A three-dimensional (3D) manganese (II) coordination polymer: Synthesis, structure and catalytic activities

Article abstract of DOI:10.1002/aoc.4447

A new Mn (II)-containing coordination polymer, [Mn₆(Ipa)₆(ad)?6H₂O] (1; Ipa?=?isophthalate ligand; ad?=?adenine), was synthesized by reacting hydrated manganese nitrate with isophthalic acid and adenine under solvothermal

Full text of DOI:10.1002/aoc.4447

Received: 15 February 2018
DOI: 10.1002/aoc.4447
Revised: 24 April 2018
Accepted: 3 May 2018
F U L L P A P E R
A three‐dimensional (3D) manganese (II) coordination
polymer: Synthesis, structure and catalytic activities
Souvik Pal | Sudip Maiti | Hari Pada Nayek
Department of Applied Chemistry, Indian
A new Mn (II)‐containing coordination polymer, [Mn6(Ipa)6(ad)⋅6H2O] (1;
Institute of Technology (Indian School of
Mines), Dhanbad – 826004, Jharkhand,
India
Ipa = isophthalate ligand; ad = adenine), was synthesized by reacting hydrated
manganese nitrate with isophthalic acid and adenine under solvothermal reac-
tion conditions. Polymer 1 was characterized using single‐crystal X‐ray diffrac-
Correspondence
Hari Pada Nayek, Department of Applied
tion analysis and other techniques such as Fourier transform infrared
Chemistry, Indian Institute of Technology
spectroscopy, elemental analyses and powder X‐ray diffraction. The solid‐state
(Indian School of Mines), Dhanbad –
826004, Jharkhand, India.
structure of 1 confirmed the formation of a three‐dimensional framework
structure based on Mn6 secondary building units. Phase purity of bulk 1 and
its thermal stability were investigated. Polymer 1 was evaluated for its perfor-
mance as a heterogeneous catalyst for the Henry (nitroaldol) reaction of nitro-
methane with several aldehydes. The recyclability of 1 and heterogeneity of the
reaction were also explored. A plausible mechanism for such reaction is pro-
posed. To the best of our knowledge, polymer 1 represents the first example
of a Mn (II)‐ and adenine‐containing coordination polymer as well as the first
example of a Mn (II)‐containing coordination polymer that has been employed
for the Henry reaction.
Email: hpnayek@iitism.ac.in
Funding information
Science and Engineering Research Board
(SERB), DST, India, Grant/Award Num-
ber: SB/EMEQ‐013/2014
KEYWORDS
adenine, coordination polymer, Henry reaction, heterogeneous catalyst, single‐crystal X‐ray
diffraction
1 | INTRODUCTION
peptides are preferred over synthetic ligands in the prep-
aration of such compounds.[8] These biomolecules are
Presently, metal–organic frameworks (MOFs)/coordina-
tion polymers (CPs) are of immense interest among
chemists, physicists and material scientists. These highly
demanding compounds are synthesized by connecting
inorganic metal nodes with organic linkers. Owing to
their stable and tunable porous structures, they have
emerged as promising functional materials in catalysis,[1]
chemical separations,[2] gas storage,[2c,3] molecular sens-
ing,[4] contaminant removal,[5] ion exchange[3b,6] and
drug delivery.[7] A large number of interesting and
diverse polydentate ligands have been synthesized and
employed in the formulation of MOFs/CPs. Nowadays,
biomolecules such as nucleobases, amino acids and
inexpensive, nontoxic and capable of forming hydrogen
bonds, inducing chirality as well as providing multiple
donor sites.[9] Interestingly, nucleobases are of prime
interests among biomolecules for the construction of
CPs. They can offer a rigid and porous framework. In
contrast, other biomolecules (peptides, proteins and
amino acids) would result in flexible, interpenetrated
and nonporous frameworks which limit their applica-
tions. Among nucleobases, adenine is a more attractive
building unit because of its rigid, planar and π‐conjugated
structure.[10] Moreover, it offers five potential donor sites
including heterocyclic and imidazole nitrogen atoms
(Scheme 1) which can coordinate many metal ions or
Appl Organometal Chem. 2018;e4447.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4447

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PAL ET AL.
were introduced as heterogeneous catalysts for the
nitroaldol reaction.[19b,20]
As adenine‐containing CPs contain multiple Lewis
acid and Lewis base sites, we presumed that these CPs
could exhibit significant catalytic activity towards the
Henry (nitroaldol) reaction. Therefore, we report herein
the synthesis and characterization of a new adenine‐
based Mn (II) coordination polymer of formula [Mn6
(Ipa)6(ad)⋅6H2O] (1; Ipa = isophthalate; ad = adenine).
