A series of [Na2MnII2MnIII6] clusters derived from trigonal bipyramidal [NaMnIIMnIII3] subunits bridged by mono-, di- and tri-fold azide groups: synthesis, crystal str

Article abstract of DOI:10.1016/j.poly.2018.12.007

A series of [Na₂Mn^II₂Mn^III₆] clusters derived from trigonal bipyramidal [NaMn^IIMn^III₃] subunits bridged by mono-, di- and tri- fold azide groups Na[Na₂Mn

Full text of DOI:10.1016/j.poly.2018.12.007

Polyhedron 161 (2019) 34–39
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
A series of [Na2MnI2IMn6III] clusters derived from trigonal bipyramidal
[NaMnIIMnI3II] subunits bridged by mono-, di- and tri-fold azide groups:
synthesis, crystal structures and magnetic properties
⇑
Jiang Liu, Quanling Suo, Jian Song, Lijuan Zhang, Yuanyuan Gao
College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
a r t i c l e i n f o
a b s t r a c t
A series of [Na2MnI2IMnI6II] clusters derived from trigonal bipyramidal [NaMnIIMnI3II] subunits bridged by
Article history:
mono-, di- and tri- fold azide groups Na[Na2MnI2IMn6III
(
l
3-O)2(HL1)6(
l
1,3-N3)(HCOO)8(H2O)2](ClO4)2 (1),
Received 18 September 2018
Accepted 8 December 2018
Available online 18 December 2018
[Na2MnI2IMnI6II
(
l
3-O)2(L2)6(
l
1,1-N3)4(
l
1,3-N3)2(N3)2(CH3OH)2] (2) and [Na2MnI2IMnI6II 3-O)2(L3)6(
(
l
l
1,1-N3)7
(N3)2(H2O)2] (3) have been obtained via the self-assembly of different potentially multidentate Schiff base
ligands and auxiliary ligands (azide ions and formate ions) with divalent manganese salt in an air-exposed
water-methanol solution. The structures of 1, 2 and 3 were characterized by elemental analysis, FT-IR spec-
troscopy and single-crystal X-ray diffraction analysis. Crystal structures reveal that all the three similar
interesting decanuclear clusters [Na2MnI2IMn6III] are derived from double trigonal bipyramid subunits
bridged by mono-, di- and tri- fold azide groups, respectively. The magnetic susceptibility studies of 1, 2
and 3 in the temperature range 2–300 K shows that predominantly antiferromagnetic interactions between
the manganese centers.
Keywords:
Coordination polymers
Decanuclear clusters
Crystal structure
Magnetic properties
Multidentate Schiff base ligands
Ó 2018 Elsevier Ltd. All rights reserved.
1. Introduction
procedure, tunable steric properties, and good solubility. Addition-
ally, introducing short bridging ligands such as the azide anion
Over the past decades, the rational design and constructing new
type of polynuclear clusters based on the assembly of multifunc-
tional organic ligands and auxiliary bridged ligands with metal
ions are increasingly interesting because of their intriguing struc-
tural diversities and potential applications. Polynuclear clusters
with highly intriguing properties that render them attractive can-
didates for single-molecular magnets [1–3], ferroelectric materials
[4–7], luminescent materials [5,8,9] and catalysis [10–12], and so
on. Up to now, many kinds of polynuclear clusters have been
reported such as 3d transition metal clusters and 3d–4f mixed
metal clusters [13–15]. Among them, mixed-valence manganese
clusters have been the research focus of coordination chemists
due to their potential large ground spin state and magnetic aniso-
tropy. So far, an increasing number of mixed-valence manganese
polynuclear clusters presenting different nuclear number, versatile
bridge mode, interesting topology structure and various bulk mag-
netic properties have been reported [13,16–20].
(Nꢀ3 ) and formate anion (HCOOꢀ), serving as auxiliary ligands, also
play an important role in modulating skeleton structure of the
polynuclear clusters. Indeed, the Nꢀ3 anion has been widely used
to generate coordination polymers owing to the versatile coordina-
tion modes of l1,1-(end-on, EO), l1,3-(end-to-end, EE) bridges [21–
25]. Furthermore, the formate anion also can act as a triatomic
bridging ligand in metal–organic complexes.
