clearly noted from Fig. 1a that the ligand did not coor-
dinate to manganese center. Rather, the ligand is protonated
and this protonated cation interacted with the manganese
containing anion. So, that is also reflected from the UV–Vis
spectrum of the complex. The absorption spectrum (Fig. 3)
of ethanol solution of C5MnCl show peaks at ~209 nm and
259.0 nm which may be attributed to the intra-ligand (n–π*
and π–π*) charge transfer processes. Moreover, a very weak
absorption at 520 nm, characteristics of Mn(II) center was
also observed.
0.416
0.524 eÅ−3
−0.665 eÅ−3
This work
Figure 4 show the FTIR spectrum of C5MnCl
in the range 4000–400 cm−1. The bands at region
4000–3000 cm−1 were due to internal stretching of the
diammonium cation. The C–H bonds of the protonated
ligand show IR bands in the range 3188−3060 cm−1. More-
over, N–H stretching bands were observed in the range
3360−3100 cm−1. The unique band at 2941−2885 cm−1
were characteristics and indication of hydrogen bond
formed [1, 4, 30].
The band at 1492 cm−1 was probably due to the
(NH3) symmetric deformation mode. The strong band
at 1583 cm−1 was assigned to asymmetric mode, δas
(NH3). Bands near 1200 cm−1 were assigned to the wag-
ging mode of the CH2 group. The coupling with the
(NH3)+might be the reason for strong enhancement of
the intensity of CH2 stretching frequency. For C5MnCl4,
δr (CH2) was found at 1400–1123 cm−1, and wagging
coupled with (NH3)+was found at 1176 cm−1. Bands at
Fig. 1 Molecular structure of hybrid C5MnCl
1 3

P. Mondal et al.
Fig. 2 Layer structure of
C5MnCl in the unit cell along
010 plane
1.0
3.4 Catalytic Activity
209 nm
3.4.1 Oxidation of Sulfides with H2O2 Using C5MnCl
0.8
Catalyst
259 nm
0.6
0.4
0.2
0.0
For optimization of the reaction conditions, oxidation
of diphenyl sulfide was carried out as a probe reaction
(Scheme 1). The C5MnCl catalyst was very efficient for
the oxidation of diphenylsulfide to produce sulfoxide as
a major product. First, the oxidation of diphenylsulfide
with H2O2 using C5MnCl catalyst was examined in sev-
eral polar and non-polar solvents (Table 2). Quantitative
yields were obtained with polar solvents like acetonitrile,
dimethylformamide and methanol (Table 2, runs 1–3),
however, the efficiency of the catalyst was not satisfactory
in non-polar solvents like toluene and p-xylene (Table 2,
runs 5, 6). The higher catalytic activity in acetonitrile
was attributed to its dielectric constant, polarity and
higher miscibility of the organic substrate and H2O2. It
was observed that less polar solvents constituted a hetero-
geneous system with aqueous hydrogen peroxide which
was ineffective. The reaction temperature played a signif-
icant role on the catalytic activity as evident from Fig. 5.
At room temperature, moderate yield of the product was
observed. Upon increase of reaction temperature to 40 °C,
complete conversion of diphenylsulfide, along with the
highest selectivity to yield the corresponding sulfoxide
were observed. At much higher temperature (60 °C), con-
version efficiency remain unaltered however the selectiv-
ity of product yield decreased. The catalytic activity of
C5MnCl for oxidation of diphenylsulfide was also inves-
tigated using a variable amount of H2O2 (n = 3). Table 2
indicated that the conversion to the product increased
with increasing amount of H2O2 (from 5 mmol, run 7 to
10 mmol, run 1). However, further increase of H2O2 to
15 mmol caused no significant increase in the conversion
efficiency (Table 2, run 8) under said reaction conditions.
Rather, the selectivity of yielding sulfoxide decreased at
15 mmol H2O2. This might be due to further oxidation of
sulfoxide to corresponding sulfone derivative. The results
were presented in Fig. 6. With the increase of the catalyst
200
300
400
500
600
700
800
Wavelength (nm)
Fig. 3 UV–vis spectrum of C5MnCl
900–700 cm−1 were assigned to the CH2 rocking mode
δr (CH2). Bands below 700 cm−1 were assigned to the
stretching mode of C–N bond. The observed IR bands
were in good agreement to the similar compounds found
in literature [1, 4].
