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Synthesis, crystal structure, magnetic property and DFT

Cite this: Dalton Trans., 2013, 42, 12274 calculations of an unusual dinuclear µ2-alkoxido
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bridged iron(III) complex†

Rituparna Biswas,a Carmen Diaz,b Antonio Bauzá,c Antonio Frontera*c and
Ashutosh Ghosh*a

A new dinuclear di(μ-alkoxido) bridged complex [Fe2L2] (1) (H3L = N,N’-bis{1-(2-hydroxyphenyl)-

Received 2nd May 2013,
Accepted 21st June 2013
DOI: 10.1039/c3dt51153g
www.rsc.org/dalton
ethylidene}-2-hydroxy-1,3-propanediamine) has been synthesized and characterized. The structure of
1 consists of a centrosymmetric dimer where two crystallographically equivalent metal ions are asymme-
trically bridged by two alkoxido oxygen atoms. In the structure, each ligand coordinates to one Fe(III)
centre and consequently the imino nitrogen atoms are in cis positions, which is rather unusual for this
ligand. Variable-temperature magnetic susceptibility measurements of the complex indicate that the two
iron(III) centres are antiferromagnetically coupled (J = −17.46 cm−1). The exchange mechanism has been
investigated by means of DFT calculations. In addition, the theoretical study has been also used to ration-
alize the unusual coordination mode of the Schiff base ligand. Moreover, the influence of the weak
forces or solvent molecules present in the solid-state structure for the conformational change is also ana-
lysed theoretically. This theoretical calculation incorporates two more similar structures, [Fe2L’2]·CH2Cl2 (2)
and [Fe2L’2]·2CH3CN (3) (H3L’ = N,N’-bis(salicylidene)-1,3,-diaminopropan-2-ol), for a comparative study.
Complex 2 has been reported previously in the literature with the usual binding mode of the ligands.
We have repeated its synthesis and recrystallized it from another solvent (acetonitrile) to get complex
3 which is isostructural with 2 but has acetonitrile as solvent molecule.

Introduction been of considerable interest for several decades, in relation to

The chemistry of iron(III) complexes is dominated by oxygen-
bridged species because of the high oxygen affinity of the
iron(III) ion.1 The interest in oxygen-bridged dinuclear iron(III)
units is largely due to their biological relevance.2 Recently,
special attention has been paid to oxygen-bridged diiron(III)
complexes, stimulated mainly by the discovery of the Fe–O–Fe
core in the active sites of a number of non-heme metallo-
enzymes and metalloproteins such as hemerythrin, a dioxygen
carrier protein.3 Synthetic efforts are made to prepare several
interesting oxygen-bridged polyiron compounds, which have
a
Department of Chemistry, University College of Science, University of Calcutta, 92,
A.P.C. Road, Kolkata-700 009, India. E-mail: ghosh_59@yahoo.com
b chelated to one metal centre (Scheme 1b).10 In the case of tri-
Departament de Química Inorgànica, Universitat de Barcelona, Marti i Franques
1-11, 08028 Barcelona, Spain
c
Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km
7.5, 07122 Palma de Mallorca (Balears), Spain. E-mail: toni.frontera@uib.es
† Electronic supplementary information (ESI) available: Cyclic voltammograms
of complex 1 and crystal data, structure refinement and dimensions in the metal
coordination sphere of complex 3 are included. CCDC 930142 (for 1) and
930143 (for 3). For ESI and crystallographic data in CIF or other electronic
format see DOI: 10.1039/c3dt51153g
magnetic superexchange studies.4 Oxygen-bridged diiron(III)
complexes fall into three classes: oxido-bridged,5 hydroxido
bridged,5a,6 and alkoxido or phenoxido7 bridged species. It has
been noted that the antiferromagnetic interaction mediated
via oxido-bridge is much stronger than that mediated via other
bridges.8
Among the ligands that produce µ-alkoxido bridged com-
plexes, the binucleating Schiff base ligand N,N′-bis(salicyli-
dene)-1,3,-diaminopropan-2-ol (H3L′) and its derivatives are of
special importance because they afford binuclear complexes
rather easily with most of the 1st transition elements. These
ligands bind to the metal centres in two different ways
(Scheme 1). Most commonly, it is shared by the two adjacent
metal centres (Scheme 1a).9 However, in a few cases it is also
valent metal ions [M(III) = Fe(III), Mn(III) and Co(III)], usually
binuclear complexes of MIII2L′2 type are formed with these
ligands. Among them, in all the Mn(III) complexes11 the
ligands are shared but in the only reported Co(III) complex,
each Schiff base ligand binds to one metal center.10a However,
in Fe(III) complexes, both types of coordination are found.
Among the seven10b,12 reported dinuclear bis-µ-alkoxido-

12274 | Dalton Trans., 2013, 42, 12274–12283 This journal is © The Royal Society of Chemistry 2013

