2D Ferromagnetic sheet of antiferromagnetic trimeric metal cores

Article abstract of DOI:10.1016/j.poly.2013.01.053

A new 2D polymeric Mn-acetate complex [Mn₃(CH ₃COO)₆·2H₂O]_n has been synthesized in a two step reaction process and characterized by single crystal X-ray crystallography, IR and thermal analyses. Structural analysis indicates that complex 1 crystallized in the P2_1/n space group and also shows that syn-syn and μ-oxo bridging of acetate ligands forms antiferromagnetic trimeric metal cores which are further connected by syn-anti and anti-anti bridging of acetates, leading to the formation of a 2D coordination sheet structure. These 2D coordination sheets are further connected by supramolecular hydrogen bonding interactions, leading to the formation of a 3D supramolecular structure. During the 3D supramolecular structure formation, the complex forms both right handed and left handed helical supramolecular chains. A variable temperature magnetic study indicates that complex 1 is antiferromagnetic above 105 K, while at lower temperatures (<105 K) it exhibits long range ferromagnetic-like ordering along with slow magnetization vector relaxation. The relaxation in complex 1 get completely wiped out at 5 K and it exhibits a clear hysteresis loop.

Full text of DOI:10.1016/j.poly.2013.01.053

Polyhedron 53 (2013) 258–263
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
2D Ferromagnetic sheet of antiferromagnetic trimeric metal cores
Susobhan Biswas , Rajat Saha , Ian M. Steele , Kamalendu Dey , Sanjay Kumar a,
a
a
c
b,
⇑
⇑
a
Department of Physics, Jadavpur University, Jadavpur, Kolkata 700032, India
Department of Chemistry, University of Kalyani, Kalyani, Nadia 741235, India
Department of Geophysical Sciences, The University of Chicago, IL 60637, USA
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
A new 2D polymeric Mn–acetate complex [Mn (CH COO) ꢀ2H O] has been synthesized in a two step
3
3
6
2
n
Received 13 September 2012
Accepted 29 January 2013
Available online 10 February 2013
reaction process and characterized by single crystal X-ray crystallography, IR and thermal analyses.
Structural analysis indicates that complex 1 crystallized in the P21/n space group and also shows that
syn–syn and
l-oxo bridging of acetate ligands forms antiferromagnetic trimeric metal cores which are
further connected by syn–anti and anti–anti bridging of acetates, leading to the formation of a 2D coor-
dination sheet structure. These 2D coordination sheets are further connected by supramolecular hydro-
gen bonding interactions, leading to the formation of a 3D supramolecular structure. During the 3D
supramolecular structure formation, the complex forms both right handed and left handed helical supra-
molecular chains. A variable temperature magnetic study indicates that complex 1 is antiferromagnetic
above 105 K, while at lower temperatures (<105 K) it exhibits long range ferromagnetic-like ordering
along with slow magnetization vector relaxation. The relaxation in complex 1 get completely wiped
out at 5 K and it exhibits a clear hysteresis loop.
Keywords:
2
D Coordination polymer
Supramolecular helical structure
Antiferromagnetic trimeric metal core
Ferromagnetic 2D coordination sheet
Ó 2013 Elsevier Ltd. All rights reserved.
1
. Introduction
Much attention has been paid to the design and synthesis of dis-
which a noteworthy extent of structural data is available. In addi-
tion, the famous Mn12–acetate family [43–47] as well as various
polynuclear manganese carboxylate complexes [48–60] show
intriguing single-molecule magnet behavior, which may find pro-
spective application in information storage. Researchers are en-
gaged in the syntheses of ‘extended structures of Mn–acetates
where the acetate ligands act as multifunctional bridges and link
corner sharing octahedral Mn(II) centers, which may favor a strong
long-range super exchange coupling’ [37,61–64].
Up until now, several Mn(II) clusters have been published by
several research groups where the carboxylate groups act as bridg-
ing ligands, but it is interesting to note that only in a few cases do
the carboxylate bridged Mn(II) complexes show ferromagnetism.
There are only scattered examples in literature [65–68]. With this
background, we are going to report the anomalous magnetic
crete polynuclear molecules and molecule-based coordination
polymers of various dimensions, not only to understand the under-
lying principles of crystal engineering but also for developing func-
tional molecular magnetic materials with other potential
applications [1–13]. In this context, the carboxylato group is the
most extensively studied bridging ligand for its versatility in coor-
dination chemistry and a great number of discrete polynuclear and
infinite polymeric metal–carboxylato coordination complexes with
diverse structural motifs and magnetic properties have been re-
ported [14–16]. The different coordination modes adopted by the
carboxylato groups execute the transmission of the magnetic inter-
actions to different degrees, e.g., carboxylate anions can adopt dif-
ferent bridging modes such as syn–syn, anti–anti, syn–anti,
l-oxo
behavior of a Mn–acetate polynuclear complex, {[Mn
3 6
(acetate) ,
and mono-atomic which mediate either ferro- or antiferromag-
netic interactions [12,17–24].