3.3 General Procedure for Oxidation Reactions
The solution phase oxidation reactions were carried out
in a double necked round bottom flask equipped with a
water condenser and refluxed at different temperatures
under vigorous stirring for a certain period of time over
an oil bath. Substrates (5 mmol) were dissolved in ace-
tonitrile (5 mL) along with 5 mg C5MnCl and 10 mmol
of H2O2 (30% aqueous solution). Monitoring of product
formation was performed using Varian 3400 gas chroma-
tographic instrument equipped with a 30 m CP-SIL8CB
capillary column and a FID detector. All products
were identified by GC by comparing with the reference
samples.
1 3

Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing…
Fig. 4 FTIR spectrum of C5MnCl
Scheme 1 Oxidation of diphe-
O
S
O
S
O
nyl sulfide
S
Mn-catalyst
+
H2O2, CH3CN
400C
diphenyl sulfone
diphenyl sulfoxide
diphenyl sulfide
Table 2 Effect of different reaction parameters on the oxidation of
diphenyl sulfide using C5MnCl catalyst
100
80
60
40
20
0
Conversion (%)a
Conversion
Selectivity
Run
Solvent
Amount of 30% aq.
H2O2 (mmol)
1
2
3
4
5
6b
7
8
9
CH3CN
DMF
Methanol
CHCl3
Toluene
p-Xylene
CH3CN
CH3CN
CH3CN
10
10
10
10
10
10
5
97
56
38
20
12
07
36
87
15
–
60
25
40
No reaction
Temperature (0C)
Conditions: Diphenyl sulfide (5 mmol), solvent (5 mL); catalyst
(5 mg), temp. (40°C), time 5 h
Fig. 5 Effect of temperature on the oxidation of diphenyl sulfide
using C5MnCl catalyst. Reaction conditions: diphenyl sulfide
(5 mmol), CH3CN (5 mL); C5MnCl catalyst (5 mg), Time, 5 h
aConversion and selectivity were determined by GC
bProducts were characterized by GC by comparing with the authentic
samples
1 3

P. Mondal et al.
For wider application of the catalyst, oxidation of other
sulfides were also examined (Table 3). Substrate scope was
extended to various aliphatic and aromatic sulfides. In all
cases, sulfoxides were selectively obtained under optimum
reaction conditions. A series of substrates, aryl alkyl, aryl
allyl and dialkylsulfides, could be oxidized to the cor-
responding sulfoxides in good yields. The reactivity and
conversion efficiencies were dependent on the nature of
the substituent present in the ArSMe. The introduction of
electron donating substituents in the phenyl ring of ArSMe
accelerated the rate whereas the electron withdrawing sub-
stituents retarded the rate (Table 3, runs 7 and 8). The sul-
fur center of substituted sulfides containing other oxidation
prone functional groups such as C–C and OH (Table 3, runs
9 and 10) gave good conversion with the present catalyst.
100
80
60
40
20
0
Conversion
Selectivity
0.0
2.5
5.0
7.5
10.0
Amount of catalyst (mg)
Fig. 6 Effect of catalyst load on the oxidation of diphenyl sulfide.
Reaction conditions: diphenyl sulfide (5 mmol), CH3CN (5 mL); tem-
perature (40°C), time, 5 h
3.4.2 Oxidation of Alkenes with H2O2 Using C5MnCl
Catalyst
load to 2.5 mg, the conversion efficiency increased to
72% while a little amount of sulfone was detected. A fur-
ther increase of catalyst load to 5 mg increased the con-
version to 97%. Interestingly, at a much higher amount
of the catalyst (7.5 and 9 mg), the conversion efficiency
remained almost constant, however, the selectivity of sul-
foxide production was reduced. These findings indicated
that the oxidation of sulfide was highly dependent on the
amount of the catalyst. A blank experiment in presence
of oxidant under same experimental conditions without
C5MnCl was also investigated and found a very poor
conversion of diphenylsulfide. Thus, it was concluded
that 5 mg of C5MnCl catalyst, 10 mmol 30% H2O2 in
acetonitrile medium was the optimum condition for the
oxidation of sulfides to sulfoxides with very good selec-
tivity. Moreover, in absence of H2O2, C5MnCl catalyst
alone failed to oxidize sulfides (Table 2, run 9).