Dalton Transactions
Scheme 1 (a) Sharing of ligands by two metal ions; (b) chelation of ligands to
one metal ion.
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bridged Fe(III) complexes, the ligand is shared by two adjacent
Fe(III) centres in four compounds and in the other three where
the Schiff base has been reduced, it coordinates to one metal
ion. It may also be noted that imino nitrogen atoms occupy
the trans positions when the ligand is shared by the two
metals but are bonded to the cis positions when the ligand is
chelated to one metal ion.
In the present work we report the synthesis, crystal struc-
ture, magnetic property, electrochemistry and DFT calculations
of a new dinuclear double µ2-alkoxido bridged Fe(III) com-
pound [Fe2L2] (1) (H3L = N,N′-bis{1-(2-hydroxyphenyl)-ethyli-
dene}-2-hydroxy-1,3-propanediamine). The complex is a rare
example in which each Schiff base ligand coordinates to one
Fe(III) centre. The two different coordination modes of the
Schiff base ligand as described above have not been rationali-
zed theoretically to date. We, therefore, perform a DFT calcu-
lation on complex 1 along with two other Fe(III) compounds
(2 and 3) in which the ligands are shared by the two adjacent
metal centres. Complex 2, a bis-µ-alkoxido bridged dinuclear
Fe(III) compound, [Fe2L′2]·CH2Cl2 (H3L′ = N,N′-bis(salicylidene)-
1,3-diaminopropan-2-ol), has been reported previously.12a We
repeated the synthesis of 2 and crystallized it from a different
solvent (acetonitrile instead of dichloromethane) and obtained
[Fe2L′2]·2CH3CN (3). Single crystal X-ray analysis confirms that
it has the same molecular structure as 2. We have computed
the energies of dimers 1–3 and the results established that
weak forces, such as hydrogen bonds and the presence of
different solvent molecules, are capable of directing the for-
mation of a particular geometrical isomer either by compen-
sating for the energy differences or by providing stabilization
through weak noncovalent interactions.
Experimental section
Starting materials
1,3-Diaminopropan-2-ol, 2-hydroxyacetophenone and anhy-
drous iron(III) chloride were purchased from Merck and used
as received. All other solvents were of reagent grade and were
used without further purification.
Physical measurements
Elemental analyses (carbon, hydrogen and nitrogen) were per-
formed using a 2400 series II CHN analyzer. IR spectra in KBr
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(4500–500 cm−1) were recorded using a Perkin-Elmer RXI
FT-IR spectrophotometer. Electronic spectra (1200–200 nm) in
CH3CN (for 1 and 3) were recorded in a Hitachi U-3501 spec-
trophotometer. The magnetic measurements were carried out
in the “Servei de Magnetoquimica (Universitat de Barcelona)”
on polycrystalline samples (20 mg) with a Quantum Design
SQUID MPMSXL susceptometer in an applied field of 5000 G
and 300 G in the temperature ranges of 2–300 K and 2–30 K,
respectively. Field dependence of magnetization measure-
ments were carried out in the same instrument at 2 K. The
experimental magnetic susceptibility data were corrected for
the diamagnetism estimated from Pascal’s tables and sample
holder calibration.13
Theoretical methods
The energies of all compounds described in the present study
were computed at the BP86-D3/def2-TZVPD level of theory
within the program TURBOMOLE version 6.4.14 This DFT
method (BP86-D3)15 has been successfully used before to
study energetic features of coordination compounds.16 To
compare the relative stabilities of the compounds, the geome-
tries have been fully optimized in the gas phase without sym-
metry constraints starting from the crystallographic
coordinates. Frequency calculations have been performed at
the same level of theory to confirm that the geometries corre-
spond to true minima. The experimental and theoretical dis-
tances and angles obtained for compounds 1 and 3 are very
similar (see Table S2†), giving reliability to the level of theory.
To evaluate the noncovalent interactions in the solid state, we
have used the crystallographic coordinates. The interaction
energies were calculated with correction for the basis set
superposition error (BSSE) by using the Boys–Bernardi coun-
terpoise technique.17
For the magnetic properties, we have used the crystallo-
graphic coordinates. The magnetic coupling constants are
described using the Heisenberg model (see the DFT calcu-
lations of magnetic properties subsection). For DFT-based wave
functions, a reasonable estimate of the exchange coupling con-
stants can be obtained from the energy difference between the
state with the highest spin, EHS, and the low spin wave function,
EBS (namely the broken-symmetry18 solution) obtained by just
flipping one of the spins through eqn (1), where J is the
exchange coupling constant and S1 and S2 the local spins on
centres 1 and 2 (for dinuclear FeIII complexes, S1 = S2 = 5/2):
J ¼ ðEBS  EHS Þ=ð2S1 S2 þ S2 Þ ð1Þ
The hybrid B3LYP functional19 has been used in all calcu-
lations as implemented in Gaussian-0920 using the 6-31+G*
basis set for all atoms. Due to the small magnitude of the
exchange coupling constant, all energy calculations must be
performed including the SCF = tight option of Gaussian to
ensure sufficiently well converged values for the calculated
energies. The approach used for determining the exchange
coupling constants for dinuclear complexes has been
described before in the literature.21
Dalton Trans., 2013, 42, 12274–12283 | 12275