(H O) ] 2H O}n (1), synthesized via two step reaction method. This
complex is a 2D coordination polymer which shows overall
ferromagnetic interactions, while the basic structural unit, the
2
4
2
As a simple carboxylato bridging ligand, the acetate anion
ꢁ
(
OAc ) has been found to form various metal–acetate complexes.
3
Mn metal core, shows antiferromagnetic behavior, Scheme 1.
Due to the various fascinating structures, metal acetates with var-
ious topologies and dimensions have attracted more attention than
any other metal–carboxylates [25–42]. In this context, the Mn(II)–
carboxylate system is one of the few areas of Mn chemistry in
2. Experimental
2.1. General
⇑
Corresponding authors. Tel.: +91 9831115427 (S. Kumar).
E-mail addresses: kdey_chem@rediffmail.com (K. Dey), kumars@phys.jdvu.ac.in
The chemicals used were of A.R. grade. The solvents and chem-
(
S. Kumar).
icals were purified and dried before use by standard procedures.
0
277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.01.053

S. Biswas et al. / Polyhedron 53 (2013) 258–263
259
Table 1
Crystal data and details of the structure determination of complex 1.
Crystal data
Formula
C
12
H
26Mn
627.18
monoclinic
P2 /n (No. 14)
3 2
O16, 2(H O)
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
1
8.8870(18)
9.1100(18)
15.135(3)
90
98.08(3)
90
1213.2(4)
2
1.717
Scheme 1.
a
(°)
b (°)
(°)_
The elemental analyses were carried out at the Regional Sophisti-
cated Instrumentation Centre, the Central Drug Research Institute,
Lucknow, India. Manganese, halogen and nitrogen contents were
also analyzed in our laboratory by conventional methods. The elec-
tronic spectra (in DMSO) were recorded on Hitachi 200-20 and Shi-
madzu UV-2401 PC spectrophotometers and infrared spectra (KBr)
on Perkin Elmer 1330 and L120-000A FTIR spectrophotometers.
c
3
V (Å )
Z
D
calc [g/cm3]
Mu (Mo K
F(000)
Crystal size (mm)
a
/mm)
1.616
642
0.08 ꢂ 0.24 ꢂ 0.24
0
The ligand N,N -(2-hydroxy)propylenebis(2-imino-3-oximino) bu-
Data collection
tane [69–71] and the complex [Mn(III)(dampnol)OAc] [72] were
prepared by our previously published method. The thermal analy-
sis was carried out using a Mettler Toledo TGA-DTA 85 thermal
T (K)
Radiation (Å)
Theta minimum–maximum (°)
Dataset
Total
Uniq. data
293
Mo Ka 0.71073
2.5–28.3
ꢁ11:10; ꢁ12:9; ꢁ19:19
ꢁ1
analyzer under a flow of N
at a rate of 10 °C min with inert alumina as a reference. The pow-
2
(30 ml min ). The sample was heated
7375
2880
0.019
2645
ꢁ
1
R
int
der XRD pattern of the complex was recorded using Cu K
tion (Bruker D8; 40 kV, 40 mA).
a radia-
Observed data [I > 2.0r(I)]
Refinement
N
N
R
wR
2
S
ref
2880
183
2
.2. Synthesis of complex 1
par
0.0302
0.0869
1.07
0.00 0.00
ꢁ0.86 and 0.73
To an ethanolic solution of [Mn(III)(dampnol)(OAc)] (0.92 g,
.0025 mol), 0.5 ml of glacial acetic acid were added and the solu-
0
Maximum and Av. shift/error
Minimum and maximum resd. dens. [e Å ]
tion was stored at room temperature for 6 months. Several light
brown crystals, along with little colorless crystals were separated
mechanically from the gummy solution. The light brown com-
3
2
2) + (0.0571 P)2 + 0.2832 P] where P = (F 2 + 2F 2
)/3.
o o c
w = 1/[ns (F
3 3 6 2 n
pound was identified as [Mn (CH COO) 2H O] by X-ray crystal-
lography. The colorless compound was X-ray crystallographically
identified as dimethylglyoxime. A schematic representation of
the whole reaction process is given below. Anal. Calc. for C12
Mn 18: C, 22.98; H, 4.82. Found: C, 22.87; H, 4.93%.
H
30-
Table 2
3
O
Some selected bond lengths and bond angles of complex 1.