During our continuing efforts to construct polynuclear param-
agnetic clusters, especially mixed-valence manganese clusters,
we choose three similar multidentate Schiff base ligands
(Scheme 1) together with azide anion and/or formate anion as aux-
iliary ligands to prepare polynuclear manganese clusters. The steric
effects derived from different multidentate Schiff base ligands and
the modulating roles of auxiliary ligands lead to the difference in
the structures and magnetic properties of the clusters.
Herein, the synthesis, crystal structure of three mixed-valence
polynuclear manganese clusters Na[Na2MnI2IMnI6II 3-O)2(HL1)6
(l
The multidentate Schiff base ligands are important in control-
ling the structure of clusters and have been extensively used in
assembling of polynuclear clusters due to their facile synthesis
(
l
1,3-N3)(HCOO)8(H2O)2](ClO4)2 (1), [Na2MnI2IMn6III(
1,3-N3)2(N3)2(CH3OH)2] (2) and [Na2MnI2IMn6III(
l
l
3-O)2(L2)6(
1,1-N3)4
3-O)2(L3)6(
l1,1-N3)7
l
(l
(N3)2(H2O)2] (3) have been synthesized. It should be noticed that
these three clusters contains similar interesting double trigonal
bipyramid subunits bridged by mono-, di- and tri- fold azide groups,
⇑
Corresponding author.
E-mail address: gaoyuanyuan@imut.edu.cn (Y. Gao).
https://doi.org/10.1016/j.poly.2018.12.007
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.

J. Liu et al. / Polyhedron 161 (2019) 34–39
35
2083m, 2060m, 1622s, 1589s, 1437m, 1306m, 1235w, 1092w,
742m, 624w.
2.2.3. [Na2MnI2IMn6III( 3-O)2(L3)6
l (l1,1-N3)7(N3)2(H2O)2] (3)
A mixture of H2L3 (1 mmol) and NaOH (0.2 mmol) in methanol–
water (10/10 mL) was stirred for 30 min at room temperature.
Then Mn(ClO4)2ꢁ6H2O (1 mmol) were added to the above solution
and stirred for further an hour. Finally NaN3 (0.5 mmol) was added
and the solution was stirred for 1 hour under aerobic conditions.
The resulting deep brown solution was filtered off and allowed
to evaporate slowly in air. Dark brown bulk crystals were obtained
after 7 days. Yield: 52% based on Mn(ClO4)2ꢁ6H2O. Elemental Anal.
Calc. for 3 (C78H106Mn8N33Na2O22): C, 39.59; H, 4.51; N, 19.53%.
Found: C, 40.05; H, 4.79; N, 19.96%. FT-IR (cmꢀ1) for 3: 3422m,
2933m, 2067s, 1612m, 1444m, 1302w, 1223w, 1089w, 750w,
619w.
Scheme 1. Structural diagram of the multidentate Schiff base ligands.
respectively. And the magnetic properties of the three clusters have
been explored.
2. Experimental
2.1. Materials and physical measurements
Caution! Although no problems were encountered during the
preparation of the clusters, as sodium azide and perchlorate salts
are potentially explosive, these basic materials should be treated
with caution and used in small quantities.
2.3. X-ray crystallography
All the starting chemicals and solvents were of AR grade and
used as received. C, H and N analysis was carried out with a Per-
kin-Elmer 2400 elemental analyzer. The Fourier transform infrared
spectra were recorded in the range of 4000–400 cmꢀ1 using
pressed KBr tablets on a MAGNA-IR750 type FT-IR spectrometer.
Magnetic measurements between 2 and 300 K were carried out
with a Quantum Design SQUID MPMS-7 magnetometer under a
constant magnetic field of 1 kOe. Data were corrected for a capsule
sample holder as well as for diamagnetic contributions.
X-ray crystallography measurements for 1–3 were determined
at 293(2) K on Rigaku Saturn724+ and Bruker Apex II CCD diffrac-
tometer with Mo Ka radiation (k = 0.71073 Å) operating in a x–2h
scanning mode for the data collection. The suitable structures of
them were both solved by direct methods and refined anisotropi-
cally by full-matrix least squares techniques on F2 values, using
the SHELX-97 program [26,27]. Hydrogen atoms were added at
appropriate theoretical positions and refined with isotropic ther-
mal parameters riding on those parent atoms. The corresponding
crystallographic and refinement data for 1–3 listed in Table 1.