Paper
It should be mentioned that the widely and successfully
used22 broken symmetry DFT approach is not a unique
methodology to compute and interpret magnetic properties in
quantum chemistry. For instance ab initio methods based on
Difference Dedicated Configuration Interaction23 (e.g. CASSCF/
DDCI) give excellent results and offer the possibility to finely
analyse the mechanisms and origin of magnetic properties
taking advantage of the access to the wavefunction of all spin
states of interest. This approach has been recently used for the
study of cis/trans isomeric effects on the magnetic properties
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of copper complexes.24
Crystallographic data collection and refinement
Suitable single crystals of each of the complexes were mounted
on a Bruker SMART diffractometer equipped with a graphite
monochromator and Mo-Kα (λ = 0.71073 Å) radiation. The
structures were solved by the Patterson method using SHELXS
97. Subsequent difference Fourier synthesis and least-square
refinement revealed the positions of the remaining non-
hydrogen atoms. Non-hydrogen atoms were refined with in-
dependent anisotropic displacement parameters. All the
hydrogen atoms were placed in idealized positions and their
displacement parameters were fixed at 1.2 times larger than
those of the attached non-hydrogen atom except the hydrogen
atoms on C(6) in 3 which were located in the difference
Fourier map. Successful convergence was indicated by the
maximum shift/error of 0.001 for the last cycle of the least
squares refinement. All calculations were carried out using
SHELXS 97,25 SHELXL 97,26 PLATON 99,27 ORTEP-3228 and
WinGXsystemVer-1.64.29 Data collection and structure refine-
ment parameters and crystallographic data for the two com-
plexes are given in Table 1.
Table 1 Crystal data and structure refinement of complex 1
Formula
M 758.42
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
V/Å3
Z 1
Dc/g cm−3
µ/mm−1
F (000)
R(int)
Total reflections
Unique reflections
I > 2σ(I)
R1, wR2
Temp./K
12276 | Dalton Trans., 2013, 42, 12274–12283
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Synthesis of the complexes
[Fe2L2] (1). A 5 ml methanolic solution of FeCl3 (0.324 g,
2 mmol) was allowed to react with the Schiff-base ligand H3L,
formed by the in situ condensation of 1,3-diaminopropan-2-ol
(0.118 g, 2 mmol) and 2-hydroxy acetophenone (0.48 ml,
4 mmol) in methanol (10 ml) with constant stirring. Triethyl-
amine (0.84 ml, 6 mmol) was added dropwise to the solution
and the stirring was continued for about 15 minutes. The
colour of the solution turned to dark red and a crystalline pre-
cipitate was separated out within a few minutes. The precipi-
tate was collected by filtration, washed, dried and
recrystallized from acetonitrile. X-ray quality dark red single
crystals of complex 1 were obtained on slow evaporation of the
solvent.
Complex 1. Yield 0.493 g (65%). Anal. Calcd for
C38H38Fe2N4O6 (758.42): C, 60.18; H, 5.05; N, 7.39. Found: C,
60.07; H, 5.01; N, 7.28. IR (KBr pellet, cm−1): 1595.6 ν(CvN).
λmax/nm (CH3CN), 459, 312, 252.
[Fe2L′2]·2CH3CN (3). A methanolic solution of FeCl3 (0.324 g,
2 mmol) was reacted with the Schiff base ligand H3L′ (0.596 g,
2 mmol), synthesized by the previously reported procedure30
in the presence of triethylamine (0.84 ml, 6 mmol). The colour
of the reaction mixture turned to dark brown on stirring and a
precipitate was separated out which was filtered, washed with
cold methanol and dried under vacuum. It was then dissolved
in acetonitrile solvent and dark-red X-ray quality single crystals
of 3 appeared at the bottom of the vessel on slow evaporation
of the solvent.
Complex 3. Yield 0.588 g (75%). Anal. Calcd for
C38H36Fe2N6O6 (784.43): C, 58.18; H, 4.63; N, 10.71. Found: C,
59.07; H, 4.59; N, 10.67. IR (KBr pellet, cm−1): 1633.3 ν(CvN).
λmax/nm (CH3CN), 421, 322, 260.
Result and discussion
Synthesis of complexes 1 and 3
The Schiff base was synthesized by the condensation of 1,3-
diaminopropan-2-ol and 2-hydroxyacetophenone in a
1
1 : 2 molar ratio. FeCl3 reacted with the Schiff base ligand in a
C38H38Fe2N4O6 1 : 1 molar ratio in the presence of triethylamine to result in
the formation of the dinuclear di-μ-alkoxido bridged iron(III)
Triclinic
P1ˉ (No. 2) complex 1 (Scheme 2). Following a similar reaction procedure
8.823(5) to complex 1, we synthesized another complex 3 using a
9.225(5) slightly different Schiff base ligand (N,N′-bis(salicylidene)-1,3,-
10.639(5)
83.287(5) diaminopropan-2-ol).30 Complex 3 is also a dinuclear di-
83.219(5) μ-alkoxido bridged complex but with a different coordination
84.359(5) mode of the ligand (Scheme 2). The same molecule has been
850.8(8)
reported earlier12a with a different solvent of crystallization
1.480 (dichloromethane instead of acetonitrile that is present in 3).
0.907
394 IR and electronic spectra
0.024
6347 The IR spectra of complex 1 showed characteristic CvN
3208 stretching at 1595 cm−1, slightly lower in comparison to
2756
0.0364, 0.1087 complex 3 which shows CvN stretching at 1633 cm−1. Two
293 other Fe(III) complexes in which the ligand is the same as in
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Table 2 Dimensions in the metal coordination sphere, distances (Å) and angles (°)
of complex 1