Bond lengths (Å)
Bond angles (°)
2.3. Crystallographic data collection and refinement
Mn1–O1
Mn1–O2W
Mn1–O3
Mn1–O4
Mn1–O5
Mn1–O6
Mn2–O4
Mn2–O6
Mn2–O8
2.1302(13)
2.1802(14)
2.1825(14)
2.2314(13)
2.1945(14)
2.2367(13)
2.1828(13)
2.1871(13)
2.1630(14)
2.1828(13)
2.1871(13)
2.1630(14)
O1–Mn1–O2W
O1–Mn1–O3W
O1–Mn1–O4
O1–Mn–O5
89.86(6)
85.20(6)
176.00(6)
86.91(6)
104.87(6)
101.35(6)
94.15(6)
169.04(6)
85.19(6)
94.03(6)
88.82(6)
168.13(6)
89.16(6)
75.49(5)
85.53(6)
77.50(5)
90.88(6)
180.00
102.50(5)
89.12(6)
91.19(6)
102.50(5)
180.00
88.81(6)
89.12(6)
88.81(6)
180.00
A suitable single crystal of the complex was mounted on a Bru-
ker SMART diffractometer equipped with a graphite monochroma-
tor and Mo K (k = 0.71073 Å) radiation. The structure was solved
a
O1–Mn1–O6
using Patterson methods with SHELXS97. Subsequent difference Fou-
rier synthesis and least-squares refinement revealed the positions
of the remaining non-hydrogen atoms. The non-hydrogen atoms
were refined with independent anisotropic displacement parame-
ters. The hydrogen atoms were placed in idealized positions and
their displacement parameters were fixed to be 1.2 times larger
than those of the attached non-hydrogen atoms. All calculations
were carried out using SHELXS97 [73], SHELXL97 [74], PLATON 99 [75],
ORTEP-32 [76] and WINGX system Ver-1.64 [77]. Data collection,
structure refinement parameters and crystallographic data for
the complex are given in Table 1. Selected bond lengths, and bond
angles are given in Table 2 and non-covalent interaction parame-
ters are summarized in Table S1.
O2W–Mn1–O3W
O2W–Mn1–O4
O2W–Mn1–O5
O2W–Mn1–O6
O3W–Mn1–O4
O3W–Mn1–O5
O3W–Mn1–O6
O4–Mn1–O5
*
Mn2–O4
Mn2–O6
Mn2–O8
*
*
O4–Mn1–O6
O5–Mn1–O6
O4–Mn2–O6
O4–Mn2–O8
*
O4–Mn2–O4
*
O4–Mn2–O6
*
O4–Mn2–O8
O6–Mn2–O8
*
O4 –Mn2–O6
*
O6–Mn2–O6
3
. Result and discussion
*
O6–Mn2–O8
*
O4 –Mn2–O8
*
The polynuclear complex 1 is synthesized in two steps. First, we
O6 –Mn2–O8
*
synthesized
a
mononuclear Mn(III) complex, [Mn(III)(damp-
O8–Mn2–O8
*
*
*
*
0
O4 –Mn2–O6
O4 –Mn2–O8
O6 –Mn2–O8
77.50(5)
90.88(6)
91.19(6)
nol)(OAc)] [dampnol = N,N -(2-hydroxy)propylenebis(2-imino-3-
oximino) butane] [72]. This monomeric complex was kept in gla-
cial acetic acid medium for 6 months and finally we obtained light
brown crystals of complex 1, Scheme 2. The ligands, which were
*
*
*
2
ꢁ x, 1 ꢁ y, 1 ꢁ z.

2
60
S. Biswas et al. / Polyhedron 53 (2013) 258–263
form a 3D supramolecular structure. Each asymmetric unit con-
2
+
tains one and half Mn ions, three uninegative acetate ions, two
coordinated water molecules and one guest water molecule. The
ORTEP diagram of complex 1 is shown in Fig. 1. Some selected
coordination bond lengths and bond angles of the complex are gi-
ven in Table 2. Complex 1 contains two independent Mn(II) ions
within the asymmetric unit. Extension of the asymmetric unit
3
forms a Mn trimeric unit. The central atom, Mn2, is positioned
at a crystallographic inversion center. Both the Mn atoms Mn1
and Mn2 are six coordinated with a distorted octahedral geometry.
For Mn1, three oxygen atoms (O1, O4 and O6) and one water mol-
ecule (O3W) form the basal plane and one oxygen atom (O5) and
one water molecule (O2W) are at the axial positions; similarly
for Mn2, four oxygen atoms (O4, O4ꢃ, O6 and O6ꢃ) form the basal
plane while O8 and O8ꢃ are at the axial positions (where ꢃ = 2 ꢁ x,
1
ꢁ y, 1 ꢁ z). Distortion from an ideal octahedral geometry is re-
flected in the cisoid (75.49(5)–104.87(6)° for Mn1 and 77.49(5)–
02.51(5)° for Mn2) and transoid angles (168.13(6)–175.99(6)°
1
for Mn1, whilst for Mn2 all trans angles are 180°). The Mn1–Mn2
distance within the asymmetric unit is 3.382 Å.
Scheme 2. Conversion of [Mn(III)(dampanol)(OAc)] into [Mn
3
(CH
3
COO)
6 2 n
ꢀ2H O] .
In the asymmetric unit, amongst the six carboxylato oxygen
atoms of three different acetate groups only one oxygen atom,
O7, does not take part in coordination with metal ions. Among
the acetate groups, one acetate ligand (C5, C6, O1 and O4) shows
expected to act as tetradentate chelates under normal reaction
conditions, were found to undergo hydrolytic cleavage to form
dimethylglyoxime and complex 1. Coordination to metal can cause
weakening or strengthening of the –C@N– group, and here the for-
mer occurs resulting in immediate hydrolytic cleavage, and the
intermediate could not be isolated. The cleavage is expected to
be caused by trace amounts of water present in the ethanol [78].
