FULL PAPER
First Manganese (II) Bio-MOF: An Effective Heterogeneous
Catalyst for Henry Reaction
Souvik Pal,[a] Sudip Maiti[a] and Hari Pada Nayek*[a]
Abstract: A new Mn(II) containing bio-MOF, [Mn6(Ipa)6(ad)·6H2O] (1)
(where Ipa = isophthale ligand and ad = adenine) have been
synthesized by reacting hydrated manganese nitrate with isophthalic
acid and adenine under solvothermal reaction condition. The MOF
has been characterized by single crystal X-ray diffraction analysis and
other analytical techniques such as FT-IR spectroscopy, elemental
analyses and power X-ray diffraction. The solid state structure of 1
confirms the formation of a three dimensional (3D) framework
structure based on Mn6 secondary building units (SBUs). Phase purity
of bulk material of 1 and its thermal stability has been investigated.
Compound 1 has been evaluated for its performance as
heterogeneous catalyst for the Henry (nitroaldol) reaction of
nitromethane with several aldehydes. The results show that catalyst
1 acts as an excellent heterogeneous catalyst with excellent
conversions. The recyclability test of 1 and heterogeneity of the
reaction have also been performed. A plausible mechanism for such
reaction has been proposed. To the best of our knowledge, compound
1 represents first example of a Mn(II) containing bio-MOF as well as
a first example of a Mn(II) containing MOF that has been employed
for Henry reaction.
Introduction
Presently, metal–organic frameworks (MOFs) are of immense
interests among chemists, physicists and material scientists.
These highly demanding MOFs are synthesized by connecting
inorganic metal nodes with organic linkers. Owing to their stable
and tunable porous structures, they have emerged as one of the
promising functional materials in catalysis,[1] chemical
separations,[2] gas storage,[2c, 3] molecular sensing,[4] contaminant
removal,[5] ion exchange[3b, 6] and drug delivery system.[7] A large
number of interesting and diverse polydentate ligands have been
synthesized and employed in the synthesis of MOFs. Now a days,
biomolecules such as nucleobases, amino acids and peptides are
preferred than synthetic ligands in the preparation of MOFs. [8]
These biomolecules are inexpensive, nontoxic and capable of
forming hydrogen bond, induce chirality as well as provide
multiple donor sites.[9] Such biomolecules containing MOFs are
recognized as bio-MOFs. Interestingly, nucleobases are of prime
interests among biomolecules for the construction of bio-MOFs.
They could offer a rigid and porous framework. In contrary, other
biomolecules (peptides, proteins and amino acids) would result
[a] M.Sc. S. Pal, M.Sc. S. Maiti, Dr. H. P. Nayek
Department of Applied Chemistry
Indian Institute of Technology (ISM) Dhanbad
Dhanbad-826004, Jharkhand, India
E-mail: hpnayek@yahoo.com
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
For internal use, please do not delete. Submitted_Manuscript
flexible, interpenetrated and non-porous frameworks which inhibit
their applications. Among nucleobases, adenine is more attractive
building units 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 form hydrogen bond and thus it
leads to new framework structures.[9-11]
Scheme 1. Five potential donor sites of adenine ligand.
Its rich coordination ability and hydrogen bonding capabilities
resulted in the formation of diverse framework structures with
applications mainly in gas adsorption, drug
encapsulation/delivery.[12] For instance, bio-MOF-1 exhibited
exceptional gas adsorption properties and suited for loading and
controlled release of cationic drug, procainamide HCl. [13] Even,
anticancer drug methotrexate (MTX) was successfully loaded into
two bio-MOFs (ZJU-64 and ZJU-64-CH3) and delivered in specific
cancer cell to kill the cell with low side effect. [14] In addition, these
adenine based bio-MOFs are also useful for adsorption and/or
separation of hydrocarbons, gases and organic dyes. [15] Sensing
abilities of bio-MOFs have recently been investigated against
explosives (nitro aromatic compounds), volatile organic amines
and toxic metal (Hg).[16] Many MOFs were already proven to be
an effective heterogeneous catalyst for organic conversion.
Despite the existence of Lewis acid sites (metal ions) and Lewis
basic sites (nitrogen atoms on adenine) in bio-MOF, catalytic
abilities of bio-MOF towards organic transformations in
heterogeneous reaction condition are scarcely investigated. One
could witnessed a single report where a Zn(II) containing bio-MOF
was tested for its catalytic activities only in Knoevenagel
condensation reaction.[17] Based on the previous discussion, we
were interested to develop a new bio-MOF and investigate its
catalytically activity towards organic reaction (Henry reaction).
The Henry or nitroaldol reaction is an important C−C bond
formation technique in progressive organic chemistry. Generally,
the reaction was performed by various basic catalysts, such as
alkoxide, alkali metal hydroxides or amines etc.[18] Many transition
metal complexes have also used as homogeneous catalyst for
such conversion.[19] Occasionally, one could observe a
heterogeneous catalyst for such transformation. Recently, few
transition metal and lanthanide containing MOFs were introduced
as heterogeneous catalysts for nitroaldol reaction. [19b, 20] As bio-
MOFs contain multiple Lewis acid and basic sites, we presumed
that bio-MOFs could exhibit significant catalytic activity towards
FULL PAPER
Henry (nitroaldol) reaction. Therefore, we report herein on the
synthesis and characterization of a new adenine based Mn(II)-
bio-MOF of formula [Mn6(Ipa)6(ad)·6H2O] (1), where Ipa =
isophthale and ad = adenine ligands. Detailed experimental
process and characterizations of 1 have been discussed. Solid
state structures of 1 have been determined by single crystal X-ray
diffraction analysis. In addition, we have explored its catalytic
activity towards Henry reaction of nitromethane with various
aldehydes. The stability, recyclability and heterogeneity of 1 were
established. To the best of our knowledge, this is the first report
of any bio-MOF investigated for its catalytic activity towards Henry
reaction. In addition to that 1 represents a first example of a Mn(II)
containing bio-MOF.
coordinated water molecules. 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 observations for Mn 3 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
carboxylate moieties of Ipa exhibit bidentate and tridentate
coordination fashion to assemble Mn(II) ions as displayed in figure