Atom labels Dist./angle Atom labels Angle

Fe(1)–O(1) 2.058(2) O(2)–Fe(1)–O(3) 89.53(8)

Fe(1)–O(2) 1.902(2) O(2)–Fe(1)–N(1) 105.97(8)
Fe(1)–O(3) 1.927(2) O(2)–Fe(1)–N(2) 83.12(8)
Fe(1)–N(1) 2.127(2) O(1)′–Fe(1)–O(2) 103.73(8)
Fe(1)–N(2) 2.188(2) O(3)–Fe(1)–N(1) 83.23(7)
Fe(1)–O(1)′ 1.981(2) O(3)–Fe(1)–N(2) 163.36(7)
O(1)–Fe(1)–O(2) 160.62(8) O(1)′–Fe(1)–O(3) 96.86(7)
O(1)–Fe(1)–O(3) 109.76(7) N(1)–Fe(1)–N(2) 84.47(7)
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O(1)–Fe(1)–N(1) 75.59(7) O(1)′–Fe(1)–N(1) 150.30(8)

O(1)–Fe(1)–N(2) 77.78(7) O(1)′–Fe(1)–N(2) 99.38(7)
O(1)–Fe(1)–O(1)′ 76.51(7) Fe(1)–O(1)–Fe(1)′ 103.49(7)

Scheme 2 Synthetic route to 1 and 3.
complex 3 exhibit CvN stretching at 1625 and 1629 cm−1.12a,c
Another noticeable difference is the appearance of a weak
band at 2248 cm−1 in the IR spectra of 3 due to the presence of
a solvent acetonitrile molecule.
Since the high-spin Fe(III) is under an octahedral field, the
d–d transitions should be very weak because they are not spin-
allowed. The electronic spectra of complexes 1 and 3 show a
high intensity band at 459 and 421 nm assignable to a charge
transfer transition from the pπ orbital of phenoxido oxygen to
the half filled dπ* orbitals of the iron(III).31 The higher energy
transition bands for 1 and 3 at 312, 322 nm and 252, 260 nm
respectively arise from the intraligand transitions.12a
Structure of complex [Fe2L2] (1)
The asymmetric unit of 1 is shown in Fig. 1 together with the
atomic numbering scheme. Selected bond lengths and angles
are summarized in Table 2. The crystal structure of 1 consists
of a centrosymmetric dimer where the two six-coordinated
crystallographically equivalent metal ions are bridged by two
deprotonated alkoxido oxygen atoms of the pentadentate
Fig. 1 ORTEP-3 view of the asymmetric unit of 1 with ellipsoids at the 30%
probability level. The intramolecular hydrogen bonds are shown as dashed lines.
Schiff base ligand. The four donor atoms of the ligand (two
imino, N(1) and N(2), and two phenoxido, O(2) and O(3)) co-
ordinate to only one Fe(III) center, while the two remaining sites of
Fe(III) are coordinated by the two bridging µ2-alkoxido atoms (O(1)
and O(1)′). The central Fe2O2 core is significantly asymmetric
with Fe(1)–O(1) = 2.058(2) Å and Fe(1)–O(1)′ = 1.981(2) Å which
is a common feature of such dimers. The longest Fe–O(alko-
xido) bond is trans to the phenoxido oxygen atom O(2), and the
shortest one is trans to the imino nitrogen atom N(1). The brid-
ging Fe(1)–O(1)–Fe(1)′ angle is 103.49(7)° leading to a Fe⋯Fe
distance of 3.172 Å, comparable to that in the other dialkoxido
bridged iron(III) complexes.12 Each Fe(III) ion possesses a dis-
torted octahedral geometry coordinated by the ligand in such
a way that one phenoxido oxygen atom O(3) and one imino
nitrogen atom N(2) are in trans axial positions, while the other
phenoxido oxygen O(2) atom and imino nitrogen atom N(1)
are cis. These two cis atoms (O(2) and N(1)) along with the two
bridging alkoxido oxygen atoms O(1) and O(1)′ define the
equatorial plane. The four donor atoms in the basal plane
show a tetrahedral distortion with deviations of −0.257(2),
−0.161(2), 0.217(2) and 0.201(2) Å for O(1), O(2), O(1)′, and
N(1), respectively from the mean plane passing through them.
The iron atom Fe(1) is 0.126(4) Å from this plane in the direc-
tion of the axial O(3) atom. The basal bond distances are in
the range of 1.902(2)–2.127(2) Å. The axial bond distances are
Fe(1)–N(2) 2.188(2) Å and Fe(1)–O(3) 1.927(2) Å. In general, all
the cis and trans angles deviate from 90 or 180°; the range of
cis bond angles is 75.59(7)–109.76(7)° and of the trans angles
is 150.30(8)–163.36(7)°. The CvN bond distance in the
complex is 1.291 Å indicating its double bond character. As
shown in Fig. 1, the phenoxido oxygen atom O(3) forms an
intramolecular C–H⋯O hydrogen bond with the hydrogen
atom H(9B) of the Schiff base ligand having C⋯O = 3.204(4) Å,
O⋯H = 2.40(3) Å and ∠C–H⋯O = 131(2)°.
It is worth mentioning that in complex 1 each ligand is
bonded to one metal center. As a consequence, the two imino
nitrogen atoms (N(1) and N(2)) coordinate to the Fe(III) centres
at the cis positions unlike the cases where the ligands are
shared between the two adjacent metal centres with the imino
nitrogen atoms at the trans positions. It should also be men-
tioned that compound 1 is the first report of a Fe(III) complex