During the reaction process, Mn(III) is reduced to Mn(II) through
oxidation of ethanol to acetic acid [79]. It may be noted that we
have tried to improve the synthetic procedure (to increase the
reaction rate and the yield) by adding dimethylglyoxime (dmg)
to the reaction medium. However in this case, instead of initiating
the reduction of Mn(III) to Mn(II), it leads to the polymerization of
the complex [Mn(III)(dampnol)(OAc)]. The obtained reddish-
brown compound is completely different from complex 1. In the
literature there are some examples of polymerization of Mn(II)
complexes in presence of dmg [80].
l
3-bridging with three metal centers using two carboxylato oxy-
gen atoms, O1 and O4. O1 binds one metal center while O4 shows
the -oxo bridging mode, binding two metal centers, and thus both
syn–anti and anti–anti bridging patterns are generated. The second
acetate group (C1, C2, O5 and O8) shows the 2-bridging mode,
l
l
having a syn–syn pattern with two metal centers using two car-
boxylato oxygen atoms, and the third acetate group (C3, C4, O6
and O7) shows the
ters using one carboxylato oxygen atom (O6), while O7 remains in-
ert. Two -oxo bridging modes of the first type of acetate, two 2-
bridging modes of the second type of acetate and two -oxo bridg-
l-oxo bridging mode, binding two metal cen-
l
l
l
ing modes of the third type of acetate group participate in Mn tri-
3
mer formation, Fig. 2. Each trimeric unit is connected to four others
using a
l3-bridging pattern of the first type of acetate group
through O1, and thus polymeric 2D coordination sheet formation
3.1. Crystal structure and supramolecular structure description
takes place along the diagonal of the ac-plane, Fig. 3.
These 2D coordination sheets are further connected by O2W–
H2W2ꢀ ꢀ ꢀO1W, O1W–H1W1ꢀ ꢀ ꢀO7 and O2W–H2W2ꢀ ꢀ ꢀO1W hydro-
gen bonding interactions to form a 3D supramolecular structure
Single crystal X-ray analysis shows that complex 1 is a 2D coor-
dination polymer connected by hydrogen bonding interactions to
Fig. 1. ORTEP diagram of complex 1.

S. Biswas et al. / Polyhedron 53 (2013) 258–263
261
3
Fig. 2. Mn trimer formed by syn–syn (blue color bridging Mn–O–C–O–Mn) and l-
oxo (magenta color bridging Mn–O–Mn) bridging patterns of acetate ligands. (Color
online)
Fig. 4. 3D supramolecular structure of complex 1.
3
Fig. 3. Each Mn trimer is connected to four others through syn–anti (blue color
bridging Mn–O–C–O–Mn) and anti–anti (magenta color bridging Mn–O–C–O–Mn)
bridging patterns of acetate ligands. (For interpretation of the references to colour
in this figure legend, the reader is referred to the web version of this article.)
using the guest water molecule, Fig. 4. As a result, both right
handed and left handed supramolecular helical chains are formed,
Fig. 5. Due to the presence of both left and right handed helical
chains, the complex becomes achiral. All the hydrogen bonding
interactions are given in Table S1.
3.2. Thermal and PXRD analysis
The phase purity of the complex is established by PXRD analy-
sis. The PXRD pattern is given in Fig. S2. Thermal analysis of the
compound was performed over the temperature range 25–500 °C,
as shown in Fig. S3. The thermogravimetric analyses of the com-
pound shows the occurrence of three consecutive steps. It is clear
from the TG curve that the mass loss of complex 1 up to 80 °C is
5
.6% (5.7% theoretically), which corresponds to the loss of one
guest water molecule. The second mass loss up to 160 °C is 14%
11.4% theoretically), which corresponds to the loss of two coordi-
nated water molecules. The dehydrated framework is stable up to
20 °C without any weight loss.
Fig. 5. Both left (a) and right (b) handed helical chain formation takes place through
hydrogen bonding interactions.
(
2
ꢁ
1
mol at 8 K. Further cooling leads to an increase of the
m
v value
3
ꢁ1
3
ꢁ1
3.3. Variable temperature magnetic study
to 0.656 cm mol at 4 K. The
m
v T value is 9.67 cm mol K at
room temperature, which is lower than that expected for three
3
ꢁ1
Variable temperature magnetic studies have been performed on
non-interacting Mn(II) centers (13.125 cm mol K). Upon cool-
3
ꢁ1
complex 1 in the temperature range 4–300 K. The
v
m
versus T and
ing, the
behavior indicates the presence of an antiferromagnetic interac-
tion amongst the Mn(II) ions. Below 105 K, the T value increases
m
v T value decreases to 9.12 cm mol K at 105 K and such
v
m
T versus T plots of complex 1 are shown in Fig. 6. The value of
3
ꢁ1
3
v
m
at 300 K is 0.032 cm mol , and upon cooling
v
m
gradually in-
v
m
ꢁ1
3
ꢁ1
creases to a value of 0.127cm mol at 75 K. Below 75 K, the
v
m
abruptly and reaches a maximum value of 23.627 cm mol K at
35.62 K, which suggests that complex 1 possesses long range ferro-
magnetic-like ordering along with slow relaxation. Further cooling
value increases very sharply to reach a maximum value of
3
ꢁ1
3
0
.73 cm mol at 20 K and afterward it decreases to 0.51 cm -

2
62
S. Biswas et al. / Polyhedron 53 (2013) 258–263
Fig. 7. M vs. H plot of complex 1.