2.2. Preparation of Schiff base ligands and complexes 1–3
3. Results and discussion
H3L1, H2L2 and H2L3 Schiff base ligands were prepared as
described elsewhere in literature by a condensation reaction
between 2-hydroxy-3-methoxybenzaldehyde and the correspond-
ing amino alcohol (2-amino-2-methyl-1,3-propanediol, 1-amino-
2-propanol, and 2-amino-2-methyl-1-propanol, respectively)
under refluxing in the methanol solution. The resulting orange yel-
low solution containing the required product was used without
further purification.
Complexes 1–3 were readily obtained by the reaction of a diva-
lent manganese salt with the multidentate Schiff-base ligands
H3L1, H2L2, H2L3 (Scheme 1) which are formed by the in situ con-
densation of o-vanillin with the corresponding amino alcohol,
and in the presence of NaOH and auxiliary ligands sodium formate
or sodium azide. During the reaction, the MnII ions is partially oxi-
dized to the MnIII ions in the open air. Dark brown single crystals of
1–3 suitable for X-ray analysis were obtained by slow evaporation
at room temperature. The results of single crystal structure analy-
sis indicate that when the formate and azide anion serves as the
auxiliary ligand in the self-assembling procedure, a polynuclear
cluster 1 which contains mono-azide group bridging trigonal
bipyramid subunits was formed. While, di- and tri- fold azide
groups bridged trigonal bipyramid complexes of 2 and 3 were
obtained only using the azide anion as auxiliary ligand.
2.2.1. Na[Na2MnI2IMn6III( 3-O)2(HL1)6(
l l1,3-N3)(HCOO)8(H2O)2](ClO4)2
(1)
A mixture of H3L1 (1 mmol) and NaOH (0.2 mmol) in methanol–
water (10/10 mL) was stirred for 30 min at room temperature.
Then Mn(ClO4)2ꢁ6H2O (1 mmol) were added to the above solution
and stirred for further an hour. Finally HCOONa (1.5 mmol) and
NaN3 (0.5 mmol) were added and the solution was stirred for 1
hour under aerobic conditions. The resulting deep brown solution
was filtered off and allowed to evaporate slowly in air. Dark brown
bulk crystals were obtained after 7 days. Yield: 57% based on Mn
3.1. Description of crystal structures
(ClO4)2ꢁ6H2O. Elemental Anal. Calc. for 1 (C80H104Mn8N9Na3O52
-
3.1.1. Crystal structure of 1
Cl2): C, 39.00; H, 4.28; N, 5.25. Found: C, 39.69; H, 4.13; N, 4.95%.
FT-IR (cmꢀ1) for 1: 3422m, 2909m, 2091m, 2057s, 1620s, 1586m,
1436m, 1307w, 1238w, 1095w, 741m, 624w.
Single-crystal X-ray diffraction analysꢀes reveal that complex 1
crystallizes in the triclinic space group P1. The coordination envi-
ronment of 1 is depicted in Fig. 1(a) and the skeleton structure
for the cluster is shown in Fig. 1(b). The skeleton structure of com-
plex 1 consists of two perfectly symmetrical double trigonal
2.2.2. [Na2MnI2IMn6III( 3-O)2(L2)6(
l l1,1-N3)4(l1,3-N3)2(N3)2(CH3OH)2] (2)
A mixture of H2L2 (1 mmol) and NaOH (0.2 mmol) in methanol–
water (10/10 mL) was stirred for 30 min at room temperature.