Detailed experimental processes and characterizations of
1 are discussed. Solid‐state structures of 1 were deter-
mined using single‐crystal X‐ray diffraction (XRD) analy-
sis. In addition, we explored its catalytic activity towards
the Henry reaction of nitromethane with various alde-
hydes. The stability, recyclability and heterogeneity of 1
were established. To the best of our knowledge, this is
the first report of any biomolecule‐derived coordination
polymer investigated for its catalytic activity towards the
Henry reaction.
SCHEME 1 Five potential donor sites of adenine ligand
form hydrogen bonds and thus leading to new polymeric
structures.[9–11]
Its rich coordination ability and hydrogen bonding
capabilities result in the formation of diverse framework
structures with applications mainly in gas adsorption
and drug encapsulation/delivery.[12] For instance, bio‐
MOF‐1 exhibits exceptional gas adsorption properties
and is suited for loading and controlled release of the cat-
ionic drug procainamide HCl.[13] The anticancer drug
methotrexate was successfully loaded into two bio‐MOFs
(ZJU‐64 and ZJU‐64‐CH3) and delivered in specific can-
cer cells to kill the cells with low side effects.[14] In addi-
tion, these adenine‐based CPs are also useful for
adsorption and/or separation of hydrocarbons, gases and
organic dyes.[15] Sensing abilities of such compounds
have recently been investigated against explosives (nitro
aromatic compounds), volatile organic amines and toxic
metal (Hg).[16] Many CPs have already been proven to
be effective heterogeneous catalysts for organic conver-
sion. Despite the existence of Lewis acid sites (metal ions)
and Lewis base sites (nitrogen atoms on adenine), cata-
lytic abilities of such CPs towards organic transforma-
tions under heterogeneous reaction condition are
scarcely investigated. One can cite a single report where
a Zn (II)‐containing complex was tested for its catalytic
activities only in Knoevenagel condensation reaction.[17]
Based on the previous discussion, we were interested
in developing a new biomolecule‐derived CP and investi-
gating its catalytic activity towards an organic reaction
(Henry reaction). The Henry or nitroaldol reaction is an
important C─C bond formation technique in progressive
organic chemistry. Generally, the reaction is performed
using various basic catalysts, such as alkoxides, alkali
metal hydroxides, amines, etc.[18] Many transition metal
complexes have also been used as homogeneous catalysts
for such conversion.[19] Occasionally, a heterogeneous
catalyst has been used for such transformation. Recently,
a few transition metal‐ and lanthanide‐containing CPs
2 | RESULTS AND DISCUSSION
2.1 | Synthesis and Structure
The formation of 1 was achieved by solvothermal reaction
of isophthalic acid (H2Ipa) and adenine (ad) with Mn
(OAc)2⋅4H2O in a mixture of ethanol and water. Polymer
1 appeared as a white crystalline solid. The Fourier trans-
form infrared (FT‐IR) spectrum of 1 shows a strong
absorption band at 1667 cm−1 assigned to asymmetric
stretching vibration of coordinated carboxylate group
(Figure S1 in the supporting information). A broad band
at approximately 3400 cm−1 is assigned to O─H
stretching vibrations and thus it confirms the presence
of water molecules (coordinated) in 1. The phase purity
and reproducibility of bulk samples of 1 were established
using powder XRD (Figure S2 in the supporting informa-
tion). The composition of the as‐synthesized 1 was deter-
mined using single‐crystal XRD analysis, elemental
analysis and thermogravimetric analysis (TGA). Detailed
experimental procedures and data are given in Section 4.