Results and Discussion

Synthesis and Structure

The formation of [Mn6(Ipa)6(ad)·6H2O] (1) was achieved by
solvothermal reaction of isophthalic acid (H2Ipa) and adenine (ad)
with Mn(OAc)2·4H2O in EtOH-H2O. The compound 1 was
appeared as white crystalline solid. The FT-IR spectrum of 1
3.
shows a strong absorption band at 1667 cm-1 because of
asymmetric stretching vibration of coordinated carboxylate group Figure 1. Solid state structure of 1. Color code: Pink Manganese, grey carbon,
(figure S1 in the supporting information). A broad band red oxygen and blue nitrogen atoms. Hydrogen atoms and other isophthalate
approximately at 3400 cm-1 is assigned to O-H stretching ligands are not shown for clarity.
vibrations and thus it confirms the presence of water molecules
(coordinated) in 1. The phase purity and reproducibility of the
bulky samples of were established by powder X-ray diffraction
(figure S2 in the supporting information). The composition of the
as-synthesized 1 was determined by single crystal X-ray
diffraction analysis, elemental analysis and TGA. Detailed
experimental procedures and data are given in the experimental
section.
The result of single crystal X-ray structural analysis reveals that 1
Figure 2. Coordination environment of Mn(II) ions in 1.
crystallizes in orthorhombic centrosymmetric space group Pmn21.
Detailed single crystal data and refinement parameters are
provided in table 1. Complex 1 reveals a three dimensional (3D)
framework structure based on Mn6 secondary building units Interestingly, adenine adopts bidentate coordination modes
(SBUs). Each Mn6 SBU is formed from two Mn3 units assembled (figure 1) and bonded to two Mn(II) ions despite its various
by an adenine molecule (figure 1). Compound 1 consists of six coordination mode discussed elsewhere. [9] Similar binding mode
Mn(II) ions, six isophthalate ligands, one bridging adenine was previously observed in a Cd(II) complexes derived from
molecule and six coordinated water molecules. There are three adenine and isophthalate ligands. [22] A fragment of framework of
crystallographically independent Mn(II) ions in an asymmetric unit 1 is depicted in figure 4.
of 1. The coordination 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 (Ipa),
one nitrogen atom (N3) of a neutral adenine molecule and one
oxygen atom O(13) of an aqua ligand. The central Mn(II) ion
(Mn2) is occupying the centre of a distorted octahedron and
coordinated by six oxygen atoms (O1, O4, O9, O5, O7 and O12)
of the carboxylates 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, O7, O8 and O11) of bridging
Figure 3. Binding modes of isophthalate anion (IPA) in 1.
isophthalate ligands and two oxygen atoms (O14 and O15) of two

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FULL PAPER

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.