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in which each Schiff base ligand (H3L or its derivatives) is co-
ordinated to one metal ion. In the other three Fe(III) complexes
where this coordination of the ligand was found, the Schiff
base had been reduced (either partially or fully). The higher
flexibility of CH2NHCH2 linkage in the reduced Schiff base
ligand was thought to be responsible for coordination of one
ligand to one metal centre as such a coordination requires
considerable puckering of the ligand.12a However, in complex
1, the Schiff base is not reduced suggesting that other factors,
e.g. various weak interactions, may play an important role in
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stabilizing each structure. Therefore, we undertake DFT calcu-
lations to gain insight into the stability of these two different
structures.
Electrochemistry
Cyclic voltammetric studies of complex 1 were carried out in
acetonitrile solvent using a platinum electrode at scan rates of
20 to 100 mV s−1. It shows two irreversible waves at E1/2 =
−0.92 V and −1.7 V (vs. Ag–Ag+) due to the reduction of FeIII to
FeII species at a scan rate of 100 mV s−1. On decreasing the
scan rate, the peaks shifted towards less negative potentials,
corroborating the irreversible nature of the redox behaviour of
the complex (see Fig. S1, ESI†). In a previously reported dia-
lkoxido bridged Fe(III) complex,12a [Fe2L′2]·CH2Cl2, (H3L′ = N,N′-
bis(salicylidene)-1,3,-diaminopropan-2-ol) where the ligands
have been shared by two metal centers, a reversible wave at
E1/2 = −0.75 V (ΔE = 80 mV) followed by a quasi-reversible wave
at −1.35 V (ΔE = 200 mV) was observed. Thus, the change of
the coordination modes of the ligands seems to influence the
redox property. However, the electrochemical behaviour of
some other Fe(III) complexes with these two types of cores is
required to be studied to observe any general trend (Fig. 2).
Magnetic study of complex 1
The variable temperature magnetic susceptibility of complex 1
has been recorded in the region of 2–300 K, under an applied
Fig. 2 Cyclic voltammograms at 298 K in CH3CN solvent (0.1 mol dm−3, Ag–
AgCl reference electrode) at a platinum working electrode of complex 1 at a
scan rate of 100 mV s−1.
12278 | Dalton Trans., 2013, 42, 12274–12283
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Dalton Transactions
Fig. 3 Plot of χMT and χM vs. T of compound 1. The solid line is the best fit to
the experimental data.
field of 5000 G in all ranges of temperature and 300 G at low
temperatures. A plot of χMT vs. T, for complex 1, is shown in
Fig. 3. The χMT value at 300 K is 7.78 emu mol−1 K, which is
well below the spin-only value of 8.75 emu mol−1 K (assuming
g = 2) expected for two non-interacting high-spin Fe3+ ions.
Upon cooling, the χMT product decreases continuously and
reaches 0 emu mol−1 K at 2 K, indicating the occurrence of
antiferromagnetic intramolecular interaction between the two
Fe3+ ions that leads to a diamagnetic (S = 0) spin ground state.
Indeed the susceptibility curve reaches a maximum value of
0.044 emu mol−1 at 80 K and decreases upon further cooling.
The experimental susceptibility data were analysed by
means of the theoretical equation32 derived for a Heisenberg
exchange model (H = −JS1S2) with S1 = S2 = 5/2. The best fit
gave J = −17.46 cm−1, g = 2.15 and R = 42.6 × 10−6 (Fig. 3). The
agreement factor R is defined as R = Σi[(χMT)obsd − (χMT)calcd]2/
Σi[(χMT)obsd]. The value of the exchange coupling constant of
complex 1 is perfectly in line with the values reported for other
dimethoxido-bridged and dialkoxido-bridged iron(III) com-
plexes with similar structural features: Fe⋯Fe distances, Fe–O–
Fe angles and Fe⋯O distances.7b,8a,12b,c,33
In Table 3 we list the examples of dimethoxido-bridged iron(III)
complexes for which both structures and magnetic studies
have been performed, along with J values and the three struc-
tural parameters. Although it is clear that the above geometri-
cal parameters play a role in their contribution to the coupling
constant J, the trend of the J parameter in systems with analo-
gous geometrical parameters and similar J values is still under
investigation. In this regard, several works have been devoted
to correlate the magnetic behaviour of dialkoxido-bridged
iron(III) systems with either the Fe–O–Fe bond angle or the
Fe⋯Fe distance.34 Recently, a combined experimental and
theoretical study in dialkoxido bridged diiron(III) complexes
was conducted35 where the authors were able to correlate the
magnetic exchange interaction in these systems. They have
found that there exists a correlation between the Fe–O distance
and the Fe–O–Fe angle (the smaller the angle, the longer the
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Table 3 Relative bond angle and bond distances of the reported methoxido-bridged and alkoxido-bridged diiron(III) complexes