The result of single‐crystal X‐ray structural analysis
reveals that 1 crystallizes in orthorhombic centrosymmet-
ric space group Pmn21. Detailed single‐crystal data and
refinement parameters are provided in Table 1. Polymer
1 reveals a three dimensional framework structure based
on Mn6 secondary building units. Each Mn6 secondary
building unit is formed from two Mn3 units assembled
with an adenine molecule (Figure 1). Polymer 1 consists
of six Mn (II) ions, six isophthalate ligands, one bridging
adenine molecule and six coordinated water molecules.
There are three crystallographically independent Mn (II)
ions in an asymmetric unit of 1. The coordination

PAL ET AL.
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TABLE 1 Single‐crystal data and structure refinement parame-
ters for 1
environment of Mn (II) ions in 1 is shown in Figure 2.
The Mn1 atom is hexa‐coordinated and bonded to four
oxygen atoms (O1, O2, O3 and O9) of isophthalate
ligands, one nitrogen atom (N3) of a neutral adenine mol-
ecule and one oxygen atom O(13) of an aqua ligand.
The central Mn (II) ion (Mn2) occupies the centre of a
distorted octahedron and is coordinated by six oxygen
atoms (O1, O4, O9, O5, O7 and O12) of the carboxylate
groups of isophthalate anions. The terminal Mn (II) ion
Mn3 also adopts a distorted octahedral coordination
geometry environment. The coordination number of
Mn3 is satisfied by four oxygen atoms (O6, O12, O8 and
O11) of bridging isophthalate ligands and two oxygen
atoms (O14 and O15) of two coordinated water mole-
cules. The Mn─O and Mn─N bond lengths are
2.090(7)–2.334(7) and 2.231 (10) Å, respectively. The
Mn⋅⋅⋅Mn non‐bonded distances are 3.511 (Mn1⋅⋅⋅Mn2)
and 3.561 (Mn2⋅⋅⋅Mn3) Å, respectively. Similar observa-
tions for Mn3 system were previously reported.[21]
Selected bond lengths are given in Table S1 in the
supporting information. Three different binding modes
of isophthalate anions are observed, in which the carbox-
ylate moieties exhibit bidentate and tridentate coordina-
tion fashion to assemble Mn (II) ions as displayed in
Figure 3.
Formula
C53H40Mn6N5O30
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
1556.54
100(2)
Orthorhombic
Pmn21
22.0677 (11)
7.7758(4)
17.6217 (10)
90
b (Å)
c (Å)
β (°)
Z
2
dcalc (g cm−3
)
1.710
μ(mm−1
)
1.311
F (000)
1566
Total reflections
Unique reflections
Observed data [I > 2σ(I)]
No. of parameters
R (int)
19521
5579
4930
413
0.0474
0.0546
0.1610
1.118
R1 [I > 2σ(I)]
Interestingly, adenine adopts bidentate coordination
modes (Figure 1) and is bonded to two Mn (II) ions
despite its various coordination modes discussed else-
where.[9] Similar binding mode was previously observed
in a Cd (II) complex derived from adenine and
isophthalate ligands.[22] A fragment of the framework of
1 is depicted in Figure 4.
wR2 (all data)
Goodness‐of‐fit (all data)
Max. peak/hole
1.682/−0.527
2.2 | Thermogravimetric Analysis
The thermal stability of 1 was investigated using TGA. The
TGA curve shows no weight loss up to 125 °C. Polymer 1
shows a weight loss of ca 6.77% (calculated 6.93%) between
125 and 245 °C (Figure 5). This is due to the loss of six water
molecules coordinated to Mn (II) ions in 1. The dehydrated
framework of 1 is stable up to 300 °C and slowly decom-
poses on further temperature increase.
FIGURE 1 Solid state structure of 1. Color code: Pink Manganese,
grey carbon, red oxygen and blue nitrogen atoms. Hydrogen atoms
and other isophthalate ligands are not shown for clarity.
FIGURE 2 Coordination environment of Mn (II) ions in 1
FIGURE 3 Binding modes of isophthalate anion in 1

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PAL ET AL.