Then Mn(ClO4)2ꢁ6H2O (1 mmol) were added to the above solution
and stirred for further an hour. Finally NaN3 (0.5 mmol) was added
and the solution was stirred for 1 h under aerobic conditions. The
resulting deep brown solution was filtered off and allowed to evap-
orate slowly in air. Dark brown bulk crystals were obtained after
7 days. Yield: 52% based on Mn(ClO4)2ꢁ6H2O. Elemental Anal. Calc.
for 2 (C68H74Mn8N30Na2O22): C, 37.90; H, 3.74; N, 19.50%. Found: C,
38.31; H, 3.51; N, 19.09%.FT-IR (cmꢀ1) for 2: 3426m, 2921m,
bipyramid units ([NaMnIIMnI3II] cluster) bridged by one
l-1,3 (end-
to-end) azide. In detail, the core of each subunit contains one MnII,
three MnIII, one NaI ions and three Schiff base ligands (H3L1). Each
of the ligands coordinates to three metal ions (MnII, MnIII and NaI)
along the blade of the propeller-shaped molecule. Three six-coordi-
nated MnIII (Mn1, Mn2, Mn3) ions are linked to each other via
l
3-O
bridge forming the planar [MnI3IIO] moiety and further connected by
one 1, 3-HCOO and two
1,1-HCOO bridges. Then one NaI ion and
one MnII ion is linked to the triangle plane by three Schiff base
l
l

36
J. Liu et al. / Polyhedron 161 (2019) 34–39
Table 1
Crystal data and structure refinement for complexes 1–3.
1
2
3
Formula
Mr
Crystal system
Space group
C
80H104Mn8N9Na3O52Cl2
C68H74Mn8N30Na2O22
C78H106Mn8N33Na2O22
2343.46
monoclinic
2603.12
2149.08
monoclinic
P2(1)/c
triclinic
ꢀ
P2(1)/m
P1
a (Å)
b (Å)
c (Å)
13.074(3)
13.156(3)
15.854(3)
93.08(3)
95.86(3)
90.82(3)
2708.2(1)
1
19.1307(1)
11.7131(7)
25.1793(1)
90
128.921(3)
90
12.393(3)
35.557(7)
13.123(3)
90
115.44(3)
90
a
(°)
b (°)
c
(°)
V (Å3)
4389.7(4)
2
5222.0(1)
2
Z
T (K)
293(2)
1.596
1.060
293(2)
1.626
1.208
293(2)
1.490
1.023
Dcalc (g cmꢀ3
)
l
(mmꢀ1
)
F(0 0 0)
1330.0
2180
2406
h range (°)
1.56–25.01
18 411
9379
0.0455
1.082
1.37–25.02
21 616
7730
0.0307
1.041
1.15–25.01
33 114
9332
0.0697
1.148
Reflections collected
Unique reflections
Rint
Goodness-of-fit (GOF) on F2
R1/wR2 [I > 2
R1/wR2 (all data)
r
(I)]
0.0963, 0.2872
0.1133, 0.3039
0.0506, 0.1340
0.0715, 0.1538
0.1142, 0.2905
0.1519, 0.3211
deprotonated hydroxyl oxygen atoms, a formic oxygen atom, a
water oxygen atom and a nitrogen atom of azide. The NaI ion above
the [MnI3IIO] plane is six-coordinated by three oxygens of the depro-
tonated hydroxyls and three oxygens of the methoxyls from three
Schiff-base ligands. The selected bond lengths and angles for com-
plex 1 are given in Table S1. The valences of the manganese metal
ions are confirmed by bond-valence sum (BVS) calculations, which
are listed in Table S4.
3.1.2. Crystal structures of 2
According to X-ray crystallographic analysis, complex 2 crystal-
lizes in the monoclinic space group P21/c. The structure of 2 has
been previously reported in literature [28]. As shown in Fig. 2,
the skeleton structure of complex 2 consists of two perfectly sym-
metrical double trigonal bipyramid units bridged by two
l-1,3
(end-to-end) azide. In detail, the core of each subunit contains
one MnII, three MnIII, and one NaI ions, which has similar trigonal
bipyramid skeleton structure as in complex 1. The coordination
environments of each metal ions are similar as that of in complex
1. In each of the trigonal bipyramid subunit ([NaMnIIMn3III]), three
deprotonated Schiff base ligands (H2L2) coordinate to metal ions
Fig. 1. Views showing (a) polyhedral representation of the structure of complex 1,
(b) the skeleton structure for the core.
ligands (H3L1) separately. From the magnetic points of view, four
paramagnetic metal ions in each subunit can be described as a super
tetrahedron in which MnII ion acts as apex and [MnI3IIO] is the trian-
gle plane. As a whole, two symmetrical double trigonal bipyramid
subunits bridged by one
l1,3-N3 (end-to-end) azides via connecting
the MnII apexes.