Table 1. Single crystal data and structure refinement parameters for 1. dehydrated framework of 1 is stable up to 300 °C and slowly
decomposes on further temperature increase.
Compound 1
Formula C53H40Mn6N5O30
Formula weight 1556.54
Temperature (K) 100(2)
Crystal system orthorhombic
Space group Pmn21
a(Å) 22.0677(11)
b(Å) 7.7758(4)
c(Å) 17.6217(10)
β (º) 90
Z 2
dcalc (g cm-3) 1.710
μ(mm-1) 1.311
F(000) 1566
Total Reflections 19521
Unique Reflections 5579
Observed data [I > 2 σ (I)] 4930
No. of parameters 413
R(int) 0.0474
R1[I > 2 σ (I)] 0.0546
wR2 (all data) 0.1610
GooF (all data) 1.118 Figure 5. Thermogravimetric curve of 1.
Max. peak/hole 1.682/-0.527

Thermogravimetric Analysis Catalytic Activity and Henry Reaction

Thermal stability of 1 was tested by thermogravimetric (TG)
analysis. The TG curve shows no weight loss up to 125 °C.
Compound 1 shows a weight loss of ~ 6.77 % (calculated 6.93%)
between 125 οC and 245 οC (figure 5). This is due to the loss of
six water molecules coordinated to Mn(II) ions in 1. The
To test the use of 1 as a heterogeneous catalyst for Henry
(nitroaldol) reaction, nitromethane was reacted with different
aldehydes. Initial reaction was carried out using 4-
nitrobenzaldehyde and nitromethane in the presence of 1 mol%
of catalyst 1 at 70 oC for 18 hours (Scheme 2). It was observed