FIGURE 4 A fragment of framework of 1 viewed along crystallographic b axis. Color code: pink manganese, red oxygen, grey carbon and
blue nitrogen atoms.
SCHEME 2 Henry (nitroaldol) reaction between nitromethane
and 4‐nitrobenzaldehyde
The effect of catalyst loading on reaction conversion was
investigated in the Henry reaction in methanol at 70 °C. It
was observed that the conversion was enhanced from 80
to 94% with increasing catalyst loading 1.0 to 5.0 mol%
(Table 2, entries 4–6). However, further rise in catalyst load-
ing decreases the reaction conversion. The reaction was car-
ried out in various solvents to establish the solvent effects. It
FIGURE 5 TGA curve of 1
was found that 1 exhibit highest activity in methanol
(Table 2, entry 4). Aprotic and less polar solvents such as
2.3 | Catalytic Activity and Henry
acetonitrile, tetrahydrofuran, dichloromethane and toluene
Reaction
were found to be not suitable media and the reaction did not
To explore the use of 1 as a heterogeneous catalyst for the
Henry (nitroaldol) reaction, nitromethane was reacted
with various aldehydes. Initial reaction was carried out
using 4‐nitrobenzaldehyde and nitromethane in the pres-
ence of 1 mol% of polymer (catalyst) 1 at 70 °C for 18 h
(Scheme 2). It was observed that the reaction could offer
80% conversion of 4‐nitrobenzaldehyde under these reac-
tion conditions. With this initial result, we screened sev-
eral reaction parameters such as catalyst loading,
solvent, temperature and reaction time (Table 2).
proceed in those solvents (Table 2, entries 9–12). These
results indicate the plausible role of polar and protic sol-
vents in the proton transfer phenomena of the Henry
reaction.[20c] The conversion of 4‐nitrobenzaldehyde
increased from 0 to 94% with increase in temperature from
25 to 70 °C (Table 2, entries 4 and 13). However, the yield
decreased with increasing temperature beyond 70 °C. To
explore the optimum reaction time for the highest yield,
the yield of the reaction was monitored with respect to time.
Initially, the rate of conversion of 4‐nitrobenzaldehyde was

PAL ET AL.
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TABLE 2 Henry reaction of 4‐nitrobenzaldehyde with nitromethane catalysed by 1a
Catalyst amount
Entry
Catalyst
Time (h)
(mol%)
Temp. (°C)
Solvent
Yield (%)
1
1
6
9
5
5
70
70
70
70
70
70
70
70
70
70
70
70
25
40
55
70
70
70
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
CH3CN
THF
63
70
78
94
94
80
82
85
—
—
—
—
—
45
84
—
5
2
1
3
1
12
18
24
18
18
18
18
18
18
18
18
18
18
18
18
18
5
4
1
5
5
1
5
6
1
1
7
1
3
8
1
7
9
1
5
10
11
12
13
14
15
16
17
18
1
5
1
5
Toluene
DCM
1
5
1
5
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
1
5
1
5
Blank
—
5
Adenine
Mn (OAc)2·4H2O
5
92
aReaction conditions: 4‐nitrobenzaldehyde (1.0 mmol), nitromethane (4.0 mmol); yield calculated by 1H NMR spectroscopy.
very high and it resulted 63% conversion in the first 6 h.
Prolonging the time of the reaction, the yield increased
slowly and reached 94% in 18 h (Table 2, entry 4). No
improvement in yield was observed when the reaction was
performed for 24 h (Table 2, entry 5; and Figure S3 in the
supporting information). A blank experiment was also per-
formed using 4‐nitrobenzaldehyde and nitromethane as the
substrates in the absence of 1 at 70 °C in methanol. No
detectable product was obtained in the blank run even after
a reaction time of 18 h (Table 2, entry 16). Only 5% conver-
sion occurred when the reaction was performed in the pres-
ence of adenine (Table 2, entry 17). However, 92%
conversion was achieved when manganese acetate
tetrahydrate was used as a catalyst in a homogenous reac-
tion condition (Table 2, entry 18). Therefore, the Henry
reaction of nitromethane with various aldehydes was per-
formed under the optimum reaction condition: nitrometh-
ane (4.0 mmol), aldehyde (1.0 mmol) and polymer 1
(5 mol%) in MeOH at 70 °C for 18 h.
influenced by the presence of electron‐withdrawing and
electron‐donating groups attached to aromatic aldehydes.