In cluster 1, each of the three Schiff base ligands provides four
different coordination sites from one deprotonated phenol O, one
deprotonated hydroxyl O, imino N and methoxy O while another
oxygen atom of hydroxyl is not involved in the coordination. All
MnIII ions are six-coordinated with distorted octahedral geome-
tries. Among them, the coordination sites of Mn1 are occupied by
phenolate oxygen, hydroxyl oxygen and imino nitrogen from one
Schiff-base ligand, oxygen of
l3-O bridge and two formic oxygen
atoms. The coordination environments of Mn2 and Mn3 ions are
the same as those in Mn1. The MnII (Mn4) ion assumes a distorted
octahedral coordination geometry, which is completed by three
Fig. 2. Views showing (a) polyhedral representation of the structure of complex 2,
(b) the skeleton structure for the core.

J. Liu et al. / Polyhedron 161 (2019) 34–39
37
(MnII, MnIII and NaI) along the blade of the propeller-shaped mole-
cule. Three six-coordinated MnIII (Mn1, Mn2, Mn3) ions are linked
selected bond lengths and angles for complex 3 are given in
Table S3. The valences of the manganese metal ions are confirmed
by bond-valence sum (BVS) calculations, which are listed in Table S6.
to each other via
l
3-O bridge forming the planar [MnI3IIO] moiety.
In this planar [MnI3IIO] moiety, Mn1ꢁ ꢁ ꢁMn2 and Mn1ꢁ ꢁ ꢁMn3 are fur-
ther connected by one l1,1-N3 bridges, respectively. As it is described
3.2. Magnetic properties
in complex 1, one NaI ion and one MnII (Mn4) ion is linked to the tri-
angle plane forming a trigonal bipyramid subunit [NaMnIIMn3III].
From the magnetic points of view, four paramagnetic metal ions in
the subunit can be described as a super tetrahedron in which MnII
ion acts as apex and [MnI3IIO] is the triangle plane. Overall, two sym-
The magnetic properties of complexes 1–3 were studied to eval-
uate the magnetic interactions between the four paramagnetic
centers. Variable temperature magnetic susceptibility measure-
ments between 2 and 300 K under a constant magnetic field of
1 kOe were carried out.
metrical double trigonal bipyramid subunits bridged by two l1,3-N3
(end-to-end) azides via connecting MnIIꢁ ꢁ ꢁMnIII edges. The selected
bond lengths and angles for complex 2 are given in Table S2. The
valences of the manganese metal ions are confirmed by bond-
valence sum (BVS) calculations, which are listed in Table S5.
The magnetic properties of 1–3 as a
v
v
MT against T plot are
shown in Figs. 4–6. The room temperature
MT value is 20.35 cm3 -
K molꢀ1 for 1, 20.42 cm3 K molꢀ1 for 2 and 21.56 cm3 K molꢀ1 for 3,
much lower than the spin-only (g = 2) value of 26.75 cm3 K molꢀ1
for the six MnIII and two non interacting MnII ions. Upon cooling,
the vMT decreases continuously in both cases indicating significant
3.1.3. Crystal structures of 3
antiferromagnetic interactions between the magnetic centers. The
rapid decrease for the three complexes the lower temperature can
be due to intermolecular interactions and/or effects of zero-field
splitting. According to the results of the single crystal structure
analysis, combining with a magnetic point of view, the magnetic
behaviors of 1 and 3 should mainly depend on the double-tetrahe-
dron with MnII (Mn4) at the vertex and MnIII (Mn1–Mn3) cations in
the triangular plane. Thus, we can use the four-J isotropic Heisen-
berg model to evaluate the coupling interactions among the spin
carriers within 1 and 3 [29]. The exchange interaction models
can be represented as shown in the inset of Figs. 4 and 5, and
the corresponding spin Hamiltonian is:
Complex 3 crystallizes in the monoclinic space group P21/m.
The selected bond lengths and angles for complex 3 are shown in
Table S1. The skeleton structure of complex 3 is shown as Fig. 3.