Fe⋯Fe (Å) Fe–O–Fe (°) Fe⋯O (Å) J (cm−1)

[Fe2L2(µ-OMe)2(NCS)2]a 3.178 105.8 1.993 −29.4

[Fe2(H3L3)2(OMe)2]8MeOHb 3.145 104.2 1.992 −24.2
[Fe2(mxba)2(OMe)2]CH2Cl2 c 3.164 104.97 1.994 −27
[Fe2(HL)4(OMe)2]d 3.085 102.73 1.967 −27.4
[Fe2Cl4(amp)4(OMe)2]e 3.18 104.44 1.955 −29.4
[Fe2(Cl)2(salEen)2(OMe)2] f 3.11 104.35 2.00 −27.3
[Fe2(dbm)4(OMe)2]g 3.087 102.0 1.987 −15.4
[Fe2(dpm)4(OMe)2]g 3.105 103.7 1.974 −19.0
[Fe2(chp)4(dmbipy)2(OMe)2]2MeOHh 3.194 104.7 1.987 −26.8
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[Fe2(chp)4(phen)2(OMe)2]2MeOHh 3.153 104.3 1.948 −28.6

[Fe2Cl2L(OMe)2]i 3.106 103 1.920 −16.3
[Fe2(LBr-A)2(µ-OMe)2(OMe)2] j 3.068 100.18 2.030 −12.0
[Fe2(LI-A)2(µ-OMe)2(OMe)2] j 3.073 99.95 2.006 −12.4
[Fe2(SON(CNEt2)2)2(µ-OMe)2]k 3.148 103.96 1.998 −26.6
[Fe2(L5)2]2MeOHl 3.262 106.80 2.032 −19.32
[Fe2(LA)2(OMe)(Cl2) MeOH]m 3.149 102.76 2.009 −21.2
Complex 1 3.247 106.45 2.035 −17.46
a
HL [2-[(2-dimethylamino-ethylimino)-methyl]-phenol], ref. 8a; b H5L3 = 2-hydroxy-N-{3-hydroxy-5-[(2-hydroxybenzoyl)amino]pentyl}benzamide,
ref. 7b; c mxba = m-xylylenebis(acetylacetone); ref. 33c; d H2L = 2-salicyloylhydrazono-1,3-dithiolate; ref. 33d; e amp = 2-aminomethylpyridin; ref.
33e; f HsalEen = N-ethyl-N-(2-aminoethyl)salicylaldimine; ref. 33a; g dbm = dibenzoylmethane, dpm = dipivaloylmethanate; ref. 33f; h Hchp =
6-chloro-2-pyridone, dmbipy = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenantroline; ref. 33g; i L = 1,4-piperazinebis(N-ethylenesalicylaldimine),
ref. 33b; j LBr-A = 2,4-dibromo-6(2-pyridylmethylaminomethyl)phenolato and LI-A = 2,4-diiodo-6(2-pyridylmethylaminomethyl)phenolato, ref. 33h;
k
(SON(CNEt2)2)2 = ethyl derivative of 1,1,5,5-tetraalkyl-2-thiobiuret, ref. 33i; l H3L5 = N,N′-bis-(3-methoxy-salicyldiene)-1,3-diamino-2-propano,
ref. 12c; m H3LA = N,N′-bissalicylidene-1,3-diaminopropan-2-ol, ref. 12b.