When an electron‐withdrawing group is attached to aro-
matic aldehyde, it enhances the electrophilicity of carbonyl
group and thus favours the reaction compared with aro-
matic benzaldehydes with an attached electron‐donating
group.[20c,e] It can also be noted that electronic effects are
more prominent for para‐substituted benzaldehydes. For
example, p‐nitro‐ and p‐methylbenzaldehydes exhibit
highest and lowest conversion, respectively, among all
substituted benzaldehydes (Table 3, entries 2 and 6). There-
fore, the nature of the substrates plays crucial role in deter-
mining the yield of the reaction.
We compared the catalytic efficiency of 1 with those
of other reported MOFs/CPs utilized for the Henry reac-
tion using 4‐nitrobenzaldehyde as a model compound
(Table 4). The conversion is comparable with that for
other MOFs/CPs and maximum with 1 being the first
Mn (II)‐containing CP used for such reactions.
The catalyst was separated from the solution by filtra-
tion. The filtrate was evaporated to obtain the crude product,
which was analysed using H NMR spectroscopy (Figures
2.4 | Heterogeneity Test of Reaction
1
S4–S10 in the supporting information). It proved that poly-
mer 1 is highly active towards several mono‐substituted aro-
matic aldehydes and gives different β‐nitroalkanols
(Table 3). It is observed that the conversion is highly
To further confirm whether the catalytic reaction pro-
ceeds via 1 or any possible leached Mn (II) ions from 1
in solution, the Henry reaction was performed. We car-
ried out a controlled experiment with 1 until a

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PAL ET AL.
TABLE 3 Henry reaction of various aldehydes with nitromethane promoted by catalyst 1 in methanola
Entry
Compound
Product
Yield (%)
TONb
TOF (h−1 c
)
1
93
18.6
1.03
0.97
0.81
0.72
2
3
4
94
73
65
17.6
14.6
13.0
5
6
7
49
19
45
9.8
3.8
9.0
0.54
0.21
0.50
aReaction conditions: 5.0 mol% of polymer 1, aldehyde (1.0 mmol), nitromethane (4.0 mmol) and methanol (5 ml).
bNumber of moles of β‐nitroalkanol per mole of catalyst.
cNumber of moles of β‐nitroalkanol per mole of catalyst per hour.
TABLE 4 Comparison of catalytic activities of reported MOFs/CPs as heterogeneous catalysts for Henry reaction
Entry
Catalyst
Solvent/temperature/time
Aldehyde
Yield (%)
Ref.
1
1
MeOH/70 °C/18 h
MeOH/70 °C/24 h
Solvent free/70 °C/36 h
MeOH/70 °C/48 h
Solvent free/70 °C/72 h
Solvent free/60 °C/120 h
MeOH/70 °C/48 h
Water/75 °C/40 h
Water/75 °C/40 h
MeOH/r.t./72 h
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
94
95
78
98
15
34
97
98
94
100
96
This work
[23]
2
[Cu4 (HLala) (H2O)4 (MeO)4]n
2
[24]
3
[Cu3 (pdtc)(La)2(H2O)3]·2DMF·10H2O
[Zn2 (Lb)2(4,4′‐bipyridine)2(H2O)(DMF)]n
[Zn3 (TCPB)2·2H2O]·2H2O·4DMF
[Zn (3,3′‐TPDC) (DABCO)]·DMF·2H2O
[Zn (Lc)(H2O)2]n
[20c]
[24]
4
5
[25]
6
[20e]
[20b]
[20b]
[20d]
[20a]
7
8
[{Cu (L1)(DMF)}·DMF·H2O]n
9
[Zn (L1)(H2O)]n
10
11
[{Cd2 (L‐glu)2(bpe)3 (H2O)}⋅2H2O]
[Sm (L1)2]n·1n (HCONH2)H·2n (HCONH2)
Water/70 °C/36 h
transitional yield (ca 70%) was found (9 h) and then
removed the catalyst by filtration and kept the solution
(without catalyst) under the same reaction conditions
for an additional 9 h (total of 18 h). The yield of the prod-
uct did not further increase significantly after the removal
of the catalyst. These results indicate the heterogeneous
nature of the catalyst. Additionally the amount of manga-
nese was determined from the solution after the removal
of catalyst using inductively coupled plasma atomic emis-
sion spectroscopy (ICP‐AES). There was no Mn (II) pres-
ent in the filtrate after the nitroaldol reaction, thus ruling
out any notable leaching of the catalyst.