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FULL PAPER
that the reaction could offer 80% conversion of 4- Prolonging the time of the reaction, the yield increased slowly and
nitrobenzaldehyde under this reaction condition. With this initial reached to 94% in 18 hours (entry 4, table 2). No improvement in
result, we have screened several reaction parameters such as yield was observed when the reaction was performed for 24 hours
catalyst loading, solvents, temperature and reaction time (table 2). (entry 5, table 2 and figure S3 in the supporting information). A
blank test was also performed using 4-nitrobenzaldehyde and
nitromethane as the substrates in the absence of catalyst 1 at 70
˚C in methanol. No detectable product was obtained in the blank
test even after a reaction time of 18 hours. Therefore, the Henry
reaction of nitromethane with various aldehydes was performed
at the optimum reaction condition: nitromethane (4.0 mmol),
aldehyde (1.0 mmol), and catalyst 1 (5 mol%) in MeOH at 70 ˚C
for 18 hours. The catalyst was separated from the solution by
filtration. The filtrate was evaporated to obtain the crude product,
which was analyzed by 1H NMR spectroscopy (figure S4-S10 in
Scheme 2. Henry (nitroaldol) reaction between nitromethane and 4- the supporting information). It proved that catalyst 1 is highly
nitrobenzaldehyde
active towards several mono-substituted aromatic aldehydes and
gives different β –nitroalkanols (table 3). It observed that the
conversion is highly influenced by the presence of electron-
Table 2. Henry reaction of 4-nitrobenzaldehyde with nitromethane catalyzed by
withdrawing and electron-donating groups attached to aromatic
1.
aldehydes. When an electron-withdrawing group is attached to
Entry Time Catalyst T (°C) Solvent Yield aromatic aldehyde, it enhances the electrophilicity of carbonyl
(h) (mol %) (%) group and thus favors the reaction than aromatic benzaldehydes
1 6 5 70 MeOH 63
2 9 5 70 MeOH 70
with an attached electron-donating group.[20c, e] It can also be
3 12 5 70 MeOH 78 noted that electronic effects are more prominent for para-
4 18 5 70 MeOH 94 substituted benzaldehydes. For example, p-nitro and p-
5 24 5 70 MeOH 94
methylbenzaldehydes exhibit highest and lowest conversion
6 18 1 70 MeOH 80
7 18 3 70 MeOH 82 respectively among all substituted benzaldehydes (entries 2 and
8 18 7 70 MeOH 85 6, table 3). Therefore, the nature of the substrates plays crucial
9 18 5 70 CH3CN 0
role in determining the yield of the reaction. We have compared
10 18 5 70 THF 0
11 18 5 70 Toluene 0 the catalytic efficiency of 1 with other reported MOFs utilized for
12 18 5 70 DCM 0 henry reaction using 4-nitrobenzaldehyde as model compound
13 18 5 25 MeOH 0 (table 4). The conversion is comparable with other MOFs and
14 18 5 40 MeOH 45
15 18 5 55 MeOH 84 maximum with 1 being the first Mn(II) containing MOF used for
such reactions.
Reaction conditions: 4-nitrobenzaldehyde (1.0 mmol), nitromethane (4.0 mmol),
and methanol (5.0 mL). Yield calculated by 1H-NMR spectroscopy Recyclibility Test of 1
In order to investigate possible reusability of 1 in nitroaldol
The effect of catalyst loading on reaction conversion was reaction, a recyclability experiment was performed under
investigated in Henry reaction in methanol at 70 oC. It was optimized reaction condition using 4-nitrobenzaldehyde and
observed that the conversion was enhanced from 80 to 94% with nitromethane. After each cycle, the catalyst was collected,
increasing the catalyst loading 1.0 to 5.0 mol% respectively washed with methanol, dried in vacuum and used in consecutive
(entries 4-6, table 2). However, further rise in catalyst loading reaction without further modification. It is observed that catalytic
decreases the reaction conversion. The reaction was carried out activity of 1 gradually decreases upon reuse and conversion of 4-
in different solvents to establish the solvent effects. It was found nitrobenzaldehyde in five consecutive reactions are 94, 82, 78, 76
that the catalyst 1 exhibit highest activity in methanol (entry 4, and 68 % (figure 6). The FT-IR spectra and powder XRD patterns
table 2). Aprotic and less polar solvents such as acetonitrile, of fresh catalyst and five-time reused catalyst were recorded. No
tetrahydrofuran, dichloromethane and toluene were found to be remarkable changes were found in the FT-IR spectra suggesting
not suitable media and the reaction did not proceed in those the integrity of the polymeric structure of the catalyst remain
solvents (entries 9-12, table 2). These results indicate the constant after the reactions (figure S11 in the supporting
plausible role of polar and protic solvents in the proton transfer information). In addition, powder XRD patterns of 1 do not change
phenomena of the Henry reaction.[20c] The conversion of 4- and thus the catalyst 1 retains its crystallinity even after five
nitrobenzaldehyde increased from 0 to 94% with increase in reaction cycles (figure 7).
temperature from 25 °C to 70 °C (entries 4 and 13, table 2).
However, the yield decreased with increasing temperature Heterogeneity Test of the Reaction
beyond 70 °C. To explore the optimum time consuming for the To further confirm whether the catalytic reaction proceed by 1 or
highest yield, the yield of the reaction was monitored with respect any possible leached Mn(II) ions from 1 in solution, henry reaction
to time. Initially, the rate of conversion of 4-nitrobenzaldehyde was was performed. We carried out a controlled test with bio-MOF
very high and it resulted 63% conversion in first 6 hours.
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FULL PAPER
catalyst 1 until a transitional yield (ca. 70%) was found (9 hours) Additionally the amount of manganese was determined from the
and then removed the catalyst by filtration and kept the solution solution after the removal of catalyst by ICP-AES analysis. There
(without catalyst) under the same reaction condition for additional was no Mn(II) present in the filtrate after the nitro-aldol reaction,
9 hours (total 18 hours). The yield of the product did not further thus ruling out any notable leaching of the bio-MOF catalyst.
increase significantly after the removal of the bio-MOF catalyst.
These results indicate the heterogeneous nature of the catalyst.