The complex 3 consists of two perfectly symmetrical double trigo-
nal bipyramid subunits bridged by three
l1,1-N3 (end-on) azides
which adopt a different bridging mode from that of complex 1 or
2. In complex 3, the core of each subunit contains one MnII, three
MnIII, and one NaI ions, which has similar trigonal bipyramid skele-
ton structure as in complex 1 and 2. The coordination environ-
ments of each metal ion are similar as that of in complex 1 and
2. In each of the trigonal bipyramid subunit ([NaMnIIMn3III]), three
deprotonated Schiff base ligands (H2L3) coordinate to metal ions
(MnII, MnIII and NaI) along the blade of the propeller-shaped mole-
cule. Three six-coordinated MnIII (Mn1, Mn2 and Mn4) ions are
ꢀ
ꢁ
^
^ ^
^ ^
^ ^
^ ^
^ ^
^ ^
^ ^
H ¼ ꢀ2J1S4S5 ꢀ 2J2 S4S1 þ S4S2 þ S4S3 þ S5S6 þ S5S7 þ S5S8
ꢀ
ꢁ
ꢀ
ꢁ
linked to each other via l
3-O bridge forming the planar [MnI3IIO] moi-
^ ^
^ ^
^ ^
^ ^
^ ^
^ ^
ꢀ2J3 S2S3 þ S6S7 ꢀ 2J4 S1S2 þ S1S3 þ S7S8 þ S6S8
ety. In this planar [MnI3IIO] moiety, Mn1ꢁ ꢁ ꢁMn2 and Mn1ꢁ ꢁ ꢁMn4 are
For complex 1, the MAGPACK simulation resulted in the best-fit
further connected by one
l1,1-N3 bridges, respectively. As it is
parameters of J1 = ꢀ4.32 cmꢀ1, J2 = ꢀ1.81 cmꢀ1, J3 = ꢀ10.99 cmꢀ1
,
described in complex 1 and 2, one NaI ion and one MnII (Mn3) ion
is linked to the triangle plane forming a trigonal bipyramid subunit
[NaMnIIMnI3II]. From the magnetic points of view, four paramagnetic
metal ions in the subunit can be described as a super tetrahedron in
which MnII ion acts as apex and [MnI3IIO] is the triangle plane. On the
whole, two symmetrical double trigonal bipyramid subunits bridged
J4 = ꢀ9.20 cmꢀ1, g = 2.03. The negative value of J1 represents anti-
ferromagnetic coupling between the MnII (Mn4) ion, and the small
negative J2 value indicates antiferromagnetic interaction between
the MnII (Mn4) and MnIII (Mn1, Mn2 and Mn3) ions. J3 represents
antiferromagnetic interaction between the Mn1 and Mn2 ions. J4
represents antiferromagnetic interaction between the Mn1 and
Mn3 ions or between the Mn2 and Mn3 ions. For complex 3, the
MAGPACK simulation resulted in the best-fit parameters of
by three
l
1,1-N3 (end-on) azides via connecting MnII apex. The
J1 = ꢀ9.15 cmꢀ1, J2 = ꢀ1.41 cmꢀ1, J3 = ꢀ1.76 cmꢀ1, J4 = ꢀ0.48 cmꢀ1
,
Fig. 3. Views showing (a) polyhedral representation of the structure of complex 3,
Fig. 4. Temperature dependence of the
vMT for 1, the solid line represents a
(b) the skeleton structure for the core.
simulation of the data as a best fit. Inset: The exchange interaction model used for 1.

38
J. Liu et al. / Polyhedron 161 (2019) 34–39
4. Conclusions
In summary, a series of [Na2MnI2IMn6III] clusters (1–3) have been
obtained via the self-assembly by using different potentially multi-
dentate Schiff base ligands and auxiliary ligands (azide ions and for-
mate ions) with Mn(II) ions. The structural diversity of three
coordination compounds indicates that the structures can be tuned
by modification of Schiff base ligands. Based upon the structural fea-
tures, the temperature dependence of magnetic susceptibility of
complexes 1 and 3 was modeled with MAGPACK using isotropic
Heisenberg Hamiltonians. The magnetic coupling parameters have
been evaluated and the results indicate that there exist antiferro-
magnetic interactions between the magnetic centers.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (21761026) and the Natural Science Foundation of
Inner Mongolia (2016BS0206).