2.5 | Recyclability of 1
In order to investigate possible reusability of 1 in
nitroaldol reaction, recyclability experiment was
a
performed under optimized reaction conditions using
4‐nitrobenzaldehyde and nitromethane. After each cycle,
the catalyst was collected, washed with methanol, dried
in vacuum and used in a subsequent reaction without
further modification. It is observed that catalytic activity
of 1 gradually decreases upon reuse and conversions of
4‐nitrobenzaldehyde in five consecutive reactions are 94,
82, 78, 76 and 68% (Figure 6). There are two possible

PAL ET AL.
7 of 9
reasons for this. Firstly, polymer 1 is not stable in the
reaction mixture, which is excluded by the heterogeneity
test of the reaction. Secondly, active metal sites of 1 are
blocked after each cycle, thus resulting in a perturbation
in the structure of 1. In order to prove that, FT‐IR spectra
and powder XRD patterns of fresh catalyst and catalyst
after five recycles were recorded. Significant changes
were found in both FT‐IR spectra (Figure S11 in the
supporting information) and powder XRD patterns
(Figure 7), thus confirming a structural change of 1 dur-
ing the reaction.
2.6 | Plausible Mechanism
FIGURE 7 Powder XRD patterns of 1.
A plausible mechanism for the nitroaldol reaction of
nitromethane and benzaldehydes in the presence of 1 is
proposed, as depicted in Scheme 3. Similar to other
homogeneous or heterogeneous catalytic systems con-
taining transition metal ions (Cu (II), Zn (II) and Cd
26]
(II)),[19b,
both aldehyde and nitromethane are acti-
vated initially by Mn (II) ions ((b), Scheme 3). This fur-
ther enhances the electrophilic character of
benzaldehyde and acidity of nitromethane. In the next
step, reactive nitronate species is generated through
deprotonation of activated acidic nitromethane. This pro-
cess may further be stimulated by the presence of basic
adenine molecules, coordinated to Mn (II) ions in 1. Sub-
sequently, formation of C─C bond takes place via nucle-
ophilic attack of nitronate ion to coordinated
benzaldehyde ((c), Scheme 3). Finally, another molecule
of benzaldehyde ligates to Mn (II) and corresponding β‐
nitroalkanol is released from it, thus completing the cata-
lytic cycle.
SCHEME 3 Proposed catalytic cycle for Henry reaction catalysed
by 1
3 | CONCLUSIONS
We have successfully synthesized a Mn(II)‐containing
three‐dimensional CP (1) from affordable chemicals such
as isophthalic acid and adenine. The solid‐state structure
of 1 showed that it possesses a three‐dimensional structure
with Mn6 secondary building units. Polymer 1 exhibited
significant catalytic activity in the Henry reaction of vari-
ous aldehydes with nitromethane. Polymer 1 can also be
employed in important organic transformations demand-
ing both acidic and basic sites for activation of substrates.
4 | EXPERIMENTAL
Isopthalic acid (Loba chemie, India), adenine (SRL, India),
Mn(OAc)2⋅4H2O (Merck, India), benzaldehyde, 2‐
nitrobenzaldehyde, 4‐chlorobenzaldehyde (Sigma Aldrich,
FIGURE 6 β‐Nitroalkanol yield in five consecutive reaction
cycles employing 1 as catalyst

8 of 9
PAL ET AL.