Table 3. Henry reaction of various aldehydes with nitromethane promoted by catalyst 1 in methanol.
Entry Compounds Product Yield (%) TON TOF (h-1)

1 OH 93 18.6 1.03
CHO
NO2
2 94 17.6 0.97

3 OH 73 14.6 0.81
F CHO F
NO2
4 OH 65 13.0 0.72
CHO
NO2
NO2 NO2
5 OH 49 9.8 0.54
Br CHO Br
NO2
6 OH 19 3.8 0.21
H3C CHO H3C
NO2

7 OH 45 9.0 0.50
Cl CHO Cl
NO2

Table 4. Comparison of catalytic activities of reported MOFs as heterogeneous catalysts for the Henry reaction.
Entry Catalyst Solvent/temp/time Aldehyde Yield (%) Ref

1 1 MeOH/70˚C/18 h 4-nitrobenzaldehyde 94 This work

2 [Cu4(HLala) 2(H2O)4 (MeO)4]n MeOH/70˚C/24 h 4-nitrobenzaldehyde 95 [23]

3 [Cu3(pdtc)(La)2(H2O)3]·2DMF·10H2O Solvent free/70˚C/36 h 4-nitrobenzaldehyde 78 [24]

4 [Zn2(Lb)2(4,4′-bipyridine)2(H2O)(DMF)]n MeOH/70˚C/48 h 4-nitrobenzaldehyde 98 [20c]

5 [Zn3(TCPB)2·2H2O]·2H2O·4DMF solvent free/70˚C/72 h 4-nitrobenzaldehyde 15 [24]

6 [Zn(3,3′-TPDC) (DABCO)]·DMF·2H2O solvent free/60˚ C/120 h 4-nitrobenzaldehyde 34 [25]

7 [Zn(Lc)(H2O)2]n MeOH/70˚C/48 h 4-nitrobenzaldehyde 97 [20e]

8 [{Cu(L1)(DMF)}·DMF·H2O]n water/75 ˚C/40 h 4-nitrobenzaldehyde 98 [20b]

9 [Zn(L1)(H2O)]n water/75 ˚C/40 h 4-nitrobenzaldehyde 94 [20b]

[20d]
10 [{Cd2(L-glu)2(bpe)3 (H2O)}.2H2O] MeOH/rt/72h 4-nitrobenzaldehyde 100

11 [Sm(L1)2]n·1n(HCONH2)H·2n(HCONH2) water/70 ˚C/36 h 4-nitrobenzaldehyde 96 [20a]