Fig. 5. Temperature dependence of the
simulation of the data as a best fit. Inset: The exchange interaction model used for 3.
vMT for 3, the solid line represents a
Appendix A. Supplementary data
CCDC 1854652, 1854653 and 1854654 contains the supplemen-
tary crystallographic data for 1–3, respectively. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/conts/re-
trieving.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 to this
article can be found online at https://doi.org/10.1016/j.poly.2018.
12.007.
References
[1] G.J. Halder, C.J. Kepert, B. Moubaraki, K.S. Murray, J.D. Cashion, Science 298
(2002) 1762.
[2] M.H. Zeng, M.X. Yao, H. Liang, W.X. Zhang, X.M. Chen, Angew. Chem., Int. Ed. 46
(2007) 1832.
[3] M.Y. Li, B. Liu, B.W. Wang, Z.M. Wang, S. Gao, M. Kurmoo, Dalton Trans. 40
(2011) 6038.
[4] M.D. Allendorf, C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Chem. Soc. Rev. 38 (2009)
1330.
[5] J. Cao, Y. Gao, Y. Wang, C. Du, Z. Liu, Chem. Commun. 49 (2013) 6897.
[6] L.L. Liang, S.B. Ren, J. Zhang, Y.Z. Li, H.B. Du, X.Z. You, Cryst. Growth Des. 10
(2010) 1307.
Fig. 6. Temperature dependence of the
represents the fitted curve according to the Curie-Weiss law.
v
MT and vꢀM1 (inset) for 2. The solid line
[7] L. Cheng, L.M. Zhang, S.H. Gou, Q.N. Cao, J.Q. Wang, L. Fang, CrystEngComm 14
(2012) 3888.
[8] S. Perruchas, C. Tard, X.F. Le Goff, A. Fargues, A. Garcia, S. Kahlal, J.Y. Saillard, T.
Gacoin, J.P. Boilot, Inorg. Chem. 50 (2011) 10682.
[9] L. Zhang, Y. Ji, X. Xu, Z. Liu, J. Tang, J. Lumin. 132 (2012) 1906.
[10] C. Schotes, M. Althaus, R. Aardoom, A. Mezzetti, J. Am. Chem. Soc. 134 (2012)
1331.
[11] G. Ionescu, J.I. van der Vlugt, H.C.L. Abbenhuis, D. Vogt, Tetrahedron:
Asymmetry 16 (2005) 3970.
[12] T.L. Wang, L.G. Zhuo, Z.W. Li, F. Chen, Z.Y. Ding, Y.M. He, Q.H. Fan, J.F. Xiang, Z.
X. Yu, A.S.C. Chan, J. Am. Chem. Soc. 133 (2011) 9878.
[13] S. Nayak, H.P. Nayek, S. Dehnen, A.K. Powell, J. Reedijk, Dalton Trans. 40 (2011)
2699.
[14] X. Yang, C. Chan, D. Lam, D. Schipper, J.M. Stanley, X. Chen, R.A. Jones, B.J.
Holliday, W.K. Wong, S. Chen, Q. Chen, Dalton Trans. 41 (2012) 11449.
[15] J. Long, F. Habib, P.-H. Lin, I. Korobkov, G. Enright, L. Ungur, W. Wernsdorfer, L.
F. Chibotaru, M. Murugesu, J. Am. Chem. Soc. 133 (2011) 5319.
[16] I.J. Hewitt, J.-K. Tang, N.T. Madhu, R. Clerac, G. Buth, C.E. Anson, A.K. Powell,
Chem. Commun. (2006) 2650.
g = 2.01. The negative values of J1 and J2 represent antiferromag-
netic interaction coupling of MnIIꢁ ꢁ ꢁMnII and MnIIꢁ ꢁ ꢁMnIII. J3 and
J4 represent antiferromagnetic interaction coupling of MnIIIꢁ ꢁ ꢁMnIII.