The excellent catalytic activity of C5MnCl for sulfide oxi-
dation motivated us to explore its potentiality for alkene
oxidation. For optimization of reaction conditions, oxida-
tion of styrene was monitored as a probe reaction using
C5MnCl as catalyst and H2O2 as an oxidant while benza-
ldehyde was formed as the major product (Scheme 2). The
results of the control experiment revealed (Table 4) that the
presence of both catalyst and oxidant were essential for the
oxidation reaction to occur (run11). In absence of C5MnCl
catalyst, the oxidation proceeded only up to 8% after 24 h
(run 12).
In search of suitable reaction conditions for maximum
oxidation of styrene, the effect of solvent, concentration of
oxidant (moles of H2O2 per moles of styrene), and reaction
temperature were studied. At first, oxidation of styrene was
studied in different solvents like methanol, acetone, DMF
and CH3CN (Table 4, runs 1–4). As highest conversion
Table 3 Oxidation of sulfides
using 30% H2O2 catalyzed by
Mn-catalyst
Entry
Substrates
Conversion (%)/ Product selectivity (%)
TON
TOF h−1
time (h)a
sulfoxide/sulfonea,b
1
2
3
4
5
6
7
8
9
PhSCH3
PhSC2H5
PhSPh
PhSCH2Ph
p-CH3C6H4SCH3
p-NO2C6H4SCH3
C4H9SC4H9
PhSCH2CH=CH2
PhSC2H4OH
99/3
95/4
97/4
88/5
83/6
98/4
89/4
71/6
84/6
92/8
298
286
292
265
250
295
268
213
253
99
71
73
53
42
74
67
36
42
89/11
90/10
87/13
85/15
88/12
87/13
80/20
83/17
Conditions: Sulfide (5 mmol); 30% aq H2O2 (10 mmol); CH3CN (5 ml); catalyst (5 mg) temperature 40°C
aConversion and selectivity were determined by GC
bProducts were characterized by GC by comparing with the authentic samples
1 3

Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing…
was found in acetonitrile medium, it was chosen as the
O
CHO
reaction medium. The effect of concentration of H2O2 on
the oxidation of styrene was illustrated in Table 4. Dif-
ferent H2O2/styrene molar ratios (0.5:1, 1:1, 2:1 and 3:1)
were employed while keeping fixed amount of styrene
(1.0 mmol) and catalyst (5 mg) in CH3CN (5 mL) medium
at 50°C. Increasing H2O2/styrene ratio from 0.5:1 to 2:1
increased the conversion efficiency from 29 to 93%. The
Further increase had resulted in reduced the conversion.
The maximum styrene conversion was found in the case
of 2:1 mol ratio. The performance of the catalyst was stud-
ied at four different temperatures, viz. 30 (room tempera-
ture), 40, 50 and 60°C, keeping fixed amount of styrene
(5 mmol), H2O2 (10 mmol) and catalyst (5 mg) in 5 mL
CH3CN (Table 4, runs 4, 8–10). A maximum of 93% con-
version was achieved by carrying out the reaction at 50°C.
At lower temperature, the conversion efficiency was low.
At 60°C, the initial conversion of styrene was high than
at 50°C but the selectivity of oxidation lost to an extent.
Therefore, 50°C was chosen as the optimum temperature
for all catalytic oxidation reactions of olefins.