Fig. 6.
m m
v vs. T and v T vs. T plot of complex 1.
nation polymeric sheet structure. It is well known that syn–syn and
-oxo bridging patterns carry antiferromagnetic interactions,
while the syn–anti and anti–anti bridging patterns import ferro-
magnetic interactions [84–86]. Thus, it can be said that each tri-
meric unit is antiferromagnetic, while the trimeric units in the
3
ꢁ1
leads to a decrease of the
m
v T value to 2.67 cm mol K at 4 K, and
l
this may be due to a ZFS effect in combination with the antiferro-
magnetic interaction [68]. ZFS is not a common phenomenon to
Mn(II) (d ) systems, but when Mn centers are in an axially dis-
torted ligand field, then ZFS has been found to occur [3,81–83].
5
2
D sheet are connected by long range ferromagnetic-like exchange
In complex 1, both Mn1 and Mn2 are in distorted octahedral field
interactions. Within the temperature range 300–105 K, the antifer-
romagnetic interaction dominates, while below 105 K ferromag-
netic interaction coupled with slow relaxation appears in the
system. This slow relaxation gradually decreases on lowering the
temperature. Thus the ferromagnetic interaction builds up in the
system at lower temperatures and that in turn masks the antiferro-
magnetic interaction. Our study indicates that the slow relaxation
of magnetization gets totally suppressed at 5 K. Thus, complex 1
can be called a 2D ferromagnet containing an antiferromagnetic
trimeric metal core.
and so ZFS is a reason for such lowering of the
5 K. There is a small kink below 8 K, which also supports the in-
crease of the value below 8 K.
As the T versus T plot reveals the simultaneous presence of
antiferromagnetic and ferromagnetic-like interactions within the
system, we have fitted the susceptibility data to the Curie–Weiss
law within the temperature range 35–300 K and in the intervals
of 300–105 K and 105–35 K. For the Curie–Weiss law fitting in
the temperature range 35–300 K, the Curie and Weiss constants
are 9.31 cm mol K and h = 4.18 K, respectively, Fig. S4. The posi-
tive value of the Weiss constant suggests the presence of an overall
ferromagnetic-like interaction in the system. However, when the
susceptibility data between 300 and 105 K have been fitted to
the Curie–Weiss law, the Curie and Weiss constants are found to
be 10.05 cm mol K and h = ꢁ13.14 K, respectively, Fig. S5. This
reveals the presence of a weak antiferromagnetic interaction with-
in the system in the temperature range 105–300 K. Again, the sus-
ceptibility data between 105 and 35 K have been fitted to the
Curie–Weiss law and the values of the Curie and Weiss constants
are estimated to be 6.61 cm mol K and h = 25.72 K, respectively,
Fig. S6. This indicates that the ferromagnetic-like interaction dom-
inates in the complex below 105 K.
The compound exhibits a clear hysteresis loop at 5 K, which
indicates the relaxation has been wiped out at this temperature
and the compound exhibits ferromagnetic ordering. This strongly
supports the existence of a ferromagnetic exchange interaction be-
tween the Mn(II) centers in complex 1, as observed in the suscep-
tibility data below 105 K. The hysteresis loop shows values of the
m
v T value below
3
v
m
v
m
3
ꢁ1
4
. Conclusion
Here we have successfully synthesized a Mn–acetate 2D coordi-
nation polymer and established its unusual magnetic behavior. 2D
coordination sheets are formed by connecting trimeric metal cores
3
ꢁ1
by carboxylate bridges. The l-oxo and syn–syn bridging patterns of
the carboxylate groups induce antiferromagnetic interactions
within the trimeric core and these trimeric metal cores are inter-
linked by syn–anti and anti–anti bridging patterns of carboxylate
groups. Such interconnecting bridging patterns develop a ferro-
magnetic exchange pathway within the 2D coordination sheet.
Such ferromagnetic-like ordering in a Mn–carboxylate cluster is
unusual.
In summary, we illustrate the remarkable ability of different
bridging modes of the carboxylate ligand to induce ferro and anti-
ferromagnetic interactions in a Mn–acetate system. Simultaneous
occurrence of ferro- and antiferromagnetic interactions in a com-
plex is unusual and further study on such types of magnetic mate-
rials may even lead to a new generation of magnetic switches.