India), 4‐bromobenzaldehyde, 4‐fluorobenzaldehyde, 4‐
nitrobenzaldehyde and 4‐methylbenzaldehyde (Alfa
Aesar, India) were received and used without further puri-
fication unless otherwise noted. All solvents were distilled
prior to use. The NMR solvents CDCl3 and DMSO were
purchased from SRL, India. 1H NMR spectra were
recorded with a Bruker AVANCE II‐400 spectrometer
and a Varian (Mercury Plus) 400 NMR spectrometer. A
Cary 600 series FT‐IR spectrometer (Agilent Technology)
was used for FT‐IR measurements. Powder XRD patterns
were recorded using a CuKα radiation source with a Bruker
D2 Phaser X‐ray diffractometer. TGA was performed with
an SDT Q600 (TA Instrument) at a scan rate of 10 °C min
−1 under N2 flow at a rate of 100 ml min−1. ICP‐AES anal-
ysis was carried out with an ARCOS simultaneous ICP
spectrometer (SPECTRO Analytical Instruments GmbH,
Germany).
structure was obtained by direct methods (SIR92)[27]
and refined on F 2 by full‐matrix least‐squares methods
using SHELXL‐2013.[28] Non‐hydrogen atoms were
anisotropically refined. Hydrogen atoms were included
in the refinement on calculated positions riding on
their carrier atoms. The function minimized was
[∑w ( Fo − F c ) ] (w = 1/[σ2( Fo2) + (aP)2 + bP]),
2
2 2
where P = (Max( Fo2, 0) + 2 F c )/3 with σ2(F o
from counting statistics. The functions R1 and wR2 were
)
2
2
(σ|| Fo| − | Fc||)/σ|F o| and [σw(Fo − Fc ) /σ(wFo )]1/2
,
2
2 2
4
respectively. Crystallographic data (excluding structure
factors) for the structures reported in this paper have
been deposited at the Cambridge Crystallographic Data
Centre as supplementary publication no. CCDC
1552157. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +(44) 1223 336 033;
e‐mail: deposit@ccdc. cam.ac.uk).
4.1 | Preparation of 1
ACKNOWLEDGEMENTS
A mixture of isophthalic acid (0.033 g, 0.2 mmol), adenine
(0.027 g, 0.2 mmol) and Mn (OAc)2⋅4H2O (0.049 g,
0.2 mmol) was dissolved in a mixture of ethanol (7 ml)
and water (3 ml) at room temperature. The mixture was
sealed in a Teflon‐lined autoclave of 30 ml capacity. The
autoclave was heated to 80 °C, held for 48 h and cooled
to room temperature. Colourless needle‐shaped single
crystals of 1 were collected, washed with ethanol and
dried in vacuum. Yield: 0.217 g, 70% (with respect to
Mn (OAc)2⋅4H2O). FT‐IR (ATR, cm−1): 3420(w),
3356(w), 3244(w), 2360(m), 1667(w), 1604(s), 1558(s),
1377(s), 737(m), 713(m), 424(w).
This work was financially supported by the Science and
Engineering Research Board (SERB), DST, India (order
no. SB/EMEQ‐013/2014, dated 17/06/2014). We thank
SAIF, Punjab University and IIT Bombay for providing
analytical facilities.
ORCID
Hari Pada Nayek http://orcid.org/0000-0003-4247-547X
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A
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SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of the
article.
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This includes FT‐IR spectrum of 1, power XRD pattern of
1, plot of β‐nitroalkanol yield versus time for the Henry
reaction of 4‐nitrobenzaldehyde and nitromethane with
1
1, calculation of yield, H NMR spectra of product of
Henry reaction between various aromatic aldehydes and
nitromethane, FT‐IR spectra of 1 in five consecutive reac-
tion cycles, selected bond lengths for 1.
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How to cite this article: Pal S, Maiti S, Nayek
HP. A three‐dimensional (3D) manganese (II)
coordination polymer: Synthesis, structure
and catalytic activities. Appl Organometal Chem.
2018;e4447. https://doi.org/10.1002/aoc.4447
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