distance). Curiously, the reported magneto-structural corre-
lation based on the average Fe–O distance is not good (r2 =
0.72).35 However, a good linear relationship between the calcu-
lated J values and the Fe–O–Fe angles was found (r2 = 0.97).
Unfortunately, if this last correlation is applied to complex 1,
the value obtained for J is too high in absolute value (J ≈
−34 cm−1), twice the experimental value. In addition, the Fe–O
distance cannot be used to predict the J since it is out of the
range used in the representation reported by Hänninen et al.35
In any case, the extrapolated value is too small (J ≈ −2 cm−1)
compared to the experimental value. This is due to the fact
that complex 1 is characterized by having a long Fe–O bond
and a large Fe–O–Fe angle compared to similar structures (see
Table 3), behaving in the opposite way to the trend reported by
Hänninen et al.35
atoms. The spin density of compound 1 in the broken-sym-
metry state is represented in Fig. 4 and the spin density values
are summarized in Table 4, where positive and negative signs
denote α and β spin states, respectively. In Table 4 it is shown
that the spin densities on the two Fe(III) ions have identical
absolute values but opposite signs. The spin densities of +4.22
on one Fe(III) and −4.22 on the other reveals that they are
indeed the magnetic centres; however, some of the spin
density delocalizes onto the ligands. The spin densities on the
ligand atoms have the same signs as that of the Fe(III) atoms to
which they are bonded (see Table 4). The spin delocalization is
strong enough that ∼16% of the spin for the unpaired elec-
trons on the Fe(III) centres is delocalized to the ligand atoms.
In spite of the fact that the actual S = 0 ground state of the

DFT calculations of magnetic properties

A theoretical study of the electronic structure and magnetic
properties of the dinuclear complex 1 was performed at the
B3LYP/6-31+G* level of theory (see the theoretical methods
section). The calculated J value is −10.1 cm−1, which is in
reasonable agreement with the experimental value
(−17.4 cm−1, see above), and confirms the presence of anti-
ferromagnetic coupling. Such behaviour is quite common for
Fe(III) complexes, due to the presence of unpaired electrons in
the five d orbitals of the metal, favouring the overlap between
the magnetic orbitals of both paramagnetic centres, regardless
of the s or p nature of the bridging ligands.
In order to further study the magnetic coupling mechan-
Fig. 4 Representation of the spin density corresponding to the “broken-sym-
ism, the spin density distribution is analysed. According to the metry” configuration computed for complex 1. The blue surface corresponds to
molecular orbital theory, spin delocalization is the result of positive spin density values and the green surface to negative values. Hydrogen
electron transfer from the magnetic centers to the ligand atoms have been omitted for clarity.

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Paper
Table 4 The spin densities on the selected atoms for compound 1 at the
UB3LYP/6-31G* level of theory. See Fig. 1 for labelling
Atom Spin density
Fe1 −4.22
O1 −0.17
O2 −0.02
O3 −0.17
N1 −0.11
N2 −0.08
Fe1′ +4.22
O1′ +0.17
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O2′ +0.02
O3′ +0.17
N1′ +0.11
N2′ +0.08
Fig. 5 Two selected SOMOs of complex 1. Hydrogen atoms have been omitted
for clarity.
complex (resulting from the combination of the two “broken-
symmetry” wavefunctions) has no spin density, we have
plotted in Fig. 4 the spin density of one of the “broken-sym-
metry” wavefunctions. This representation shows that the spin
density on the iron atoms (±4.2) in Mulliken population ana-
lysis is distributed spherically due to the presence of one
unpaired electron in each d orbital. The analysis of distri-
bution of the spin density likely indicates the predominance of
the delocalization mechanism over that of polarization, as
deduced by the contribution from the atoms coordinated to
the metal centres.36 We have also computed the singly occu-
pied molecular orbitals (SOMO) of compound 1 and we have
selected two of them to illustrate the magnetic coupling inter-
action (see Fig. 5), where the p orbitals of the bridging ligands
present the major contribution. The SOMO diagrams show
that the dx2−y2 orbitals of the Fe(III) centres have a large inter-
action with the py orbitals of the bridging ligands that contrib-
ute to the magnetic coupling (Fig. 5, left). In addition, the py
orbitals of the bridging oxygen atoms also interact with the dz2
orbitals of the Fe(III) centers that further contribute to the mag-
netic coupling interaction (Fig. 5, right).
Theoretical study on the stability of the complexes
Experimentally, two different binding modes have been
observed for the coordination of Schiff base ligands in di-
nuclear Fe complexes, as explained above. In one case the imino
nitrogen atoms are bonded at the trans positions (3), which is
common in these types of complexes and in the other one the
nitrogen atoms are bonded at the cis position (1). Another
12280 | Dalton Trans., 2013, 42, 12274–12283
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Dalton Transactions
Fig. 6 Experimental (sticks) and theoretical (ball and sticks) geometries of
compounds 1 and 3. Distances are in Å.
significant difference is that in complex 1 both nitrogen atoms
of the same ligand are coordinated to the same Fe metal
center, while in complex 3 each ligand is coordinated to both
Fe ions using the two imino nitrogen atoms. The unique struc-
tural difference between the ligands is the presence of a
methyl group attached to the imino group (see Fig. 6). We also
show in Fig. 6 the optimized structures at the BP86-D3/def2-
TZVPD level of theory and the geometries are almost identical
compared to the experimental ones, giving reliability to the
level of theory. It can be observed that the X-ray structure of 1
has two intramolecular hydrogen bonds that are not formed in
structure 3. In the optimized structure these hydrogen bonds
are maintained and the C–H⋯O distance is almost equivalent.
We have computed the energetic difference between both
conformations. Since the structure that adopts a cis con-
formation has a methyl group and the trans does not, we have
added a methyl group to structure 3 (3-Me) in order to be able
to compare the energies. We have optimized the geometry and,
as a result, the energetic difference between both con-
formations (3-Me vs. 1) is only 0.4 kcal mol−1 favourable to the
cis, which is the one observed experimentally. Therefore, a
likely explanation is that the double H-bonding interaction
observed in 1 stabilizes the unfavourable cis conformation
with respect to the more common trans conformation. In any
case, the difference is very small and any other effect related to
the crystal packing may control the formation of one or the
other.
Another experimental difference between the solid state
structure of 1 and 3 is the presence of solvent molecules in 3.
We have observed that the compound that incorporates aceto-
nitrile molecules in the solid state (3) does not have the
methyl group bonded to the imino group. Interestingly, the
location of the methyl group in the solid state of compound 1
is close to the Fe2O2 rhombus core of another molecule and
vice versa. We have analysed the energetic contribution of this
methyl group that mainly interacts with oxygen atoms of the
This journal is © The Royal Society of Chemistry 2013