3
ꢁ1
C R
coercive field (H ) and remnant magnetization (M ) of 1200 Oe
ꢁ1
and 0.0027 Nb mol , respectively, being characteristic of a soft
magnet, Fig. 7. The magnetization saturates at 2T applied magnetic
field; thus this is not a spin canted system.
Acknowledgements
The
m
v T plot indicates that complex 1 exhibits antiferromag-
We thank CSIR, India for awarding a Senior Research Fellowship
Sanction No. 09/096(0565)/2008-EMR-I] to R. Saha. Thanks to
Prof. A. Ghosh, Dept. of Chemistry, University of Calcutta for his
kind assistance.
netic behavior above 105 K, while below 105 K it shows ferromag-
netic-like behavior. The genesis of simultaneous ferro- and
antiferromagnetic interactions in the complex can be explained
from the structural data. The structural analysis reveals that in
complex 1 acetate ligands exhibit three different types of binding
[
modes, as described earlier. Among these, syn–syn and
bridging patterns participate in the formation of the trimeric metal
unit (Mn ) and these trimeric metal units are connected by syn–
anti and anti–anti bridging patterns of acetate to form a 2D coordi-
l
-oxo
Appendix A. Supplementary data
3
CCDC 869696 contains the supplementary crystallographic data
for complex 1. These data can be obtained free of charge via http://

S. Biswas et al. / Polyhedron 53 (2013) 258–263
263
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.poly.2013.01.053.
[42] H.J. Yang, H.Z. Kou, Z.H. Ni, A.L. Cui, R.J. Wang, Inorg. Chem. Commun. 8 (2005)
46.
8
[
[
43] T. Lis, Acta Crystallogr. B36 (1980) 2042.
44] C. Boskovic, J.C. Huffman, G. Christou, Chem. Commun. (2002) 2502.
[45] E. Coronado, A. Forment-Aliaga, A. Gaita-Arino, C. Gimenez-Saiz, F.M. Romero,
W. Wernsdorfer, Angew. Chem., Int. Ed. 43 (2004) 6152.
[
46] M. Soler, W. Wernsdorfer, K. Folting, M. Pink, G. Christou, J. Am. Chem. Soc. 126
2004) 2156.
(
References
[47] A.J. Tasiopoulos, W. Wernsdorfer, K.A. Abboud, G. Christou, Angew. Chem., Int.
Ed. 43 (2004) 6338.
[
48] A.J. Tasiopoulos, A. Vinslava, W. Wernsdorfer, K.A. Abboud, G. Christou, Angew.
Chem., Int. Ed. 43 (2004) 2117.
[
[
1] J.S. Miller, M. Drilon, Magnetism: Molecules to Materials, vol. I–V, Willey-VCH,
Weinheim, 2002–2005.
2] D. Gatteschi, O. Kahn, J.-S. Miller, F. Palacio, Magnetic Molecular Materials,
Kluwer Academic, Dordrecht, The Netherlands, 1991.
3] O. Kahn, Molecular Magnetism, VCH, New York, 1993.
4] E. Coronado, P. Delhaes, D. Gatteschi, J.-S., Miller, Molecular Magnetism: from
Molecular Assemblies to Devices, NATO ASI Series 15, vol. 321, Kluwer,
Dordrecht, The Netherlands, 1995 (Special issue on Magnetism – Molecular,
Supramolecular Perspectives).
5] L.K. Thompson, Coord. Chem. Rev. 249 (2005) 2549.
6] J.S. Miller, Adv. Mater. 14 (2002) 1105.
7] J.-S. Miller, A.-J. Epstein, Angew. Chem., Int. Ed. Engl. 33 (1994) 385.
8] D. Gatteschi, R. Sessoli, Angew. Chem., Int. Ed. 42 (2003) 268.
9] A. Cornia, A. Caneschi, P. Dapporto, A.C. Faberetti, D. Gatteschi, W. Malevasi, C.
Sangregorio, R. Sessoli, Angew. Chem., Int. Ed. 38 (1999) 1780.
[
[
49] D. Gatteschi, R. Sessoli, Angew. Chem., Int. Ed. 115 (2003) 278.
50] G. Aromi, S.M.J. Aubin, M.A. Bolcar, G. Christou, H.J. Eppley, K. Folting, D.N.
Hendrickson, J.C. Huffman, R.C. Squire, H.L. Tsai, S. Wang, M.W. Wemple,
Polyhedron 17 (1998) 3005–3020. and references cited therein.
51] D. Cannon, R.P. White, Prog. Inorg. Chem. 36 (1988) 195.
[
[
[
[
52] R. Wu, M. Poyraz, F.E. Sowrey, C.E. Anson, S. Wocaldo, A.K. Powell, U.A.
Jayasooriya, R.D. Cannon, T. Nakanoto, M. Katada, H. Sano, Inorg. Chem. 37
(
1998) 1913.
53] J. An, Z.-D. Chen, J. Bian, X.-L. Jin, S.-X. Wang, G.-X. Xu, Inorg. Chim. Acta. 287
1999) 82.