Mn-catalyst
+
H2O2, CH3CN
500C
Benzaldehyde Styrene oxide
Styrene
Scheme 2 Oxidation products of styrene
Table 4 The effect of different reaction parameters on the oxidation
of styrene using C5MnCl catalyst
Run
Solvent
Tempera- H2O2 to sub-
Conversion (%)a
ture (°C)
strate mole ratio
1
2
3
4
5
6
7
8
Methanol
Acetone
DMF
50
50
50
50
50
50
50
30
40
60
50
50
2:1
2:1
2:1
2:1
0.5:1
1:1
3:1
2:1
2:1
2:1
0:1
2:1
38
47
78
93
29
72
91
18
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
These optimized reaction conditions were applied to
the oxidation reactions of other olefins by C5MnCl cata-
lyst and the results were shown in Table 5. This catalyst
efficiently converted olefins to the corresponding allylic
products in presence of H2O2. In the oxidation of cyclohex-
ene, allylic products, 2-cyclohexene-1-one and 2-cyclohex-
ene-1-ol were obtained. Substituted styrene selectively
produced corresponding aldehydes. Acetophenone was
detected in the oxidation of α-methyl styrene as a major
product. Trans-stilbene was also oxidized by this catalyst
in high yields and gave benzaldehyde as a major product
9
58
93
10
11
12b
No reaction
8
Conditions: styrene (5 mmol), solvent (5 mL); catalyst (5 mg), time
(6 h)
aConversion was determined by GC
bIn absence of catalyst
Table 5 Oxidation of alkenes by C5MnCl catalyst in presence of 30% H2O2
Run
Substrates
Conversion (%)a/ Product selectivity (%)b
TON
TOF h−1
time (h)
1
2
3
4
5
Cyclohexene
Styrene
4-Methylstyrene
4-Chlorostyrene
4-Nitrostyrene
83/6
93/6
74/6
72/6
85/6
2-Cyclohexene-1-one (67) 2-Cyclohexene-1-ol (30)
Benzaldehyde (88) Styrene oxide (12)
4-Methyl benzaldehyde (81) 4-Methylstyrene epoxide (17)
4-Chloro benzaldehyde (77) 4-Chlorostyrene epoxide (23)
250
280
223
217
256
42
47
37
36
43
4-Nitro benzaldehyde (80)
4-Nitro styrene oxide (20)
6
7
α-Methyl styrene
Trans-Stilbene
84/6
70/8
Acetophenone (100)
253
211
41
26
Benzaldehyde (75)
Benzil (18)
8
α-Pinene
56/8
Verbenol(23)
169
21
Verbenone (56)
α-Pinene oxide (21)
Conditions: styrene (5 mmol), solvent (5 mL); catalyst (5 mg), time (6 h)
aConversion was determined by GC
bIn absence of catalyst
1 3

P. Mondal et al.
2. Mostafa MF, Abdel-Aal SK, Tammam AK (2014) Ind J Phys
88(1):49
along with small amount of benzil. This catalyst shows
good activity for oxidation of α -pinene, where major prod-
ucts found were verbenone and verbenol. We have also
compared the catalytic results for oxidation of alkenes with
other reported catalyst in the literature [31, 32]. Our cata-
lyst shows comparable results with other reported catalysts
[31, 32].
3. Mostafa MF, El-khiyami SS, Abdel-Aal SK (2017) J Mol Struct
1127:59
4. Abdel-Aal SK (2017) Solid State Ionics 303:29
5. Pradeesh K, Baumberg JJ, Vijaya Prakash G (2009) Appl Phys
Lett 95(3):033309
6. Pradeesh K, Yadav GS, Singh M, Vijaya Prakash G (2010) Mater
Chem Phys 124(1):44
7. Wei Y, Audebert P, Galmiche L, Lauret JS, Deleporte E, (2014)
Materials 7(6):4789
8. Mitzi DB (2001) Dalton Trans 1:1
4 Conclusion
9. González-Carrero S, Galian RE, Pérez-Prieto J, (2015) Part Syst
Charact 32(7):709
We have reported the synthesis and single crys-
tal X-ray structure of 2D hybrid perovskite of
[[NH3–(CH2)5–NH3] MnCl4 (cadverin salt). The hybrid
crystallizes as an orthorhombic system having space group
I212121 non-centrosymmetric, with unit cell parameters
a=7.1742 (3) Å, b=7.3817 (3) Å, c=23.9650 (10)Å and
Z (the number of molecules per unit cell)=4. This hybrid
perovskite show excellent catalytic activity for oxidation of
sulphide and alkene using H2O2 as an oxidant, observed for
the first time in the area of organic–inorganic hybrids.
10. Maris T, Bravic G, Chanh NB, Leger JM, Bissey JC, Villesu-
zanne A, Zouari R, Daoud A, (1996) J Phys Chem Solids
57(12):1963.