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Figure 6. β-nitroalkanol yield in five consecutive reaction cycles employing 1 as
catalyst.
Figure 5. Powder XRD patterns of 1.
Plausible Mechanism
A plausible mechanism for the nitro-aldol reaction of
nitromethane and benzaldehydes in the presence of 1 is proposed
and depicted in scheme 3. Similar to other homogenous or
heterogeneous catalytic system (MOFs) containing transition
metal ions (Cu(II), Zn(II) and Cd(II)), [19b, 26] both aldehyde and
nitromethane are activated initially by Mn(II) ions (b, scheme 3).
Scheme 3. Proposed catalytic cycle for the Henry reaction catalyzed by 1.
For internal use, please do not delete. Submitted_Manuscript
This further enhances electrophilic character of benzaldehyde
and acidity of nitromethane. In the next step, reactive nitronate
species is generated through deprotonation of activated acidic
nitromethane. This process may further be stimulated by the
presence of basic adenine molecules, coordinated to Mn(II) ions
in 1. Subsequently, formation of C-C bond takes place via
nucleophilic 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 it completes the catalytic cycle.
Conclusions
We have successfully synthesized a Mn(II) containing bio-MOF
(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.
The MOF (1) exhibit significant catalytic activity in Henry reaction
of various aldehydes with nitromethane. The MOF is highly stable
even after its catalytic reaction and can be reused in a number of
cycles with a minimal loss of catalytic activity. The catalyst 1 can
also be employed in important organic transformations
demanding both acidic and basic sites for activation of substrates.
Experimental Section
Isopthalic acid (Loba chemie, India), adenine (SRL, India),
Mn(OAc)2·4H2O (Merck, India), benzaldehyde, 2-nitrobenzaldehyde, 4-
chlorobenzaldehyde (Sigma Aldrich, India), 4-bromobenzaldehyde, 4-
flurobenzaldehyde, 4-nitrobenzaldehyde, 4-methylbenzaldehyde (Alfa
Aesar, India) were received and used without further purification unless
otherwise noted. All solvents were distilled prior to use. The NMR solvent
CDCl3 and DMSO were purchased from SRL, India. 1H NMR spectra were
recorded on a BRUKER AVANCE II-400 spectrometer and Varian (model:
Mercury plus) 400 NMR spectrometer. Cary 600 series FT-IR (Agilent
Technology) was used for FT-IR measurement. Powder X-ray diffraction
(PXRD) patterns were recorded using a CuKα radiation source on a Bruker
D2 Phaser X-ray diffractometer. Elemental analysis was performed on a
Thermo Scientific (FLASH 2000) CHN Elemental Analyser System. TG
analysis was performed on a SDT Q600 (TA instrument) at scan rate of 10
ο
C/min under N2 flow of a rate of 100 mL/min. Simultaneous DTA–TGA
instrument (SDT). ICP-AES analysis was carried out in ARCOS,
Simultaneous ICP Spectrometer (SPECTRO Analytical Instruments
GmbH, Germany).
Preparation of [Mn6(Ipa)6(ad)·6H2O] (1)
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) were dissolved in a
mixture of EtOH (7 mL) and H2O (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 hours and cooled to a room temperature.
Colorless needle shaped single crystals of 1 were collected, washed with
ethanol and dried in vacuum. Yield: 0.036 g, 70% (with respect to
Mn(OAc)2·4H2O). Anal. Calcd for C53H40Mn6N5O30 (%): C, 40.90; H, 2.59;
N, 4.50; Found: C, 40.53; H, 2.66; N, 4.17. 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).
FULL PAPER
General Procedure for Henry Reaction Catalyzed by 1
A mixture of aldehyde (1.0 mmol), nitromethane (4.0 mmol) and catalyst
(5 mol%) in 5 mL methanol contained in a 10 mL round bottom flask was
stirred at 70˚C for 18 hrs. The solution was filtered to remove the catalyst.
The crude product was collected after the evaporation of the solvent. The
product was identified by 1H NMR. The yield of the reaction is calculated
based on the relative amount of unreacted aldehyde and β-nitroalkanol
present in the crude product. Detailed calculation of yield is provided in the
supporting information.
X-Ray Crystallography
The data of 1 collected on a XtaLAB SuperNova (Rigaku oxford diffraction)
diffractometer equipped with EosS2 CCD detector and graphite-
monochromatic Mo-Kα (0.71073 Å) radiation. The structure was solved by
direct methods (SIR92)[27] and refined on F2 by full-matrix least-squares
methods using SHELXL-2013.[28] Non-hydrogen atoms were
anisotropically refined. H atoms were included in the refinement on
calculated positions riding on their carrier atoms. The function minimized
was [w(Fo2 - Fc2)2] (w = 1/[ϭ2(Fo2) + (aP)2 + bP]), where P = (Max(Fo2,0) +
2Fc2)/3 with ϭ2(Fo2) from counting statistics. The function R1 and wR2 were
(ϭ||Fo|-|Fc||)/ϭ|Fo| and [ϭw(Fo2-Fc2)2/ϭ(wFo4)]1/2, respectively.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited in the Cambridge
Crystallographic Data Centre as a supplementary publication no. CCDC
1552157. Copies of the data can be obtained free of charge on application
to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: + (44)1223-336-
033; email: deposit@ccdc.cam.ac.uk).
Supporting Information
FT-IR spectrum of 1, power XRD pattern of 1, plot of β-nitroalkanol yield
vs. time for the Henry reaction of 4-nitrobenzaldehyde and nitromethane
with 1, calculation of yield, 1H NMR spectra of product of Henry reaction
between various aromatic aldehydes and nitromethane, FT-IR spectra of
1 in five consecutive reaction cycles, Selected bond lengths (Å) for 1.
Acknowledgements
Acknowledgements Text. This work was financially supported by
the Science and Engineering Research Board (SERB), India
(Order No. SB/EMEQ-013/2014, dated 17/06/2014). We thank
SAIF Punjab University for providing analytical facilities.
Keywords: Adenine • Bio-MOF • Mn-MOF • Heterogeneous
Catalyst • Henry Reaction • Single crystal X-ray Diffraction.
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FULL PAPER
Entry for the Table of Contents

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A new Mn(II) containing bio- S. Pal, S. Maiti and Dr. H. P.
MOF (1) have been Nayek*
synthesized and employed as
a heterogeneous catalyst in Page No. – Page No.
Henry reaction. MOF 1 exhibits
Title
excellent conversions, stability
and recyclability. It also
represents first example of an
Mn(II) containing bio-MOF as
well as a first example of an
Mn(II) containing MOF that has
been employed for Henry
reaction.

For internal use, please do not delete. Submitted_Manuscript