[
[
[
[
[
[
(
[
[
54] J. Ribas, B. Albela, H. Stoeckli-Evans, G. Christou, Inorg. Chem. 36 (1997) 2352.
55] J.K. McCusker, H.G. Jang, S. Wang, G. Christou, D.N. Hendrickson, Inorg. Chem.
31 (1992) 1874.
[
[
56] J.B. Vincent, H.-R. Chang, K. Folting, J.C. Huffman, G. Chritou, D.N. Hendrickson,
J. Am. Chem. Soc. 109 (1987) 5703.
57] K. Brechin, C. Boskovic, W. Wernsdorfer, J. Yoo, A. Yamagu Chi, E.C. Sanudo, T.R.
Concolino, A.L. Rheingold, H. Ishimoto, D.N. Hendrickson, G. Christou, J. Am.
Chem. Soc. 124 (2002) 9710–9711.
58] E.K. Brechin, R.A. Coxall, A. Parkin, A. Parsons, P.A. Tasker, R.E.P. Winpenny,
Angew. Chem., Int. Ed. 40 (2001) 2700.
59] S. Wang, M.S. Wemple, J. Yoo, K. Folting, J.C. Huffman, K.S. Hagen, D.N.
Hendrickson, G. Christou, Inorg. Chem. 39 (2000) 1501.
60] J. Kim, H. Cho, A.K. Gupta, J.M. Lim, Y. Do, Int. J. Nanosci. 1 (2002) 455.
61] S.G. Torres, G. Meyer, z. Anorg. Allg. Chem. 34 (2008) 231.
62] H.J. Chen, Z.W. Mao, S. Gao, X.M. Chen, Chem. Commun. (2001) 2320.
63] Y.H. Liu, H.L. Tsai, Y.L. Lu, Y.S. Wen, J.C. Wang, K.L. Lu, Inorg. Chem. 40 (2001)
[
[
[
[
[
[
10] D.N. Dybtsev, H. Chun, S.H. Yoon, D. Kim, K. Kim, J. Am. Chem. Soc. 126 (2004)
2.
11] Z.-M. Wang, B. Zhang, H. Fujiwara, H. Kobayashi, M. Kurmoo, Chem. Commun.
2004) 416.
12] M. Viertelhaus, H. Henke, C.E. Anson, A.K. Powell, Eur. J. Inorg. Chem. (2003)
283.
13] X.Y. Wang, S.W. Gan, S.W. Zhang, S. Gao, Inorg. Chem. 43 (2004) 4615–4625.
and references therein.
14] S.J. Rettig, R.C. Thompson, J. Trotter, S. Xia, Inorg. Chem. 38 (1999) 1360–1363.
and references therein.
3
(
[
[
2
[
[
[
[
15] V. Tangoulis, G. Psomas, C. Dendrinou-Samara, C.P. Raptopoulou, A. Terzis, D.P.
Kessissoglou, Inorg. Chem. 35 (1996) 7655.
16] E. Colacio, M. Ghazi, R. Kiveka, J.M. Moreno, Inorg. Chem. 39 (2000) 2882.
17] R.M. Yolanda, R.P. Catalina, S. Joaquin, L. France, J. Miguel, Inorg. Chim. Acta
[
[
6426.
[
[
64] R.G. Xiong, Y.R. Xie, C.M. Che, J. Chem. Soc., Dalton Trans. (2001) 777–779.
65] S. Liu, M.T. Bremer, J. Lovaasen, A.N. Caruso, K. O’Neill, L. Simpson, P.A. Parilla,
M.J. Heben, D.L. Schulz, Inorg. Chem. 47 (2008) 1568.
3
18 (2001) 159.
[
[
18] C. Zhang, D. Liao, Z. Jiang, S. Yan, Transition Met. Chem. 28 (2003) 621.
19] P. Chaudhuri, K. Oder, K. Wieghardt, S. Gehring, W. Haase, B. Nuber, J. Weiss, J.
Am. Chem. Soc. 110 (1988) 3657.
20] P.S. Mukherjee, S. Konar, E. Zangrando, T. Mallah, J. Ribas, N.R. Chaudhuri,
Inorg. Chem. 42 (2003) 2695.
[
66] R. Wang, E. Gao, M. Hong, S. Gao, J. Luo, Z. Lin, L. Han, R. Cao, Inorg. Chem. 42
(
2003) (2003) 5487.
[
[
[
[
[
[
[
67] H. Yang, H. Kou, Z. Ni, A. Cui, R. Wang, Inorg. Chem. Commun. 8 (2005) 846.
68] M. Zeng, M. Wu, H. Liang, Y. Zhou, X. Chen, S. Ng, Inorg. Chem. 46 (2007) 7241.
69] K. Dey, S. Biswas, S. Sarkar, Synth. React. Inorg. Met.–Org. Chem. 34 (2004)
21] W. Zhang, S. Bruda, C.P. Landee, J.L. Parent, M.M. Turnbull, Inorg. Chim. Acta.