11. Drabowicz J, Kielbsinski P, Mikolajczyk M, Patai S, Rappoport
Z, Stirling C (eds) (1988) The chemistry of sulphone and sulph-
oxide. Wiley, New York
12. Frenanez I, Khiar N (2003) Chem Rev 103:3651
13. Romanelli GP, Vázquez PG, Tundo P (2005) Synlett 1:75
14. Kaczorowska K, Kolarska Z, Mitka K, Kowalski P (2005) Tetra-
hedron 61:8315
15. Bahrami K (2006) Tetrahedron Lett 47:2009
16. Lane BS, Burgess K (2003) Chem Rev 103:2457
17. Venkat-Reddy C, Verkade JG (2007) J Mol Catal A 272:233
18. Jeyakumar K, Chand DK (2006) Tetrahedron Lett 47:4573
19. Kirihara M, Yamamoto J, Noguchi T, Hirai Y (2009) Tetrahe-
dron Lett 50:1180
5 Supplementary materials
20. Choudary BM, Bharathi B, Reddy CV, Kantam ML, (2002) J
Chem Soc Perkin Trans 1:2069
All crystallographic data for the structure reported in this
manuscript may be obtained free of charge through Cam-
bridge Crystallographic Data Centre as supplementary
publication, deposit number. CCDC. 1401387. Copies
of the data may be obtained on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336
033; e-mail: deposit@ccdc.cam.ac.uk).
21. Shaabani A, Rezayan AH (2007) Catal Commun 8:1112
22. Fredrich B, Gerhartz W (eds.) (1985) Ullmann’s encyclopedia of
industrial chemistry, vol 3 Wiley, Weinheim, New York, p. 470
23. Kroschwitz JI, Othmer K (1992) Encyclopedia of chemical tech-
nology. Wiley, New York
24. Ullmann F (2003) Ullmanns encyclopedia of industrial chemis-
try. Wiley, Weinheim
25. Otwinowski Z, Minor W, Carter CW, Jr., Sweet RM (ed) (1997)
Cell refinement: HKL scalepack. in: Methods in enzymology,
vol 276 Publishing Academic Press, New York, p 30
26. Altomare A, Cascarano G, Giacovazzo C, Guagliardi A, Burla
MC, Polidori G, Camalli M, (1994) J Appl Cryst 27:435.
27. Mackay S, Gilmore CJ, Edwards C, Stewart N, Shankland K,
maXus Computer Program for the Solution and Refinement of
crystal Structures. Bruker Nonius, The Netherlands, MacSci-
ence, Japan and The University of Glasgow (1999).
28. Blessing RH, (1995) Acta Cryst A 51:33.
29. Johnson CK, ORTEP–II (1976) A fortran thermal-ellipsoid plot
program, Report ORNL-5138, Oak Ridge National Laboratory,
Oak Ridge, Tennessee. USA
Acknowledgements P.M. is thankful to the University Grant
Commission (UGC) for funding in the form of Dr. D.S. Kothari
post-doctoral research fellowship (Award no. F4-2/2006 (BSR)/
CH/15–16/023). We sincerely thank Department of Chemistry of the
University of Burdwan for infrastructural facilities. S.M.I. acknowl-
edges the Council of Scientific and Industrial research, (CSIR, pro-
ject reference no. 02(0284)/16/EMR-II), New Delhi, Govt. India, and
Department of Science and Technology, Govt. of West Bengal (DST-
W.B.), Project Reference Number 811(Sanc.) /ST/P/S&T/4G-8/2014,
dated: 04/01/2016, for funding. We acknowledge Department of
Science and Technology (DST) and University Grant Commission
(UGC) New Delhi, India for providing support to the Department of
Chemistry, University of Kalyani under PURSE, FIST and SAP pro-
gram. S. K. A. is grateful to the financial support of Faculty of Sci-
ence, Cairo University, Egypt.
30. Dhara K, Sarkar K, Srimani D, Saha SK, Chattopadhay P, Bhau-
mik A (2010) Dalton Trans 39:6395
31. Nandi M, Roy P, Uyama H, Bhaumik A (2011) Dalton Trans
40:12510
32. Paul L Banerjee B, Bhaumik A, Ali M, (2016) J Solid State
Chem 237:105
References
1. Abdel-Aal SK, Abdel-Rahman AS (2017) J Cryst Growth
457:282
1 3