Dalton Transactions
Fig. 7 X-ray fragments of compounds 3 (right) and 1 (left) and a model of
compound 1 (middle) without methyl groups.
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core by computing the dimers shown in Fig. 7 (left). The inter-
action energy of the dimer is reduced by 12 kcal mol−1 when
the methyl groups are replaced by hydrogen atoms (see the
structure and energy in the middle of Fig. 7). Therefore the
methyl groups clearly contribute, among many other inter-
actions, to the final architecture in 1. Curiously, compound 3
that does not have the methyl groups incorporates solvent
molecules into the structure. The location of the solvent mole-
cules resembles the position of the methyl groups observed in
compound 1, since the methyl group of the solvent is also
located near the Fe2O2 rhombus core. The interaction energy
is −9.8 kcal mol−1, which is similar to the interaction energy
difference between the both dimers computed for compound
1. Therefore, the presence/absence of the methyl group likely
influences the different coordination modes observed in the
solid state for the Schiff base ligands in the dinuclear Fe
complexes 1 and 3.
To further analyse this aspect, we found in the literature a
crystal structure (2) similar to compound 3 (the same ligand
and the same Fe2O2 core) that incorporates a different solvent
molecule into the structure. In this case a dichloromethane
interacts with the rhombus core in the same position as the
acetonitrile does in 3 (see Fig. 8). A fragment of the X-ray struc-
ture (CSD code LOQDIE) is shown in Fig. 8. The computed
interaction energy is comparable (−10.9 kcal mol−1) to 3, con-
firming the ability of the core to interact with hydrogen bond
donors, either coming from the solvent molecule as in 3 or
from the self-assembly of the coordination complex as in 1.
Fig. 8 X-ray fragment of LOQDIE (2) and the interaction energy of the solvent
molecule with the Fe2O2 core.
This journal is © The Royal Society of Chemistry 2013
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Paper
Concluding remarks
A new dinuclear di(μ-alkoxido)-bridged complex with an
unusual coordination mode (imino nitrogen atoms in cis posi-
tion) has been synthesized and characterized. The antiferro-
magnetic coupling of the complex has been measured by
variable-temperature magnetic susceptibility measurements.
DFT calculations also confirm that the magnetic exchange
between these high spin (S = 5/2) centres is antiferromagnetic.
The calculated J value is in agreement with the value obtained
experimentally. The analysis of the SOMO orbitals and spin
density surface gives hints about the main contributions to the
magnetic coupling. The theoretical study also demonstrated
that the cis arrangement of the imino nitrogen atoms in the
complex is stabilized by the presence of two intramolecular
C–H⋯O hydrogen bonding interactions. In addition, the
methyl group plays a prominent role in stabilizing the solid
state structure of 1 by means of relevant CH3⋯Fe2O2 inter-
actions, which are possible thanks to the cis arrangement of
the N atoms. In compounds 2 and 3, which adopt the usual
trans conformation, the ligand (L′) lacks the methyl group and,
interestingly, both compounds incorporate a solvent molecule
into the structure that precisely occupies the position of the
methyl group establishing similar Cl2CH2⋯Fe2O2 (2) or
CNCH3⋯Fe2O2 (3) interactions, which are energetically very
similar and comparable to the strength of the L–CH3⋯Fe2O2
interaction in 1.
Acknowledgements
We thank CSIR, Government of India [Senior Research Fellow-
ship to R.B.; sanction no. 09/028(0746)/2009-EMR-I]. Crystallo-
graphy was performed at the DST-FIST, India-funded Single
Crystal Diffractometer Facility at the Department of Chemistry,
University of Calcutta. A.B. and A.F. acknowledge the Spanish
Ministerio de Economía y Competitividad (MINECO) for
funding (CTQ2011-27512/BQU, and CONSOLIDER INGENIO
2010, CSD2010-00065), FEDER funds and the Direcció General
de RecercaiInnovació del Govern Balear ( project 23/2011,
FEDER funds). C.D. acknowledges the Spanish Government
(grant CTQ2012-30662, FEDER funds).
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