3
42 (2003) 193.
1615.
22] J.-M. Rueff, J.-F. Nierengarten, P. Gilliot, A. Demessence, O. Cregut, M. Drillon, P.
Rabu, Chem. Mater. 16 (2004) 2933.
23] Z. Wang, Y. Kou, J. Lu, C. Gao, J. Tian, S. Yan, Appl. Organomet. Chem. (2012),
http://dx.doi.org/10.1002/aoc.2889.
24] J.D. Martin, R.F. Hess, P.D. Boyle, Inorg. Chem. 43 (2004) 3242.
25] S.R. Batten, R. Robson, Angew. Chem. 110 (1998) 1558.
26] D.J. Martin, F.R. Hess, Chem. Commun. (1996) 2419.
27] F. Sapina, M. Burgos, E. Escriva, J.-V. Folgado, D. Marcos, A. Beltran, D. Beltran,
Inorg. Chem. 32 (1993) 4337.
[
[
[
[
70] K. Dey, z. Anorg. Allg. Chem. 376 (1970) 209.
71] K. Dey, J. Indian Chem. Soc. 48 (1971) 641.
72] S. Biswas, T. Kar, S. Sarkar, K. Dey, J. Coord. Chem. 65 (2012) 980.
73] G.M. Sheldrick, SHELXS 97, University of Göttingen, Germany, Program for
Structure Solution, 1997.
74] G.M. Sheldrick, SHELXL 97, University of Göttingen, Germany, Program for
Crystal Structure Refinement, 1997.
75] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7.
76] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
77] L.J. Farrugia, J. Appl. Crystallogr. 32 (1999) 837.
78] S. Biswas, S. Sarkar, K. Dey, B. Jana, T. Basu, G.P. Yap, K. Kresiel, Spectrochim.
Acta, Part A 65 (2006) 523–528. and reference cited therein.
79] D. Huang, X. Zhang, C. Ma, H. Chen, C. Chen, Q. Liu, C. Zhang, D. Liao, L. Li,
Dalton Trans. (2007) 680.
80] F. Birkelbach, Inorg. Chem. 37 (1998) 2000.
81] S. Naskar, D. Mishra, S.K. Chattopadhyay, M. Corbella, Alexander J. Blake,
Dalton Trans. (2005) 2428–2435.
82] J. Rich, C.E. Castillo, I. Romero, M. Rodríguez, C. Duboc, M. Collomb, Eur. J. Inorg.
Chem. (2010) 3658.
83] T.K. Karmakar, B.K. Ghosh, A. Usman, H. Fun, Inorg. Chem. 44 (2005) 2391.
84] M.L. Tong, M. Monfort, J.M.C. Juan, X.M. Chen, X.H. Bu, M. Ohba, S. Kitagawa,
Chem. Commun. (2005) 233.
[
[
[
[
[
[
[
[
[
[
[
[
[
28] C. Cheng, W.M. Reiff, Inorg. Chem. 16 (1977) 2097.
29] C.V. Gurumurthy, V.M.H. Gonindaro, Ind. J. Chem. (1967) 326.
30] D.A. Ewards, R.N. Hayeard, Can. J. Chem. 46 (1968) 3443.
31] K.C. Patil, G.V. Chandrashekhar, H.V. George, C.N.R. Rao, Can. J. Chem. 46 (1968)
[
2
57.
[
32] T.C. Stamatatos, E. Katsoulakou, V. Nastopoulos, C.P. Raptopoulou, E.M. Zoupa,
S.P. Perlepes, Z. Naturforsch. B58 (2003) 1045.
33] J.N.V. Niekerk, F.R.L. Schoening, Acta Crystallogr 6 (1953) 609.
34] P. Burlet, Solid State Commun. 14 (1974) 665.
35] E.F. Bertaut, T.Q. Duc, Acta Crystallogr. B30 (1974) 2234.
36] C.Y. Cheng, S.L. Wang, Acta Crystallogr. C47 (1991) 1734.
37] Y.Z. Zheng, M.L. Tong, W. Xue, W.X. Zhang, X.M. Chen, F. Grandjean, G.J. Long,
Angew. Chem., Int. Ed. 46 (2007) 6076.
38] K.C. Malhotra, D.S. Katoch, Aust. J. Chem. 29 (1976) 573.
39] W. Clegg, I.R. Little, B.P. Straughan, Acta Crystallogr. C42 (1986) 1701.
40] H.S. He, Acta Crystallogr. E62 (2006) m3291.
[
[
[
[
[
[
[
[
[
[
[
[
[
[
[
[
85] M.-H. Zeng, W.-X. Zhang, X.-Z. Sun, X.-M. Chen, Angew. Chem., Int. Ed. 44
(
2005) 3079.
86] M.-H. Zeng, X.-L. Feng, W.-X. Zhang, X.-M. Chen, Dalton Trans. (2006) 5295.
41] S.G. Torres, G. Meyer, Z. Anorg, Allg. Chem. 634 (2008) 231.