According to this previous literature, the magnetic properties of
those reported complexes were mainly associated with their crys-
tallographic condition, magnetic orbitals of spin centers (Mn ions),
bond distances (Mnꢁ ꢁ ꢁMn) and angles (Mn–O–Mn and Mn–N
(azido)–Mn) [30–33]. Based on theoretical predictions and experi-
mental studies, the crossover angle from antiferromagnetic to fer-
romagnetic interactions of the end-on azido-bridges Mn(II)
complexes is predicted to be 98° [33]. The general pattern presents
an antiferromagnetic interaction with a bridging Mn(II)–N(azido)–
Mn(II) bond angle of less than 98°. According to the literature, it
may be reasonable that the Mn(II)–N(azido)–Mn(II) bond angles
of 1 and 3 less than 98° producing values of J1 < 0 (antiferromag-
netic interaction). For 2, because of the topological complexity of
the molecule, it is not possible to determine the individual pair-
wise Mn ions exchange interactions using the Heisenberg method.
The inverse magnetic susceptibilities curve shows a linear behavior
in 50–300 K range and obeys the Curie-Weiss law, with
C = 23.62 cm3 K molꢀ1 and h = ꢀ50.44 K. The negative h value indi-
cates antiferromagnetic interaction between Mn ions.
[17] L.-L. Fan, F.-S. Guo, L. Yun, Z.-J. Lin, R. Herchel, J.-D. Leng, Y.-C. Ou, M.-L. Tong,
Dalton Trans. 39 (2010) 1771.
[18] Y. Deawati, D. Onggo, I. Mulyani, I. Hastiawan, D. Kurnia, P. Lönnecke, S.
Schmorl, B. Kersting, E. Hey-Hawkins, Inorg. Chim. Acta 482 (2018) 353.
[19] E. Molnár, B. Váradi, Z. Garda, R. Botár, F.K. Kálmán, É. Tóth, C. Platas-Iglesias, I.
Tóth, E. Brücher, G. Tircsó, Inorg. Chim. Acta 472 (2018) 254.
[20] N. Burkovskaya, G. Aleksandrov, E. Ugolkova, N. Efimov, I. Evstifeev, M. Kiskin,
Z. Dobrokhotova, V. Minin, I. Eremenko, New J. Chem. 38 (2014) 1587.
[21] J.-B. Tommasino, G. Chastanet, B.L. Guennic, V. Robert, G. Pilet, New J. Chem. 36
(2012) 2228.
[22] A. Escuer, G. Aromí, Eur. J. Inorg. Chem. (2006) 4721.
[23] X.-B. Li, Y. Ma, X.-M. Zhang, J.-Y. Zhang, E.-Q. Gao, Eur. J. Inorg. Chem. (2011)
4738.

J. Liu et al. / Polyhedron 161 (2019) 34–39
39
[24] T.-F. Liu, D. Fu, S. Gao, Y.-Z. Zhang, H.-L. Sun, G. Su, Y.-J. Liu, J. Am. Chem. Soc.
125 (2003) 13976.
[30] Y. Song, G.N. Zhang, X.T. Qin, Y.F. Gao, S. Ding, Y.Q. Wang, C.F. Du, Z.L. Liu,
Dalton Trans. 43 (2014) 3880.
[25] L. Li, Z. Liu, S.S. Turner, D. Liao, Z. Jiang, S. Yan, New J. Chem. 27 (2003) 752.
[26] G. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
[27] G.M. Sheldrick, SADABS, The Siemens Area Detector Absorption Correction,
University of Göttingen, Göttingen, 2005.
[31] D. Liu, Q. Zhou, Y. Chen, F. Yang, Y. Yu, Z. Shi, S.H. Feng, Dalton Trans. 39 (2010)
5504.
[32] L.L. Cong, X.Y. Qin, W. Sun, Y.Q. Wang, S. Ding, Z.L. Liu, New J. Chem. 38 (2014)
545.
[28] B. Gole, K.C. Mondal, P.S. Mukherjee, Inorg. Chim. Acta 415 (2014) 151.
[29] J.J. Borrás-Almenar, J.M. Clemente-Juan, E. Coronado, B.S. Tsukerblat, J.
Comput. Chem. 22 (2001) 985.
[33] Y.-F. Zeng, X. Hu, F.-C. Liu, X.-H. Bu, Chem. Soc. Rev. 38 (2009) 469.